CN1888001A - Dry composite water-thined adhesive in soft package and its prepn - Google Patents
Dry composite water-thined adhesive in soft package and its prepn Download PDFInfo
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- CN1888001A CN1888001A CNA2006100362313A CN200610036231A CN1888001A CN 1888001 A CN1888001 A CN 1888001A CN A2006100362313 A CNA2006100362313 A CN A2006100362313A CN 200610036231 A CN200610036231 A CN 200610036231A CN 1888001 A CN1888001 A CN 1888001A
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- water
- acrylate
- based adhesive
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- 239000000853 adhesive Substances 0.000 title claims abstract description 43
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000000839 emulsion Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000013530 defoamer Substances 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003429 antifungal agent Substances 0.000 claims abstract 4
- 229940121375 antifungal agent Drugs 0.000 claims abstract 4
- 238000009459 flexible packaging Methods 0.000 claims abstract 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 51
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 23
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 23
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- -1 acetoacetyl ethyl Chemical group 0.000 claims description 14
- 239000000872 buffer Substances 0.000 claims description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical group O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 4
- 229920001223 polyethylene glycol Polymers 0.000 claims 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims 1
- 239000006172 buffering agent Substances 0.000 claims 1
- 229940049964 oleate Drugs 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 8
- 238000004806 packaging method and process Methods 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002612 dispersion medium Substances 0.000 abstract 1
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract 1
- 238000009396 hybridization Methods 0.000 description 22
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 19
- 238000010792 warming Methods 0.000 description 18
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 8
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 7
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical class CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 239000004970 Chain extender Substances 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
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004836 Glue Stick Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明公开了一种软包装干式复合水性胶粘剂及其制备方法，该水性胶粘剂可用于塑料与塑料间的复合。该水性胶粘剂制备方法如下：在聚氨酯自乳化水分散液中进行丙烯酸酯乳液聚合，丙烯酸单体混合物一部份直接与聚氨酯水分散液混合，另一部份在反应过程中滴加，得到聚氨酯/丙烯酸酯杂化乳液；将杂化乳液加入防霉剂、消泡剂得到软包装干式复合水性胶粘剂。本发明以水为主要分散介质，无挥发性有机溶剂，具有环保节能性；该水性胶粘剂制备方法简单，成本合理；水性胶粘剂采用了自交联的固化原理，质量符合塑料干式复合要求。The invention discloses a dry-type composite water-based adhesive for soft packaging and a preparation method thereof. The water-based adhesive can be used for compounding between plastics. The preparation method of the water-based adhesive is as follows: acrylate emulsion polymerization is carried out in the polyurethane self-emulsifying water dispersion, a part of the acrylic monomer mixture is directly mixed with the polyurethane water dispersion, and the other part is added dropwise during the reaction to obtain the polyurethane/ Acrylate hybrid emulsion; adding antifungal agent and defoamer to the hybrid emulsion to obtain a dry composite water-based adhesive for flexible packaging. The invention uses water as the main dispersion medium, has no volatile organic solvent, and has environmental protection and energy saving properties; the preparation method of the water-based adhesive is simple and the cost is reasonable; the water-based adhesive adopts the curing principle of self-crosslinking, and the quality meets the requirements of plastic dry compounding.
Description
Technical field
The present invention relates to a kind of aqueous adhesive, refer in particular to compound use tackiness agent of a kind of soft packaging dry type and preparation method thereof.
Background technology
The package compound film is to become unified integral body by two or more film is bonding, thereby has improved the deficiency of single film, adapts to the requirement of extensive stock packing.Matrix material is main soft packaging base material, and China's food, spices, makeup, cigarette, wine, the daily packing of household are day by day exquisite in recent years, and the matrix material printing develops rapidly thereupon.The China plastics packaging materials ultimate production was 634.3 ten thousand tons in 2004, increased by 15.3% than 2003.152 of the Biaxially oriented polypropylene film (BOPP) BOPP film devices of domestic introduction are wherein introduced 73 of German Bruckner company production lines, 45 of Mitsubishi heavy industrys.Another kind of main compound package material biaxial stretching polyester BOPET output also increases rapidly, and 140,000 tons of 2003 annual production reached 300,000 tons in 2004, estimates can reach 560,000 tons in 2006.
The tackiness agent that present China package compound is used includes volatile organic solvent 30～60% based on the solvent borne polyurethane tackiness agent, and tackiness agent production and use pollute air, influence operator's health, and there is major hidden danger in production safety.Adopt the soft packaging of solvent-based adhesive all to need strict control solvent residual in wrapping material in addition,, cause great accident in order to avoid cause pollution to the packing content thing.The sampling result of the instrumentation package film of in September, 2003 Minister of the General Administration for Quality Supervision of country announcement, disqualification rate is up to 15%, the wherein main quality problems that exist are that sanitary index does not meet standard, and sanitary index comprises residue on evaporation (acetate, ethyl ester, hexane), potassium permanganate consumption, heavy metal, decolorization experiment.Usually food flexible packing consist of plastics film or aluminium foil, tackiness agent and printing ink, wherein film account for 70%, binder constitutes 10%, printing ink 10%, other is 10% years old.Produce 6000000 tons per year by compound package material, year needs 600,000 tons of composite adhesives.
The environmental type tackiness agent earns widespread respect at the application development of China's packaging industry in recent years, U.S.'s ROHM AND HAAS has been introduced the sophisticated environment-friendly type aqueous tackiness agent of American market, the aqueous adhesive of the said firm does not contain tolylene diisocyanate (TDI), performance also can reach dry type compound requirement between film that normal food packing adopted and film, film and the aluminium plating film, the replace solvents type polyurethane adhesive, and can use on answering a pager's call in that solvent-borne type is dried, but exist price higher, the defective of recombining process cycle stretch-out.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of dry-type compound aqueous tackiness agent between the soft packaging polythene PE that is applicable to.Aqueous adhesive of the present invention is a main component with urethane, acrylic ester self-crosslinked hybridisation emulsion.
Another object of the present invention is to provide the preparation method of above-mentioned dry composite water-thined adhesive in soft package.
Purpose of the present invention is achieved through the following technical solutions: a kind of dry composite water-thined adhesive in soft package (self-cross linking type aqueous adhesive) comprises that following component by weight makes:
100 parts of polyurethane/acrylate hybridisation emulsions
0.1～0.5 part of mould inhibitor
0.2～1.0 part of silicone defoamer.
The preparation method of a kind of dry composite water-thined adhesive in soft package (self-cross linking type aqueous adhesive) comprises following processing step and processing condition:
(1) be that 40% urethane self-emulsifying aqueous dispersions is the acrylate reactions mixture that seed emulsion adds the A part earlier with solid content, stirring is warming up to 60～80 ℃, drip the acrylate reactions mixture of B part again, after dropwising, be warming up to 80～100 ℃, after continuing to react, cool to room temperature (20～30 ℃), regulating pH is 8.0～8.5, obtains the polyurethane/acrylate hybridisation emulsion.
The weight ratio of described urethane self-emulsifying aqueous dispersions and whole acrylate reactions mixture is 60～80%: 40～20%.Described acrylate reactions mixture is divided into A and B two portions, and the acrylate reactions mixture of A part accounts for 10～30% of all acrylate reaction mixture weight, remains the acrylate reactions mixture into the B part.
(2) add entry in the polyurethane/acrylate hybridisation emulsion, making hybridisation emulsion be diluted to solid content is 30～50%, and then adds mould inhibitor and the silicone defoamer obtains dry composite water-thined adhesive in soft package.Described each composition is counted by weight: 100 parts of hybridisation emulsions, 0.1～0.5 part of mould inhibitor, 0.2～1.0 part of silicone defoamer.
In order to realize the present invention better, described mould inhibitor is that isothiazolinone, silicone defoamer are German Bi Ke 020.
Described acrylate reactions mixture is prepared from as follows: acrylate monomer, emulsifying agent, buffer reagent, initiator and water are mixed, promptly can be made into the acrylate reactions mixture.
Described acrylate monomer is methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and acetoacetyl Jia Jibingxisuanyizhi (AAEM); Described methyl methacrylate (MMA): butyl acrylate (BA): vinylformic acid (AA): acetoacetyl Jia Jibingxisuanyizhi (AAEM): emulsifying agent: buffer reagent: initiator: water is 23～28: 23～28 by weight: 4: 10～12: 0.6: 0.15: 0.5: 28.75～38.75; Acetoacetyl Jia Jibingxisuanyizhi (AAEM) weight accounts for 10～12% of acrylate monomer weight in the described acrylate monomer; Described emulsifying agent is sodium lauryl sulphate, sodium laurylsulfonate or anhydrous sorbitol polyoxyethylene (20) oleic acid ester etc.; Buffer reagent is a yellow soda ash etc., and initiator is Potassium Persulphate or ammonium persulphate etc.
Rate of addition is 0.5～2.5ml/min in the described step (1).
Described urethane self-emulsifying aqueous dispersions is prepared from as follows:
In solvent acetone, pyrrolidone or vinyl acetic monomer, add polyoxyethylene glycol or polyester diol, dimethylol propionic acid (DMPA) and isophorone diisocyanate (IPDI), be warming up to 80～90 ℃ and carry out polyreaction, 3～5 hours postcooling to 50～60 ℃, add hydrazine (chainextender) chain extension, with triethylamine (TEA) neutralization, and add entry and be made into urethane self-emulsifying aqueous dispersions, urethane has diazanyl in the aqueous dispersions.
Described reactive group isocyanate group and hydroxyl (NCO with-OH) mol ratio is 1.1～1.5: 1, described dimethylol propionic acid provides the hydroxyl mole number to account for 5～20% of total overall reaction thing hydroxyl mole number, the dimethylol propionic acid mole number equates that with the triethylamine mole number mole number of hydrazine is 10～30% of a monomer isophorone diisocyanate mole number.
Preferred polyoxyethylene glycol is the polyoxyethylene glycol of molecular weight 400～600, and the preferred polyester dibasic alcohol is the poly-hexanodioic acid caprolactone dibasic alcohol of weight-average molecular weight 500～2000 or the own ester dibasic alcohol of hexanodioic acid of weight-average molecular weight 500～2000.
A kind of dry composite water-thined adhesive in soft package is exactly that above-mentioned preparation method is prepared from.
The dry type that aqueous adhesive of the present invention can be used between soft packaging plastics and plastics is compound.It is adhering resin that the present invention adopts urethane and acrylate hybrid emulsion, and crosslinked by ketone carbonyl on the high molecular component and diazanyl makes it meet the requirement of soft packaging dry-type composite glue stick.
Principle of the present invention is to have utilized carbonyl and diazanyl can carry out the principle of crosslinking reaction after film forming, and diazanyl and carbonyl are connected on urethane and acrylate copolymer respectively, and design emulsion configuration makes carbonyl and diazanyl be distributed in the nuclear district and the shell district of emulsion particle respectively.Carbonyl and diazanyl reversible reaction generate cross-linking products and micromolecular water.Moving phase water can suppress crosslinking reaction in hybridisation emulsion, formation is filmed the back along with the water volatilization, carbonyl can contact and react with diazanyl, and the surface drying speed that has improved the polymer bonding ability and filmed makes tackiness agent have compound preferably fastness and short compounding period.
The present invention compared with prior art has following advantage and beneficial effect: the present invention is a main dispersing medium with water, has environmental protection and energy saving; The preparation method is simple for this aqueous adhesive, in the more expensive urethane of price hydridization more cheap acrylate copolymer relatively, cost is reasonable; This aqueous adhesive multipolymer can reach the compound fastness of solvent borne polyurethane tackiness agent by crosslinking reaction; After the coating of this aqueous adhesive self-crosslinking takes place at room temperature, film coated surface refers to driedly speed up, and compounding period shortens.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) synthetic-NCO with-the OH mol ratio is 1.2: 1 a base polyurethane prepolymer for use as, the solvent acetone mass percent is 30% in the performed polymer.In solvent acetone, add PEG400 (polyoxyethylene glycol), dimethylol propionic acid (DMPA), isophorone diisocyanate (IPDI), be warming up to 90 ℃, add 2 of di-n-butyltin dilaurates of catalyzer (0.05ml), carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 3.5 hours; Be cooled to 50 ℃, add the hydrazine chain extension, the mole number of hydrazine is 10% of an isophorone diisocyanate mole number, stirred 0.5 hour, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) neutralization behind the chain extension, and adding entry, to be made into solid content be 40% urethane self-emulsifying aqueous dispersions, and outward appearance is the blue light emulsion.Wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.2: 1, DMPA provides the hydroxyl mole number to account for 25% of total overall reaction thing hydroxyl mole number.
(2) the acrylate reactions mixture that acrylate monomer (methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and acetoacetyl Jia Jibingxisuanyizhi (AAEM) are formed), emulsifying agent sodium laurylsulfonate, buffer reagent yellow soda ash, initiator potassium persulfate and water are formed stirs pre-mixing.The acrylate reactions mixture weight consists of: MMA: BA: AA: AAEM: sodium laurylsulfonate: yellow soda ash: Potassium Persulphate: water=23: 23: 4: 10: 0.6: 0.15: 0.5: 38.75, the acrylate reactions mixture is divided into two part A and B, and A: the B weight ratio is 30: 70.In reactor, add urethane self-emulsifying aqueous dispersions 60 grams, acrylate reactions mixture A12 gram successively, stir and be warming up to 70 ℃, from separating funnel, splash into acrylate reactions mixture B28 gram, rate of addition 1ml/min.Be warming up to 90 ℃ after acrylate reactions mixture B dropwises, continue reaction and stop heating after 1 hour, obtain emulsion behind the cool to room temperature, adding 25% ammoniacal liquor adjusting emulsion pH is 8.5, and the emulsion behind the adjusting pH is the polyurethane/acrylate hybridisation emulsion.
(3) add water hybridisation emulsion is diluted to solid content 35%, adding mould inhibitor isothiazolinone 0.1 gram, silicone defoamer (German Bi Ke 020) 0.3 gram obtain dry composite water-thined adhesive in soft package in 100 gram hybridisation emulsions.
Embodiment 2
(1) synthetic-NCO with-the OH mol ratio is 1.2: 1 a base polyurethane prepolymer for use as, solvent pyrrolidone mass percent is 30% in the performed polymer.In the solvent pyrrolidone, add PEG600 (polyoxyethylene glycol), dimethylol propionic acid (DMPA), isophorone diisocyanate (IPDI), be warming up to 80～90 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 3 hours; Be cooled to 60 ℃, add the hydrazine chain extension, the mole number of hydrazine is 10% of an isophorone diisocyanate mole number, stirred 0.5 hour, add triethylamine (TEA) (the triethylamine mole number equates with the dimethylol propionic acid mole number) and neutralize, and adding entry, to be made into solid content be 40% urethane self-emulsifying aqueous dispersions.Wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.2: 1, DMPA provides the hydroxyl mole number to account for 15% of total overall reaction thing hydroxyl mole number.
(2) the acrylate reactions mixture that acrylate monomer (methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and acetoacetyl Jia Jibingxisuanyizhi (AAEM) are formed), emulsifier sodium lauryl sulfate, buffer reagent yellow soda ash, initiator potassium persulfate and water are formed stirs pre-mixing.Reaction mixture weight consists of: MMA: BA: AA: AAEM: emulsifier sodium lauryl sulfate: buffer reagent yellow soda ash: initiator potassium persulfate: water=28: 28: 4: 10: 0.6: 0.15: 0.5: 28.75, the acrylate reactions mixture is divided into two part A and B, and A: the B weight ratio is 10: 90.In reactor, add urethane self-emulsifying aqueous dispersions 70 grams, acrylate reactions mixture A3 gram successively, stir and be warming up to 70 ℃, from separating funnel, splash into acrylate reactions mixture B27 gram, rate of addition 0.5ml/min.Be warming up to 90 ℃ after acrylate reactions mixture B dropwises, continue reaction and stop heating after 1 hour, obtain emulsion behind the cool to room temperature, adding 25% ammoniacal liquor adjusting emulsion pH is 8.5, and the emulsion behind the adjusting pH is the polyurethane/acrylate hybridisation emulsion.
(3) add water hybridisation emulsion is diluted to solid content 40%, adding mould inhibitor isothiazolinone 0.1 gram, silicone defoamer (German Bi Ke 020) 0.4 gram obtain aqueous adhesive in 100 gram hybridisation emulsions.
Embodiment 3
(1) synthetic-NCO with-the OH mol ratio is 1.3: 1 a base polyurethane prepolymer for use as, solvent vinyl acetic monomer mass percent is 30% in the performed polymer.In solvent acetone, the own ester dibasic alcohol of hexanodioic acid, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 500, be warming up to 80 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 3.5 hours; Be cooled to 55 ℃, add the hydrazine chain extension, the mole number of hydrazine is 20% of an isophorone diisocyanate mole number, stirs 0.5 hour, add triethylamine (TEA) and neutralize, and adding entry, to be made into solid content is 40% urethane self-emulsifying aqueous dispersions, is the blue light emulsion.Wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.3: 1, DMPA provides the hydroxyl mole number to account for 15% of total overall reaction thing hydroxyl mole number.
(2) the acrylate reactions mixture that acrylate monomer (methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and acetoacetyl Jia Jibingxisuanyizhi (AAEM) are formed), emulsifying agent sodium laurylsulfonate, buffer reagent yellow soda ash, initiator potassium persulfate and water are formed stirs pre-mixing.Reaction mixture weight consists of: MMA: BA: AA: AAEM: emulsifying agent: buffer reagent: initiator: water=28: 28: 4: 10: 0.6: 0.15: 0.5: 28.75, the acrylate reactions mixture was divided into two part A and B, and A: the B weight ratio is 30: 70.In reactor, add urethane self-emulsifying aqueous dispersions 70 grams, acrylate reactions mixture A9 gram successively, stir and be warming up to 70 ℃, from separating funnel, splash into acrylate reactions mixture B21 gram, rate of addition 2.5ml/min.Be warming up to 90 ℃ after acrylate reactions mixture B dropwises, continue reaction and stop heating after 1 hour, obtain emulsion behind the cool to room temperature, adding 25% ammoniacal liquor adjusting emulsion pH is 8.5, and the emulsion behind the adjusting pH is the polyurethane/acrylate hybridisation emulsion.
(3) add water hybridisation emulsion is diluted to solid content 40%, adding mould inhibitor isothiazolinone 0.2 gram, silicone defoamer (German Bi Ke 020) 0.4 gram obtain aqueous adhesive in 100 gram hybridisation emulsions.
Embodiment 4
(1) synthetic-NCO with-the OH mol ratio is 1.4: 1 a base polyurethane prepolymer for use as, the solvent acetone mass percent is 30% in the performed polymer.In solvent acetone, the own ester dibasic alcohol of hexanodioic acid, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 1000, be warming up to 80 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 4.5 hours; Be cooled to 55 ℃, add the hydrazine chain extension, the mole number of hydrazine is 30% of an isophorone diisocyanate mole number, stirs 0.5 hour, add triethylamine (TEA) and neutralize, and adding entry, to be made into solid content is 40% urethane self-emulsifying aqueous dispersions, is the blue light emulsion.Wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.4: 1, DMPA provides the hydroxyl mole number to account for 20% of total overall reaction thing hydroxyl mole number.
(2) the acrylate reactions mixture that acrylate monomer (methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and acetoacetyl Jia Jibingxisuanyizhi (AAEM) are formed), emulsifying agent sodium laurylsulfonate, buffer reagent yellow soda ash, initiator ammonium persulfate and water are formed stirs pre-mixing.Reaction mixture weight consists of: MMA: BA: AA: AAEM: emulsifying agent: buffer reagent: initiator: water=27.5: 27.5: 4: 11: 0.6: 0.15: 0.5: 28.75, the acrylate reactions mixture is divided into two part A and B, and A: the B weight ratio is 30: 70.In reactor, add urethane self-emulsifying aqueous dispersions 80 grams, acrylate reactions mixture A6 gram successively, stir and be warming up to 70 ℃, from separating funnel, splash into acrylate reactions mixture B14 gram, rate of addition 1ml/min.Be warming up to 90 ℃ after acrylate reactions mixture B dropwises, continue reaction and stop heating after 1 hour, obtain emulsion behind the cool to room temperature, adding 25% ammoniacal liquor adjusting emulsion pH is 8.5, and the emulsion behind the adjusting pH is the polyurethane/acrylate hybridisation emulsion.
(3) add water hybridisation emulsion is diluted to solid content 40%, adding mould inhibitor isothiazolinone 0.2 gram, silicone defoamer (German Bi Ke 020) 0.4 gram obtain aqueous adhesive in 100 gram hybridisation emulsions.
Embodiment 5
(1) synthetic-NCO with-the OH mol ratio is 1.2: 1 a base polyurethane prepolymer for use as, solvent vinyl acetic monomer mass percent is 30% in the performed polymer.In the solvent vinyl acetic monomer, the own ester dibasic alcohol of hexanodioic acid, dimethylol propionic acid (DMPA), the isophorone diisocyanate (IPDI) that add weight-average molecular weight 500, be warming up to 85 ℃, add catalyzer di-n-butyltin dilaurate 0.05ml, carry out polyreaction, stop heating (with the nco value of n-Butyl Amine 99 method assaying reaction system) after 3 hours; Be cooled to 60 ℃, add the hydrazine chain extension, the mole number of hydrazine is 20% of an isophorone diisocyanate mole number, stirs 0.5 hour, add triethylamine (TEA) and neutralize, and adding entry, to be made into solid content is 40% urethane self-emulsifying aqueous dispersions, is the blue light emulsion.Wherein reactive group isocyanate group and hydroxyl mol ratio (NCO with-OH) be 1.2: 1, DMPA provides the hydroxyl mole number to account for 15% of total overall reaction thing hydroxyl mole number.
(2) the acrylate reactions mixture that acrylate monomer (methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and acetoacetyl Jia Jibingxisuanyizhi (AAEM) are formed), emulsifying agent sodium laurylsulfonate, buffer reagent yellow soda ash, initiator potassium persulfate and water are formed stirs pre-mixing.Reaction mixture weight consists of: MMA: BA: AA: AAEM: the emulsifying agent sodium laurylsulfonate: buffer reagent yellow soda ash: initiator potassium persulfate: water=27: 27: 4: 12: 0.6: 0.15: 0.5: 28.75, the acrylate reactions mixture is divided into two part A and B, and A: the B weight ratio is 30: 70.In reactor, add urethane self-emulsifying aqueous dispersions 60 grams, acrylate reactions mixture A12 gram successively, stir and be warming up to 70 ℃, from separating funnel, splash into acrylate reactions mixture B28 gram, rate of addition 1ml/min.Be warming up to 90 ℃ after acrylate reactions mixture B dropwises, continue reaction and stop heating after 1 hour, obtain emulsion behind the cool to room temperature, adding 25% ammoniacal liquor adjusting emulsion pH is 8.5, and the emulsion behind the adjusting pH is the polyurethane/acrylate hybridisation emulsion.
(3) add water hybridisation emulsion is diluted to solid content 45%, adding mould inhibitor isothiazolinone 0.2 gram, silicone defoamer (German Bi Ke 020) 0.4 gram obtain aqueous adhesive in 100 gram hybridisation emulsions.
In the table 1 the contrast sample be the unmodified PU sample mentioned in the document (plastics industry, 2005 11 phases, the application of epoxy modified aqueous polyurethane adhesive in laminated film, Guo Junjie, Zhang Hongyuan).
Table 1 aqueous adhesive performance
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | The contrast sample | |
| Viscosity mPas | 300～500 | 300～500 | 300～500 | 300～500 | 300～500 | 120～150 |
| Compound fastness N/m -1, matrix material: polyethylene/polyethylene | ||||||
| 48 hours 50 ℃ of 5 hours volatile solvent residual quantity (mg/m of initial bonding strength room temperature 2) | 380 760 830 do not detect | 456 932 986 do not detect | 432 911 946 do not detect | 483 960 1000 do not detect | 418 825 932 do not detect | 256 637 763 |
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