CN102558427B - Polymer emulsion for water-based printing ink and preparation method thereof - Google Patents
Polymer emulsion for water-based printing ink and preparation method thereof Download PDFInfo
- Publication number
- CN102558427B CN102558427B CN 201110430504 CN201110430504A CN102558427B CN 102558427 B CN102558427 B CN 102558427B CN 201110430504 CN201110430504 CN 201110430504 CN 201110430504 A CN201110430504 A CN 201110430504A CN 102558427 B CN102558427 B CN 102558427B
- Authority
- CN
- China
- Prior art keywords
- monomer
- polymer emulsion
- emulsifying agent
- emulsion
- reactive emulsifier
- 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.)
- Expired - Fee Related
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 140
- 229920000642 polymer Polymers 0.000 title claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000007639 printing Methods 0.000 title abstract description 49
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 118
- 239000000178 monomer Substances 0.000 claims abstract description 112
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 30
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 41
- 239000003999 initiator Substances 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- -1 polyoxyethylene Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 15
- 230000007704 transition Effects 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000012875 nonionic emulsifier Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000746 allylic group Chemical group 0.000 claims description 4
- 239000012874 anionic emulsifier Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- WGMANIMEEAXUCT-UHFFFAOYSA-M sodium;2-hydroxy-3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [Na+].CC(=C)C(=O)OCC(O)CS([O-])(=O)=O WGMANIMEEAXUCT-UHFFFAOYSA-M 0.000 claims description 3
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000007646 gravure printing Methods 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 68
- 238000006116 polymerization reaction Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 230000002829 reductive effect Effects 0.000 description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 235000019395 ammonium persulphate Nutrition 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000002950 deficient Effects 0.000 description 8
- 239000004160 Ammonium persulphate Substances 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical group O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- RMMPZDDLWLALLJ-UHFFFAOYSA-N Thermophillin Chemical compound COC1=CC(=O)C(OC)=CC1=O RMMPZDDLWLALLJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000913 palmityl 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])C([H])([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 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical group C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- 0 *c(cc1)ccc1OCC(COCC=C)O* Chemical compound *c(cc1)ccc1OCC(COCC=C)O* 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 101100298222 Caenorhabditis elegans pot-1 gene Proteins 0.000 description 1
- 101100298225 Caenorhabditis elegans pot-2 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 101710171243 Peroxidase 10 Proteins 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010219 correlation analysis Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides a polymer emulsion for water-based printing ink and a preparation method thereof. The polymer emulsion is prepared by mixed monomers and reactive emulsifiers containing at least an allyl or a vinyl, wherein the reactive monomers comprise a soft monomer and a hard monomer. The polymer emulsion for water-based printing ink has the disadvantages of good stability and hydrophilic-hydrophobic balance and is applicable to preparing water-based gravure printing ink.
Description
Technical field
The present invention relates to the intaglio printing field, relate in particular to a kind of used for water color ink polymer emulsion and preparation method thereof.
Background technology
Intaglio printing is a kind of web plate that adopts the ink cell structure, the China ink amount of controlling ink cell by size or the depth difference of ink cell and volume are in the mode of the level performance that realizes the printing tone, it has, and speed is fast, color is full, good brightness, the site is clear, advantages such as on line drying are specially adapted to the printing of typical products in mass production, are very important efficient mode of printings.Compare with other mode of printing, the black bed thickness of gravure product during high speed printing, requires very highly to the transferability of printing ink from intaglio plate to stock, and therefore, high-speed intaglio printing uses in a large number at present still is solvent type photogravure printing ink.Yet, when adopting this solvent type photogravure printing ink, have that objectionable impurities is residual in the printed matter exceeds standard, easily contaminate environment, be harmful to the shortcoming of HUMAN HEALTH, this is imperative with regard to making a kind of environmental protection of exploitation, health and the few printing ink of hazard residue thing get above-mentioned generation solvent type photogravure printing ink.
Water color ink has been subjected to social attention gradually by the few characteristic of its environmental protection, health and hazard residue thing, is used to substitute existing solvent type photogravure printing ink gradually.Water color ink comprises mill base, aqueous polymer resin and auxiliary agent, and by adding water and the mixture of alcohols (mainly being ethanol) is regulated viscosity.The used aqueous polymer resin difference of different mode of printings is very big, and for intaglio printing, the use polymer emulsion is as water-based ink resin usually.
Chinese patent publication number CN101575395A discloses " a kind of water-base gravure ink copolymer emulsion and binder ", and it adopts the allyloxy hydroxypropyl azochlorosulfonate acid sodium is that emulsifying agent prepares polymer emulsion.When the benzene emulsion of these method preparations was used for water-base gravure ink, color inequality, shrinkage cavity, film color when having (1) high-speed intaglio printing, (2) color and printing effect were difficult to control, wash problems such as edition difficulty.Produce the reason of these problems, may be that these polymer emulsions condense under high-shear easily, also may be that emulsion is separated out or retrogradation after contacting pigment or ethanol, the water color ink surface tension that also may be preparation is excessive, and the China ink layer can not shift smoothly when gravure.
Chinese patent publication number CN101054489A, announced " a kind of method for preparing water-base gravure ink with commodity ACRYLIC EMULSION and commodity acrylic resin ", when the printing ink of Sheng Chaning is used for high-speed intaglio printing in this way, there are color inequality, shrinkage cavity and printing effect to be difficult to problems such as control equally.
Chinese patent publication number CN101353499A has announced " a kind of preparation method of styrene-acrylate core/shell emulsion bridging agent for water-based ink; the preparation process complexity of this method; need the preparation aqueous polyurethane dispersing liquid; organic solvent content height wherein, and the aqueous polyurethane composition is influential to the use properties of printing ink.
Can be found by foregoing, although aqueous intaglio printing ink has caused concern as the substituted systems of solvent based printing ink, but existing aqueous polymer emulsion exists variety of problems when using as water color ink, printing effect is undesirable, if use printing ink substitutes existing solvent type photogravure printing ink, also need further to improve the performance of aqueous polymer emulsion.
Summary of the invention
The present invention aims to provide a kind of used for water color ink polymer emulsion and preparation method thereof, to improve the used for water color ink STABILITY OF POLYMER EMULSION.
To achieve these goals, according to an aspect of the present invention, a kind of used for water color ink polymer emulsion is provided, the raw material of polymer emulsion comprises by weight: the emulsifying agent of 100 parts mix monomer and 1～12 part, mix monomer comprises soft monomer and hard monomer, emulsifying agent comprises the reactive emulsifier that contains allyl group or vinyl-functional at least, wherein the second-order transition temperature Tg of the multipolymer that is obtained by mix monomer reaction is 60～90 ℃, the equal Hansch hydrophobicity of matter contribution margin be 2.57～3.81 and the solid content of this polymer emulsion be 33%～43%.
Further, the raw material of above-mentioned polymer emulsion comprises by weight: the emulsifying agent of 100 parts mix monomer and 5～12 parts.
Further, above-mentioned soft monomer is ethyl propenoate, propyl acrylate, butyl acrylate, Isooctyl acrylate monomer, or in the Isooctyl methacrylate one or more, hard monomer is one or more mixing in isobornyl acrylate, methyl methacrylate, isobornyl methacrylate and the vinylbenzene.Further, the quality of soft monomer is 30～50% in the above-mentioned mix monomer, and the quality of hard monomer is 70～50%.
Further, above-mentioned reactive emulsifier comprises the reactive emulsifier of anionic and/or the reactive emulsifier of non-ionic type, the vitriol that the reactive emulsifier of anionic is vinylsulfonate, contain the sulfonate of alkane phenyl, allyl group and polyoxyethylene and contain alkane phenyl, allyl group and polyoxyethylene simultaneously simultaneously; The structural formula of vinylsulfonate is: CH=CH (CH
2)
h-OSO
3Na, wherein h=14～18; The above-mentioned structural formula of reactive emulsifier that contains the sulfonate of alkane phenyl, allyl group and polyoxyethylene simultaneously and contain the vitriol of alkane phenyl, allyl group and polyoxyethylene simultaneously is:
Wherein, R is carbonatoms at 8～10 straight chained alkyl, and X-is sulfonate radical or sulfate radical, and n is that 10～20, M+ is monovalent cation;
Reactive emulsifier comprises that also the reactive emulsifier of non-ionic type for the structural formula that the reactive emulsifier that contains alkane phenyl, allyl group and polyoxyethylene ether simultaneously contains the reactive emulsifier of alkane phenyl, allyl group and polyoxyethylene ether simultaneously is:
Wherein, R ' is carbonatoms at 8～10 straight chained alkyl, and m is 10～20.
Further, mentioned emulsifier comprises that also content is 0～60% non-reacted emulsifying agent of reactive emulsifier quality, non-reacted emulsifying agent comprises anionic emulsifier and/or non-ionic emulsifier, and anionic emulsifier is one or more in the sulfonate of the sulfonate of vitriol, alkyl polyoxyethylene ether of vitriol, the alkane phenyl Soxylat A 25-7 of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl polyoxyethylene ether or alkane phenyl Soxylat A 25-7; Nonionic emulsifier is one or more in Tweens, class of department class, the alkyl polyoxyethylene ether class.
Further, mentioned emulsifier comprises that also content is 0～40% polymerizability emulsifying agent of reactive emulsifier quality, and polymerizable emulsifier is for containing alkyl and allylic succsinic acid (ester) salt simultaneously.
Further, comprise also in the above-mentioned mix monomer that content is the functional vinyl monomer that contains carboxyl or sulfonate of soft monomer and hard monomer gross weight 0～5%, this functional vinyl monomer is 3-methacryloxy-2-hydroxyl-1-propane sulfonic acid sodium salt, 2-acrylamido-2 methyl propane sulfonic acid sodium salt; 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium salt, one or more in (methyl) vinylformic acid.
Further, the raw material of above-mentioned polymer emulsion also comprises initiator and/or reductive agent, described initiator is persulphate, hydrogen peroxide or the water miscible organo-peroxide of thermolysis type, and described reductive agent is Sulfothiorine, water-soluble amine or polyvalent metal salt.
Simultaneously, also provide a kind of preparation method of above-mentioned used for water color ink polymer emulsion in the present invention, may further comprise the steps: mix monomer, first part's emulsifying agent and deionized water have been mixed, carry out pre-emulsification, obtain pre-emulsion A; Initiator and deionized water are mixed with solution B; Under nitrogen atmosphere and agitation condition, second section emulsifying agent and deionized water are mixed, be warming up to the temperature of polymerization reaction take place; Drip mixed liquor A and solution B, after dripping off, continue reaction 2～3h; Heat up 20～25 ℃ and continue reaction, obtain polymerized emulsion; With described polymerized emulsion cooling, and regulate pH value to neutral, add deionized water, regulate the solid content of polymerized emulsion to 33%-43%, namely get described used for water color ink polymer emulsion.
Further, above-mentioned preparation method may further comprise the steps: mix monomer, the emulsifying agent that is higher than emulsifying agent total content 85% and deionized water are mixed, carry out the pre-emulsification of 5-30min, obtain pre-emulsion A; Initiator and deionized water are mixed with solution B in room temperature; Under nitrogen atmosphere and agitation condition, remaining emulsifying agent and deionized water are mixed, be warming up to 30～75 ℃; Drip described pre-emulsion A and described solution B, continue reaction 2～3h in nitrogen protection with under stirring; Heat up and continue reaction 2h after 20～25 ℃, obtain described polymerized emulsion; Described polymerized emulsion is cooled to room temperature; Regulate the pH value of described mixed emulsion to neutral, add the solid content that deionized water is regulated described polymerized emulsion, make it reach 33%～43%, form described used for water color ink polymer emulsion.
Beneficial effect of the present invention: used for water color ink polymer emulsion stability provided by the present invention better.And the ability with anti-high speed dynamic shearing, the China ink layer that can adapt to high speed printing shift, wetting, dry, sticking power and wash an edition requirement.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the feature among the embodiment among the application can make up mutually.Describe the present invention in detail below in conjunction with specific embodiment.
In a kind of typical embodiment of the present invention, a kind of used for water color ink polymer emulsion, comprise polymer raw and deionized water, polymer raw comprises by weight: the emulsifying agent of 100 parts mix monomer and 1～12 part, mix monomer comprises soft monomer and hard monomer, wherein the second-order transition temperature Tg of the multipolymer that is obtained by mix monomer reaction is 60～90 ℃, the hydrophobicity contribution margin is 2.57～3.81, emulsifying agent comprises the reactive emulsifier of allyl group or vinyl at least, and the solid content of polymer emulsion is 33%～43%.
Used for water color ink polymer emulsion provided by the present invention, multipolymer by adopting soft monomer and hard monomer is as polymer raw, make the hydrophilic-hydrophobic that this used for water color ink polymer emulsion has balance, simultaneously, the reactive emulsifier that comprises allyl group or vinyl by adding, make indifferent allyl group or the vinyl of radical polymerization in the reactive emulsifier, chain transfer reaction by free radical, the perhaps high reactivity monomer generation copolymerization in mode such as the coupling reaction by free radical and soft monomer and the hard monomer makes the mode " anchor " of emulsifying agent by chemical bonding at the polymer emulsion particle surface.On the other hand, the allyl group that can react or vinyl groups are separated with suitable distance mutually with the hydrophilic radical of emulsifying agent, have improved the hydrophilic radical of emulsifying agent to STABILITY OF POLYMER EMULSION.The glass transition temperature Tg of the multipolymer by control soft monomer and hard monomer, and the equal Hansch hydrophobicity of the matter of multipolymer contribution margin, make this polymer emulsion have the ability of anti-high speed dynamic shearing, with the China ink layer that adapts to high speed printing shift, wetting, dry, sticking power and wash an edition requirement.
Above-mentioned soft monomer refers to that the Tg of its polymkeric substance is at room temperature or following monomer in the present invention, hard monomer refers to the monomer of Tg more than room temperature, wherein, the second-order transition temperature Tg of the usage quantity of soft monomer and hard monomer and both multipolymers has direct relation, the Fox formula estimation that the second-order transition temperature Tg of multipolymer can press following formula by Tg (i) and the massfraction Wi of each monomer:
1/T
g＝∑[W
i/T
g(i)]
In actual application, can be by selecting suitable soft monomer and hard monomer as raw material, according to the second-order transition temperature T of each monomer that adopts
g(i) and consumption, can calculate the second-order transition temperature Tg of multipolymer.On the other hand, selected the monomer of multipolymer, and the second-order transition temperature Tg that has determined multipolymer has just determined the usage quantity of each raw material.
When the second-order transition temperature Tg according to multipolymer regulates the usage quantity of each monomer, need also to further consider that relation between the Hansch hydrophobicity of each selected monomer and usage quantity and multipolymer is (referring to C.Hansch, T.Fujita, J.Am.Chem.Soc., 86,1616-1626 (1964); C.Hansch, A.Leo, Substitute Constants for Correlation Analysis in Chemistry and Biology, Wiley, New York (1979); C.Hansch, P.Maloney, T.Fujita, R.Muir, Nature, 194,178-180 (1962)).The Hansch hydrophobicity contribution margin of multipolymer can be by the Hansch hydrophobicity contribution margin V of each monomer
HiWith mass fraction W
iCalculate according to following formula:
Multipolymer Hansch hydrophobicity contribution margin=∑ [W
i* V
Hi]
In actual application, select monomer and consumption thereof will take into account second-order transition temperature Tg and the multipolymer Hansch hydrophobicity contribution margin of multipolymer, make this polymer emulsion have the ability of anti-high speed dynamic shearing, with the China ink layer that adapts to high speed printing shift, wetting, dry, sticking power and wash an edition requirement.
In the present invention, preferably above-mentioned soft monomer includes but not limited to ethyl propenoate, propyl acrylate, butyl acrylate, Isooctyl acrylate monomer, or in the Isooctyl methacrylate one or more.Above-mentioned hard monomer include but not limited to isobornyl acrylate, methyl methacrylate, isobornyl methacrylate and cinnamic one or more.The second-order transition temperature Tg of above-mentioned monomer (i) and Hansch hydrophobicity contribution margin are as shown in table 1.Preferred these raw material monomers that adopt are easy to get in the present invention, and can be combined into the performance of wanting required for the present invention simply, rapidly, and in addition, these monomers are cheap, can effectively reduce cost of manufacture.
Table 1
| Monomer | The hydrophobicity contribution margin | T g(℃) |
| Butyl acrylate (BA) | 3.19 | -50 |
| Isooctyl acrylate monomer (EHA) | 5.22 | -70 |
| Isobornyl acrylate (IBOA) | 1.90 | 100 |
| Methyl methacrylate (MMA) | 1.89 | 100 |
| Butyl methacrylate (BMA) | 3.51 | 20 |
| Isooctyl methacrylate (EHMA) | 5.54 | -10 |
| Isobornyl methacrylate (IBOMA) | 2.22 | 180 |
| Vinylbenzene (St) | 4.29 | 100 |
In a kind of concrete relatively embodiment of the present invention, the quality of soft monomer is 30～50% in the mix monomer of above-mentioned polymer emulsion, and the quality of hard monomer is 70～50%.The quality percentage composition of soft monomer and hard monomer is controlled in this scope, configured second-order transition temperature Tg and Hansch hydrophobicity contribution margin easily, satisfy the copolymer emulsion of intaglio printing requirement simultaneously.
Preferably, in the present invention the reactive emulsifier that contains allyl group or vinyl that adopts comprises the reactive emulsifier of anionic and/or the reactive emulsifier of non-ionic type.The usage quantity of this reactive emulsifier is based on 1-12 part of 100 parts mix monomer, preferred 5-12 part, if the emulsifying agent usage quantity is too little, emulsifying effectiveness is bad, and gel content is big, and it is unstable that prepared polymer emulsion can become; If the emulsifying agent consumption is too big, polymerization rate is slack-off, and the viscosity of prepared polymer emulsion is big, in preferred range, with printing effect the best of the water color ink of prepared emulsion allotment.The reactive emulsifier reactive emulsifier of the reactive emulsifier of anionic and non-ionic type can be used alone, but also also mix together, and mixes when using, and the ratio of ionic/nonionic emulsifier is 1/2-3/1.
The reactive emulsifier of anionic has emulsify well, to the stable strong advantage of emulsion, the reactive emulsifier of anionic includes but not limited to vinylsulfonate and/or contains the sulfonate of alkane phenyl, allyl group and polyoxyethylene simultaneously or the reactive emulsifier of vitriol in the present invention.
Wherein, the structural formula of vinylsulfonate is: CH=CH (CH
2)
h-OSO3Na, wherein h=14～18; In 14～18 scopes, emulsifying agent prepares easily with h control.
Wherein, a kind of preferred structure formula that contains the reactive emulsifier of the sulfonate of alkane phenyl, allyl group and polyoxyethylene or vitriol simultaneously is:
Wherein, R is carbonatoms at 8～10 straight chained alkyl, described X
-Be sulfonate radical or sulfate radical, n is 10～20, M
+Be monovalent cation; R is defined as carbonatoms is defined as 10～20 at 8～10 straight chained alkyl, n, emulsifying agent prepares easily, raw material is easy to get; M wherein
+Represented monovalent cation comprises Na
+, K
+, NH
4 +Deng.
Reactive emulsifier and the ionic emulsifying agent of non-ionic type are used, and have the benefit that improves polymer emulsion stability., the reactive emulsifier of non-ionic type in the present invention includes but not limited to contain simultaneously the reactive emulsifier of alkane phenyl, allyl group and polyoxyethylene ether.
In the present invention, a kind of preferred structure formula that contains the reactive emulsifier of alkane phenyl, allyl group and polyoxyethylene ether simultaneously is:
Wherein, R ' is carbonatoms at 8～10 straight chained alkyl, and described m is 10～20.
Wherein, R is carbonatoms at 8～10 straight chained alkyl, and n is 10～20.In the present invention R being defined as carbonatoms is 10～20 at 8～10 straight chained alkyl, n, and the emulsifying agent in this scope prepares easily, and raw material is easy to get.
In a kind of preferred implementation of the present invention, the preparation of above-mentioned used for water color ink polymer emulsion, emulsifying agent also comprises 0～60% non-reacted emulsifying agent of reactive emulsifier quality, add this non-reacted emulsifying agent, some properties that not only can the telomerized polymer emulsion, for example, the viscosity of emulsion, solid content, surface tension etc. can also reduce material cost simultaneously.This non-reacted emulsifying agent can be selected the non-reacted emulsifying agent of anionic for use, also can select the non-reacted emulsifying agent of non-ionic type for use.
The optional non-reacted emulsifying agent of anionic comprises but is not limited to: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate; Sulfuric acid or the sulfonate of alkyl or alkane phenyl Soxylat A 25-7, for example: Nonyl pheno (4) ether ammonium sulfate, alkyl alcohol Soxylat A 25-7 (3) ammonium sulfate; Alkyl succinic acid (ester) sulfonate, N-hexadecyl succinamide sodium sulfonate, ethoxylated alkyl alcohol ether sulfo-succinic acid Carbenoxolone Sodium salt etc.;
The optional non-reacted emulsifying agent of non-ionic type comprises but is not limited to: the tensio-active agent that tween series, class of department series, alkyl polyoxyethylene ether are serial etc.
In a kind of preferably embodiment of the present invention, in the preparation of above-mentioned used for water color ink polymer emulsion, emulsifying agent also comprises 0～40% polymerizability emulsifying agent of reactive emulsifier quality, for example, contains the allylic succsinic acid of alkyl (ester) salt.C=C unsaturated group and the hydrophilic radical of this polymerizability emulsifying agent lean on closely, separately as the effect of emulsifying agent and bad, but cooperate aforesaid reactable emulsifying agent to use, some properties that can the telomerized polymer emulsion, for example, polymer water dissolubility, viscosity, surface property etc.
Optionally contain the allylic succsinic acid of alkyl (ester) salt polymerizable emulsifier, include but not limited to: hexadecyl allyl group succsinic acid dibasic acid esters sodium sulfonate, dodecyl allyl group mono succinate sodium sulfonate.
In a kind of preferred implementation of the present invention, in the preparation of above-mentioned used for water color ink polymer emulsion, also comprise the functional vinyl monomer that contains carboxyl or sulfonate of mix monomer weight 0～5% in the polymer raw.These functional vinyl monomers that contain carboxyl or sulfonate can be adjusted the property of multipolymer, as water-soluble, stability of emulsion, viscosity, sticking power etc.
Alternatively, contain the functional vinyl monomer of carboxyl or sulfonate, include but not limited to 3-methacryloxy-2-hydroxyl-1-propane sulfonic acid sodium salt, 2-acrylamido-2 methyl propane sulfonic acid sodium salt; 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium salt, (methyl) vinylformic acid.
In the present invention, the functional vinyl monomer that contains carboxyl or sulfonate mainly plays the effect of regulating prepared polymer emulsion property, and its usage quantity is less, is not counted in the calculating of multipolymer second-order transition temperature Tg and hydrophobicity contribution margin.
In used for water color ink polymer emulsion of the present invention, also comprise some functional agents, for example initiator and reductive agent.The consumption of initiator is the 0.3%-3% of monomer mass, and the consumption of reductive agent is 0.7-1.5 according to the mass ratio of reductive agent and initiator.The use of these functional agents can be added according to the common technology means of prior art.The principle of relevant letex polymerization, composition and method further can be referring to professional books more.
Wherein, optional initiator includes, but are not limited to the persulphate of thermolysis type, for example ammonium persulphate, Potassium Persulphate, Sodium Persulfate, and hydrogen peroxide, and water miscible organo-peroxide etc.If use persulphate to be initiator, also need to add a little carbonate and persulphate and be used, with the pH value of control reaction system.
Can also use reductive agent, for example Sulfothiorine, water-soluble amine, polyvalent metal salt etc.These reductive agents cooperate with persulfate initiator, form the redox initiator system, the synthesis reaction temperature of emulsion can be reduced under 5-50 ℃ the lower temperature carry out.Because it is serious that Raolical polymerizable is subjected to the influence of oxygen, polyreaction can be taked the excluding air that outgases, then at nitrogen or CO
2Protection under carry out.
In a kind of typical embodiment of the present invention, the preparation method of above-mentioned used for water color ink polymer emulsion may further comprise the steps: mix monomer, first part's emulsifying agent and deionized water are mixed, carry out pre-emulsification, obtain pre-emulsion A; Initiator and deionized water are mixed with solution B; Under nitrogen atmosphere and agitation condition, second section emulsifying agent and deionized water are mixed, be warming up to the temperature of polymerization reaction take place; Drip described mixed liquor A and described solution B, after dripping off, continue reaction 2～3h; Heat up 20～25 ℃ and continue reaction 2h, obtain polymerized emulsion; With described polymerized emulsion cooling, and regulate pH value to neutral, add deionized water, regulate the solid content of polymerized emulsion to 33%-43%,, namely get described used for water color ink polymer emulsion.
Preferably, above-mentioned preparation method may further comprise the steps: mix monomer, the emulsifying agent that is higher than emulsifying agent total content 85% and deionized water are mixed, carry out the pre-emulsification of 5-30min, obtain pre-emulsion A; Initiator and deionized water are mixed with solution B in room temperature; Under nitrogen atmosphere and agitation condition, remaining emulsifying agent and deionized water are mixed, be warming up to 30～75 ℃; Drip described pre-emulsion A and described solution B, continue reaction 2～3h in nitrogen protection with under stirring; Continue reaction 2h after intensification 20--25 ℃, obtain polymerized emulsion; Described polymerized emulsion is cooled to room temperature; Regulate the pH value of described mixed emulsion to neutral, add the solid content that deionized water is regulated described polymerized emulsion, make it reach 33%～43%, form described used for water color ink polymer emulsion.
In aforesaid method polymeric reaction temperature is set in 30～90 ℃, this temperature range is fit to the employed decomposition initiator of polyreaction, and polymerization rate is controlled well, and initiator is decomposed fully as far as possible.Initiator will be prepared at normal temperatures, otherwise initiator can decompose, and influences effective constituent.The mode that adopts the pre-emulsification of monomer and control to drip makes emulsion particle be in " hunger " state always, reduces the formation of new latex nuclear, is conducive to control the size of emulsion particle and distribute.In order to make conversion of monomer complete, after the intensification polyreaction finishes, can also add a small amount of initiator, for example persulphate or organo-peroxide make monomer polymerization as far as possible, reduce residual quantity.
Further specify beneficial effect of the present invention below with reference to embodiment 1-10 and Comparative Examples 1-4.
Raw material: the various raw materials that adopt in embodiment 1-10 and the corresponding abbreviation of raw material be to such as table 2, and wherein the employed emulsifying agent gas chemical industry company limited that is Foshan section produces.
Table 2
For simplicity of exposition, in following embodiment 1-10, composition and the ratio of the mix monomer, function monomer, emulsifying agent, initiator etc. of preparation polymer emulsion have been listed, indicate the temperature of polyreaction, listed the solid content of gained emulsion, theory T g and the Hansch hydrophobicity contribution margin parameter of polymkeric substance.
The preparation method of polymer emulsion among the embodiment 1-10:
With mix monomer, 9/10 emulsifying agent with join in the pre-emulsor with the deionized water of weight such as mix monomer at least, carry out the pre-emulsification of 10min, obtain pre-emulsion A, and pre-emulsion A is changed over to the feed pot 1 of reactor;
With initiator and at least the deionized water of 10 times of weight of initiator under≤30 ℃, be mixed with solution B, and solution B is changed over to the feed pot 2 of reactor;
With remaining emulsifying agent and at least the deionized water of weight such as remaining emulsifying agent join in the polymerization reaction kettle, under nitrogen protection, start stirring, be warming up to the temperature of 30～75 ℃ polyreaction; Pre-emulsion A and the solution B feed pot from reactor is slowly added the polymerization reaction kettle, and reinforced time 2～3h drips the back and continues to continue in nitrogen protection and under stirring reaction 2～3h; Then polymerization liquid is heated up 20～25 ℃, continue to be cooled to room temperature behind the reaction 2h; Regulate the pH value of emulsion to neutral, add deionized water and regulate the solid content of described emulsion, make it reach 33%～43%, form the used for water color ink polymer emulsion.
Embodiment 1
Mix monomer: BMA:2.0 part, EHMA:46 part, IBOMA:44 part, St:2.67 part, MMA:5.33 part; 2.5 parts of MA (function monomer);
Emulsifying agent: SN-15:7.0 part, SDS:0.5 part;
Initiator: ammonium persulphate: 3 parts,
Polymerization temperature is: 75 ℃.
Solid content 50wt%, 60 ℃ of Tg, Hansch parameter: 3.81.
Embodiment 2
Mix monomer is formed: 3 parts of BA, 17 parts of EHMA, 11.0 parts of IBOMA, 29 parts of St, IBOA17 part, 5 parts of MMA23 part, MA (function monomer);
10 parts of emulsifying agent: SE-20,2 parts of hexadecyl allyl group succsinic acid dibasic acid esters sodium sulfonates;
Initiator: 3 parts of ammonium persulphates;
Polymerization temperature is: 75 ℃.
Emulsion solid content 45wt%, 90 ℃ of Tg, Hansch parameter: 3.28.
Embodiment 3
Monomer is formed: BMA26 part, EHA2.0 part, IBOMA9 part, 33 parts of St, IBOA21 part, MMA9 part; 5 parts of AHPS (function monomer);
2 parts of emulsifying agent: SE-15,4 parts of AOS;
Initiator: 3 parts of hydrogen peroxide
Reductive agent: 4 parts in Sulfothiorine;
Polymerization temperature is: 30 ℃;
Emulsion solid content 45wt%, Tg75 ℃, Hansch parameter: 3.20.
Embodiment 4
Monomer is formed: 9 parts of BMA, 15 parts of EHA, 17 parts of IBOMA, 19.67 parts of St, IBOA19.67 part, 19.67 parts of MMA; 2.5 parts of AHPS (function monomer);
5 parts of emulsifying agent: SE-10; 3 parts of OP-10;
Initiator: hydrogen peroxidase 10 .3 part;
Reductive agent: 0.2 part in Sulfothiorine;
Polymerization temperature is: 40 ℃;
Solid content 36wt%, 60 ℃ of Tg, Hansch parameter: 3.07.
Embodiment 5
14 parts of mix monomer: BA, 1 part of EHMA, 15 parts of IBOMA, 23 parts of St, IBOA20 part, MMA27 part; MHPS (function monomer): 5 parts;
8 parts of emulsifying agent: AOS, 0.6 part of N-hexadecyl succinamide sodium sulfonate;
Initiator: ammonium persulphate: 1.5 parts;
Polymerization temperature is: 70 ℃;
Solid content 40wt%, 75 ℃ of Tg, Hansch parameter: 2.27.
Embodiment 6
18 parts of mix monomer: BMA, 13 parts of EHMA, IBOMA43 part, 8.67 parts of St, MMA17.34 part; 5 parts of AA (function monomer);
0.8 part of emulsifying agent: SE-20; 0.3 part of dodecyl allyl group mono succinate sodium sulfonate, 0.5 part of tween-80;
Initiator: 2.5 parts of ammonium persulphates;
Polymerization temperature is: 75 ℃.
Solid content 43wt%, 90 ℃ of Tg, Hansch parameter: 3.01.
Embodiment 7,
2 parts of mix monomer: BA, 19 parts of EHA, 57 parts of IBOMA, 7 parts of St, 6 parts of IBOA, 9 parts of MMA;
1.6 parts of emulsifying agent: SN-10,0.8 part of SE-10,1.4 parts of ethoxylated alkyl alcohol ether sulfo-succinic acid Carbenoxolone Sodium salt;
Initiator: 1.5 parts of hydrogen peroxide;
Reductive agent: Sulfothiorine: 1 part;
Polymerization temperature is: 50 ℃.
Solid content 40wt%, 75 ℃ of Tg, Hansch parameter: 2.91.
Embodiment 8,
18 parts of mix monomer: BA, EHMA4 part, 10 parts of IBOMA, 23 parts of St, IBOA25 part, MMA20 part; MHPS (function monomer): 2.5 parts;
Emulsifying agent: SN-15:2.4 part; SDS:1.2 part;
Initiator: ammonium persulphate: 2.0 parts;
Polymerization temperature is: 75 ℃.
Solid content 44wt%, Tg60 ℃, Hansch parameter: 2.85
Embodiment 9,
30 parts of mix monomer: St, 15 parts of MMA, 15 parts of IBOA, 18.5 parts of BA, 10 parts of EHA, 11.5 parts of IBOMA, 1.25 parts of MA (function monomer),
Emulsifying agent: SE-10:4.0 part;
Initiator: ammonium persulphate: 1 part;
Polymerization temperature is: 75 ℃.
Solid content 38wt%, 50 ℃ of Tg, Hansch parameter: 3.41.
Embodiment 10
Mix monomer is formed: 19 parts of BA, EHA2 part, IBOMA45 part, 10 parts of St, MMA24 part;
2 parts of emulsifying agent: SE-20;
Initiator: 0.3 part of ammonium persulphate;
Polymerization temperature: 75 ℃.
Emulsion solid content 45wt%, 80 ℃ of polymer Tg, Hansch parameter: 2.59.
Comparative Examples 1
Mix monomer is formed: 19 parts of BA, EHA2 part, IBOMA45 part, 10 parts of St, MMA24 part;
2 parts of emulsifying agent: SDS;
Initiator: 0.3 part of ammonium persulphate;
The preparation method: with embodiment 1-10, wherein polymerization temperature is 75 ℃.
Emulsion solid content 45wt%, 80 ℃ of polymer Tg, Hansch parameter: 2.59.
Comparative Examples 2
The environment-friendly water-based ink resin GH-AS-AAW that the poly-power chemical industry company limited in Hangzhou produces, main component is modification vinyl acetate between to for plastic-acrylic copolymer resin.
Comparative Examples 3
The APU-66 aqueous polyurethane emulsion resin that the auspicious neat Industry investment of Dongguan City company limited produces, the solid content of this resin is 35%.
Comparative Examples 4
The light that New Orient, Zhejiang printing ink limited-liability company produces reaches the red gravure ink of 2000 types, is to be the sheet package gravure ink of main solvent with ester and alcohol.
The performance evaluation of the prepared polymer emulsion of prepared polymer emulsion and Comparative Examples 1-4 and above-mentioned polymer emulsion are as the performance evaluation of water color ink among the embodiment 1-10, and concrete outcome is as shown in table 3.
Method of evaluating performance to above-mentioned polymer emulsion and water color ink is as follows:
Stability in storage-prepared polymer emulsion is placed 12h at 5 ℃ is earlier placed 12h at 60 ℃ then, repeats aforesaid operations 20 times.Observe in the polymer emulsion demulsifying phenomenon whether occurs, if demulsifying phenomenon is that stability is defective, be labeled as X, if keep former emulsion form for passing through, be labeled as P.
Mechanical stability-prepared polymer emulsion is added iron flask, the zirconium pearl of putting into 3 times of weight of polymer emulsion again is placed on " Red Devil " board mixing machine (U.S. produces, and is called for short the quick worker) together and goes up concussion 3h.Observe in the polymer emulsion demulsifying phenomenon whether occurs, if demulsifying phenomenon is that stability is defective, be labeled as X, if keep former emulsion form for passing through, be labeled as P.
Chemical stability-add saturated calcium chloride emulsion in prepared polymer emulsion is placed 24h; Observe in the polymer emulsion demulsifying phenomenon whether occurs, if phenomenons such as breakdown of emulsion, flocculation are that stability is defective, be labeled as X, if keep former emulsion form for passing through, be labeled as P.
Anti-ethanol-add isopyknic ethanol/water (4/1, volume ratio) solution in prepared polymer emulsion is placed 0.5h, if phenomenons such as emulsion breaking, flocculation are that stability is defective, be labeled as X, if keep even, stable emulsion form for passing through, be labeled as P.
Draw a design effect-with prepared polymer emulsion of water color ink printing is diluted with water to 35% solid content, part by weight according to emulsion/red aqueous color paste/thinner=1/1/1.5 reconciles into printing ink, wherein thinner consists of ethanol/water=4/1, (volume ratio), printing is drawn a design with KPP intaglio printing proof press, speed is 40m/min, white version paperboard.Printing is labeled as √ √ but any defective, light, saturating tinctorial pattern are outstanding; But any defective, light, but saturating look poor slightly be well, be labeled as √; What printing defects was arranged is defective, is labeled as X.
Table 3
| Stability in storage | Mechanical stability | Chemical stability | Anti-ethanol | Printing effect | |
| Embodiment 1 | P | P | P | P | √√ |
| Embodiment 2 | P | P | P | P | √√ |
| Embodiment 3 | P | P | P | P | √√ |
| Embodiment 4 | P | P | P | P | √√ |
| Embodiment 5 | P | P | P | P | √√ |
| Embodiment 6 | P | P | P | P | √ |
| Embodiment 7 | P | P | P | P | √ |
| Embodiment 8 | P | P | P | P | √ |
| Embodiment 9 | P | P | P | P | √ |
| Embodiment 10 | P | P | P | P | √ |
| Comparative Examples 1 | P | P | X | X | X |
| Comparative Examples 2 | P | P | P | X | X |
| Comparative Examples 3 | P | P | P | P | X |
| Comparative Examples 4 | - | - | - | - | √√ |
By content in the table 3 as can be seen, the performance of prepared polymer emulsion and the performance that all is better than polymer emulsion and water color ink thereof prepared among the Comparative Examples 1-3 by the performance of the prepared water color ink of this polymer emulsion among the embodiment of the invention 1-10, especially preferably form emulsion with proportional range in the present invention, the printing effect of its water color ink is suitable with Comparative Examples 4 solvent borne printing ink.
Comparative Examples 1 is the polymer emulsion according to existing method preparation, the second-order transition temperature Tg of polymkeric substance and Hansch hydrophobicity contribution margin parameter meet the present invention to the requirement of polymer glass temperature T g and Hansch hydrophobicity contribution margin in this polymer emulsion, but its chemical-resistant stability and anti-ethanol are all bad, and the printing effect that adopts the prepared water color ink of Comparative Examples 1 polymer emulsion to print is poor.The raw material of polymkeric substance in raw material and the present patent application in the contrast Comparative Examples 1, be not difficult to find, in Comparative Examples 1, do not use the reactive emulsifier that contains allyl group or vinyl-functional, this shows, contain the reactive emulsifier of allyl group or vinyl-functional for the vital role of polymer emulsion performance provided by the present invention.
Comparative Examples 2 and Comparative Examples 3 all are to adopt commercially available water-base resin, the stability of these commercially available water-based emulsions still can, but very poor with the printing effect of the water color ink of their preparations, defectives such as tangible colour band, dim spot appear in printed patterns.
Not only stability and anti-ethanol are good by the prepared polymer emulsion of embodiment of the invention 1-10, and the printing effect of water color ink all obviously is better than the water color ink with existing public technology, especially preferably form emulsion with proportional range in the present invention, embodiment 1-5 for example, the anti-high speed dynamic shearing of its water color ink etc. ability the best, can realize best printing effect, reach the expection that can replace solvent type ink.The above results shows that the present invention has reached effect preferably.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. used for water color ink polymer emulsion, it is characterized in that, the raw material of described polymer emulsion comprises by weight: the emulsifying agent of 100 parts mix monomer and 1～12 part, described mix monomer comprises soft monomer and hard monomer, the quality of soft monomer described in the described mix monomer is 30～50%, the quality of described hard monomer is 70～50%, described emulsifying agent comprises the reactive emulsifier that contains allyl group or vinyl-functional at least, wherein the second-order transition temperature Tg of the multipolymer that is obtained by the reaction of described mix monomer is 60～90 ℃, and the equal Hansch hydrophobicity of matter contribution margin is 2.57～3.81; And the solid content of described polymer emulsion is 33%～43%;
Described soft monomer is ethyl propenoate, propyl acrylate, butyl acrylate, Isooctyl acrylate monomer, or in the Isooctyl methacrylate one or more, described hard monomer be isobornyl acrylate, methyl methacrylate, isobornyl methacrylate and cinnamic one or more.
2. polymer emulsion according to claim 1 is characterized in that, the raw material of described polymer emulsion comprises by weight: the emulsifying agent of 100 parts mix monomer and 5～12 parts.
3. polymer emulsion according to claim 1 and 2 is characterized in that, described reactive emulsifier comprises the reactive emulsifier of anionic and/or the reactive emulsifier of non-ionic type,
The reactive emulsifier of described anionic is vinylsulfonate, contains the sulfonate of alkane phenyl, allyl group and polyoxyethylene simultaneously, and contains in the vitriol of alkane phenyl, allyl group and polyoxyethylene one or more simultaneously;
The structural formula of described vinylsulfonate is:
CH=CH (CH
2)
h-OSO
3Na, wherein h=14～18;
The described structural formula that contains the sulfonate of alkane phenyl, allyl group and polyoxyethylene simultaneously and contain the vitriol of alkane phenyl, allyl group and polyoxyethylene simultaneously is:
Wherein, R is carbonatoms at 8～10 straight chained alkyl, described X
-Be sulfonate radical or sulfate radical, described n is 10～20, M
+Be monovalent cation;
The reactive emulsifier of described non-ionic type is for containing the reactive emulsifier of alkane phenyl, allyl group and polyoxyethylene ether simultaneously, and the described structural formula that contains the reactive emulsifier of alkane phenyl, allyl group and polyoxyethylene ether simultaneously is:
Wherein, R ' is carbonatoms at 8～10 straight chained alkyl, and described m is 10～20.
4. polymer emulsion according to claim 1 and 2, it is characterized in that, described emulsifying agent comprises that also content is the non-reacted emulsifying agent of described reactive emulsifier quality 0～60%, and described non-reacted emulsifying agent comprises anionic emulsifier and/or non-ionic emulsifier
Described anionic emulsifier is one or more in the sulfonate of the sulfonate of vitriol, alkyl polyoxyethylene ether of vitriol, the alkane phenyl Soxylat A 25-7 of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl polyoxyethylene ether and alkane phenyl Soxylat A 25-7;
Described nonionic emulsifier is one or more in Tweens, class of department class, the alkyl polyoxyethylene ether class.
5. polymer emulsion according to claim 4, it is characterized in that, described emulsifying agent comprises that also content is the polymerizability emulsifying agent of described reactive emulsifier quality 0～40%, and described polymerizable emulsifier is for containing alkyl and allylic succsinic acid (ester) salt simultaneously.
6. polymer emulsion according to claim 1 and 2, it is characterized in that, comprise also in the described mix monomer that content is the functional vinyl monomer that contains carboxyl or sulfonate of soft monomer and hard monomer gross weight 0～5%, functional vinyl monomer is one or more in 3-methacryloxy-2-hydroxyl-1-propane sulfonic acid sodium salt, 2-acrylamido-2 methyl propane sulfonic acid sodium salt, 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium salt, (methyl) vinylformic acid.
7. the preparation method as each described used for water color ink polymer emulsion among the claim 1-6 is characterized in that, may further comprise the steps:
Mix monomer, the emulsifying agent that is higher than emulsifying agent total content 85% and deionized water are mixed, carry out the pre-emulsification of 5-30min, obtain pre-emulsion A;
Initiator and deionized water are mixed with solution B in room temperature;
Under nitrogen atmosphere and agitation condition, remaining emulsifying agent and deionized water are mixed, be warming up to 30～75 ℃; Drip described pre-emulsion A and described solution B, continue reaction 2～3h in nitrogen protection with under stirring; Heat up and continue reaction 2h after 20～25 ℃, obtain described polymerized emulsion;
Described polymerized emulsion is cooled to room temperature; Regulate the pH value of described mixed emulsion to neutral, add the solid content that deionized water is regulated described polymerized emulsion, make it reach 33%～43%, form described used for water color ink polymer emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110430504 CN102558427B (en) | 2011-12-20 | 2011-12-20 | Polymer emulsion for water-based printing ink and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110430504 CN102558427B (en) | 2011-12-20 | 2011-12-20 | Polymer emulsion for water-based printing ink and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102558427A CN102558427A (en) | 2012-07-11 |
| CN102558427B true CN102558427B (en) | 2013-09-25 |
Family
ID=46405150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110430504 Expired - Fee Related CN102558427B (en) | 2011-12-20 | 2011-12-20 | Polymer emulsion for water-based printing ink and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102558427B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834233B (en) * | 2012-11-26 | 2016-03-09 | 北京印刷学院 | Water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion |
| CN103214614B (en) * | 2013-05-15 | 2015-06-17 | 天津滨联科技发展有限公司 | Preparation method of aqueous environment-friendly high speed plastic printing ink resin |
| CN103408691B (en) * | 2013-08-06 | 2016-03-16 | 中科院广州化学有限公司 | A kind of Acrylate pressure-sensitive adhesive emulsion and preparation method thereof and application |
| EP3177673B1 (en) * | 2014-08-08 | 2021-06-30 | Rhodia Operations | Allyl ether sulfate polymerizable surfactants and methods for use |
| CN105733359B (en) * | 2016-05-13 | 2018-07-13 | 深圳市布瑞特水墨涂料有限公司 | A kind of aqueous intaglio printing ink and preparation method thereof |
| CN106905810B (en) * | 2017-03-23 | 2019-04-16 | 北京东方雨虹防水技术股份有限公司 | A kind of preparation method of water-based elastic paint lotion, water-based elastic paint lotion and coating |
| CN109096440A (en) * | 2017-06-21 | 2018-12-28 | 广东华润涂料有限公司 | Water-based latex, preparation method containing the polymer beads with core-shell structure and the coating formed by the water-based latex |
| CN110204958A (en) * | 2019-07-08 | 2019-09-06 | 东莞职业技术学院 | Environment-friendly water-based printing ink of one kind and preparation method thereof |
| CN110605926B (en) * | 2019-10-11 | 2020-08-21 | 乌兰浩特森辉印务有限公司 | Cigarette case printing process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544500A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院广州化学研究所 | Core-shell particles with acroleic acid esterified polyurethane as main body of core and making method and use thereof |
| CN1876735A (en) * | 2005-06-09 | 2006-12-13 | 北京化工大学 | Room temperature crosslinked aqueous coating and preparation method thereof |
| CN101230553A (en) * | 2008-01-08 | 2008-07-30 | 牡丹江恒丰纸业股份有限公司 | Automobile industry filter paper impregnation emulsion and method for modifying the same by using polymerizable emulsifier |
| CN101289601A (en) * | 2008-05-30 | 2008-10-22 | 江苏工业学院 | Cationic binder emulsion for coating coloring, preparation method and uses |
| CN101519561A (en) * | 2009-04-03 | 2009-09-02 | 西安华泰有色金属实业有限责任公司 | Method for preparing ultraviolet-screening, transparent, heat-insulation paint |
-
2011
- 2011-12-20 CN CN 201110430504 patent/CN102558427B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544500A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院广州化学研究所 | Core-shell particles with acroleic acid esterified polyurethane as main body of core and making method and use thereof |
| CN1876735A (en) * | 2005-06-09 | 2006-12-13 | 北京化工大学 | Room temperature crosslinked aqueous coating and preparation method thereof |
| CN101230553A (en) * | 2008-01-08 | 2008-07-30 | 牡丹江恒丰纸业股份有限公司 | Automobile industry filter paper impregnation emulsion and method for modifying the same by using polymerizable emulsifier |
| CN101289601A (en) * | 2008-05-30 | 2008-10-22 | 江苏工业学院 | Cationic binder emulsion for coating coloring, preparation method and uses |
| CN101519561A (en) * | 2009-04-03 | 2009-09-02 | 西安华泰有色金属实业有限责任公司 | Method for preparing ultraviolet-screening, transparent, heat-insulation paint |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102558427A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102558427B (en) | Polymer emulsion for water-based printing ink and preparation method thereof | |
| EP0013836B1 (en) | Compositions containing acrylic emulsion copolymers and their use as thickeners | |
| CN101704913B (en) | Styrene-acrylic emulsion for priming paint as well as preparation method and application thereof | |
| CN100560621C (en) | Filming flow type polyacrylacid ester soap-free emulsion and synthesis technique and the application in printing ink thereof | |
| JPS5989313A (en) | Tackifying alkylacrylamide-containing emulsion copolymer | |
| CN107805437A (en) | It is a kind of to be used to repair aqueous woodware paint of color and preparation method thereof | |
| CN101597355A (en) | A kind of water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof | |
| CN101168650A (en) | Single-component self-crosslink emulsion adhesive for dry type composite film and preparation method thereof | |
| CN107141393A (en) | A kind of styrene-acrylic emulsion used for water color ink and preparation method thereof | |
| CN101275005A (en) | Preparation for acroleic acid emulsion having nucleocapsid structure, acroleic acid emulsion and water-based gloss oil therefrom | |
| CN101575476A (en) | Aqueous wear-resistant gloss oil and preparation method thereof | |
| CN102617771A (en) | Aqueous printing ink binding agent and ink as well as preparation methods thereof | |
| CN110204958A (en) | Environment-friendly water-based printing ink of one kind and preparation method thereof | |
| CN102875739A (en) | Epoxy resin modified styrene-acrylic emulsion and preparation method thereof | |
| CN102101947A (en) | Gloss oil of aqueous ink fountain for offset printing press and preparation method thereof | |
| CN102234345A (en) | Preparation method of environment-friendly type emulsion for water-based ink | |
| CN104910317A (en) | Acrylic resin emulsion used in water-based plastic ink, and preparation method thereof | |
| CN103194127A (en) | Waterborne over-printing varnish for environment-friendly paper | |
| CN104805732A (en) | Styrene-acrylate emulsion type efficient surface sizing agent and preparing method thereof | |
| CN105524225A (en) | Core-shell type polyacrylate emulsion printing adhesive | |
| CN101457499A (en) | Surface sizing agent and its production method | |
| CN108912832A (en) | A kind of modified aqueous acrylic acid resin flexible version water-based ink and preparation method thereof | |
| CN103936916B (en) | PET film precoating heat is mounted aqueous binder emulsion and preparation method | |
| CN107298732A (en) | Core-shell structure styrene-acrylic emulsion composition of resistance to ethanol dilution and preparation method thereof | |
| CN109181402A (en) | A kind of preparation method of watersoluble modified acrylic acid resin type hyper-dispersant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130925 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |