CN1183215C - Process for preparation of leather bottom-closing coating and decorating agent - Google Patents
Process for preparation of leather bottom-closing coating and decorating agent Download PDFInfo
- Publication number
- CN1183215C CN1183215C CNB991150902A CN99115090A CN1183215C CN 1183215 C CN1183215 C CN 1183215C CN B991150902 A CNB991150902 A CN B991150902A CN 99115090 A CN99115090 A CN 99115090A CN 1183215 C CN1183215 C CN 1183215C
- Authority
- CN
- China
- Prior art keywords
- preparation
- account
- total amount
- gram
- ammonium halide
- 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
- 239000011248 coating agent Substances 0.000 title claims abstract description 19
- 239000010985 leather Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 title claims description 19
- 238000000576 coating method Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title abstract description 4
- -1 alcohol compound Chemical class 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 108010013296 Sericins Proteins 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 15
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229940034586 silk sericin Drugs 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 239000013543 active substance Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 125000002091 cationic group Chemical group 0.000 abstract description 3
- 239000000839 emulsion Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 238000007790 scraping Methods 0.000 abstract 2
- 238000007789 sealing Methods 0.000 abstract 2
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000002932 luster Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 23
- 238000010792 warming Methods 0.000 description 10
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000005018 casein Substances 0.000 description 8
- 235000021240 caseins Nutrition 0.000 description 8
- 230000001804 emulsifying effect Effects 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001125620 Dermochelys coriacea Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to a method for preparing a bottom sealing coating agent for tanning. The preparation method of the present invention comprises the following steps: 0.4% to 6.0% of sericin, 0 to 5.0% of cationic surface active agent, 0.04% to 3.0% of micromolecule acid, 5.0% to 25% of acrylate monomer, 0.5% to 10.0% of nitrogen-containing monomer, 0 to 6.0% of hydroxyl-containing monomer and water react under the temperature of 50 to 95DEGC for 4 to 12 hours; 0 to 3.6% of alcohol compound is added to react continuously for 0.5 hours to obtain the leather bottom sealing coating agent of the present invention. The product of the present invention has the advantages of good emulsion stability, long storage period, saving of the consumption of other leather chemical products, comfort and softness of finished leather, natural and bright luster of the finished leather, firm adhesion of a coating layer, dry scraping resistance and wet scraping resistance, high hiding rate and repairing property.
Description
The present invention is the bottom-closing coating and decorating agent preparation method that a kind of process hides is used, and it belongs to the preparation of natural polymer albumen graft copolymer.
Protein finishes is the important class in the hide finishes, wherein is typical case's representative especially with the casein.Casein is commonly called as casein, lactic casein.But it has premium propertiess such as strong, high temperature resistant, withstand voltage, the anti-flatiron polishing of clinging power, and the coating gloss height that forms, hand feel and drape, and sanitation performance is good.But the casein film-forming properties is poor, crisp, the poor water resistance of gel rerum natura.So people are devoted to the modification of casein always, or seek other surrogate, as: gelatin, feather protein, Keratin sulfate.
By modification to casein and surrogate thereof, improve deficiency, improve application performance, the albumen finishing agent still is widely used.The existing many products of modified Casein finishing agent come out, as the BI of the Baysin of the Luron of German BASF AG, Bayer company, Dutch Stahl company.Czech patents CS277110 has reported and has utilized the modification of chrome tanning waste protein hydrolysate through acrylic polymers, has been prepared into hide finishes.Yet this series products all is the negatively charged ion product, as the positively charged ion bottom-closing coating and decorating agent, reports very few.
Silk sericin is present in the cocoon layer, accounts for 20～30% of silk weight, usually as the throwing byproduct with discharge of wastewater.This not only causes the waste of resource, has also aggravated the pollution of environment, thereby, be badly in need of being used.Daily use chemicals, feedstuff industry are more common in the utilization of silk sericin, also can be in order to amino acid whose refine, but do not see any bibliographical information as the cationic leather bottom-closing coating and decorating agent.
The objective of the invention is to replace casein, adopt a kind of new prescription and the agent of prepared cationic leather back cover,, improve Atom economy to reduce the use of leather chemicals with silk sericin; Utilizing waste to produce leather chemicals, save resource, reduce production costs, also is very friendly to ecotope.
Leather bottom-closing coating and decorating agent prescription of the present invention is composed as follows: sericin 0.4%～6.0% (weight, down together), cats product 0～5.0%, small molecules acid 0.04%～3.0%, acrylate monomer 5.0%～25%, nitrogen containing monomer 0.5%～10.0%, hydroxyl monomer 0～6.0%, surplus are water, are initiator with persulphate and sulphite, under 50～95 ℃, carry out emulsion graft copolymerization reaction 4～12 hours, thereby obtain leather bottom-closing coating and decorating agent of the present invention.
In above-mentioned prescription, also can add alcohol compound, add-on is 0～3.6%, gets leather bottom-closing coating and decorating agent of the present invention.
Sericin refine and getting from by product silk material or wastewater from silk reeling wherein.
Cats product is a dodecyl dimethyl benzyl ammonium halide (1227), dodecyl trimethyl-ammonium halide (1231), cetyl trimethyl ammonium halide (1631), octadecyl trimethyl-ammonium halide (1831).
Small molecules acid is hydrochloric acid, phosphoric acid, (methyl) vinylformic acid, formic acid.
Ester group is C in the acrylate monomer
2～C
20Esters monomer.
Nitrogen containing monomer is acrylamide, dimethylaminoethyl acrylate methyl base amido ethyl ester, (methacryloxy-trimethylammonium) ammonium halide, (methacryloxy-dimethyl-butyl) ammonium halide, (methacryloxy-dimethyl-ethyl) ammonium halide.
The hydroxyl monomer is (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, N hydroxymethyl acrylamide.
Alcohol compound is ethylene glycol, propylene glycol, glycerol, polyoxyethylene glycol (M=90～1200).
Reaction process of the present invention is all under agitation carried out, and rotating speed is 60～120rpm.
Form by above-mentioned prescription, concrete operations of the present invention are: silk gum and suitable quantity of water are dropped in the reactor, start stirring and slowly be warming up to 50～70 ℃, add small molecules acid more successively, cats product and nitrogen containing monomer, stir and add acrylate and hydroxyl monomer after 0.5～2 hour, supply the water yield, emulsification 1～2 hour, add persulphate and sulphite initiator, reacted 2～4 hours down, be warming up to 70～95 ℃ then at 50～70 ℃, reacted again 2～4 hours, add alcohol compound, stirred 0.5 hour, cooling discharge gets leather bottom-closing coating and decorating agent of the present invention.
The bottom-closing coating and decorating agent good emulsion stability of the present invention's preparation surpasses half a year storage period.Use positively charged ion bottom-closing coating and decorating agent of the present invention, method is simple, and effect is obvious.Behind bottom-closing coating and decorating agent back cover of the present invention, can effectively stop the further infiltration in leather of follow-up anionic materials, not only can reduce the consumption of subsequent material, and the leather softness is comfortable, gloss is bright naturally.The coating clinging power is strong, Bearable dry and wet wipe, and hiding rare is strong, has certain benefit wound property, helps improving the grade of wounded or disabled skin.
Below be embodiments of the invention.
Embodiment one
Get sericin 8 gram (account for total amount 1.6%), add reaction flask, add water 180 grams again, be heated to 50 ℃, stir and to add 36% hydrochloric acid, 0.3 gram (account for total amount 0.04%) down successively, 3,0%1,227 6.5 grams (account for total amount 0.4%), acrylamide 6 grams (account for total amount 1.2%), stir and add ethyl propenoate 30 gram (account for total amount 5.9%) after 2 hours more successively, vinylformic acid stearyl 5 grams (account for total amount 1.1%).Rocryl 410 2 gram (account for total amount 0.4%), water 275 grams are 50 ℃ of following stirring and emulsifying half an hour, add persulphate 0.5 gram and sulphite 0.2 gram then, reacted 4 hours down, be warming up to 80 ℃ of reactions 2 hours again at 50 ℃, cooling discharge gets finished product 510 grams.
Embodiment two
Get sericin 15 gram (account for total amount 2.8%), add reaction flask and add water 150 grams again, be heated to 60 ℃, stir and to add 85% phosphatase 11 .0 gram (account for total amount 0.2%) down successively, vinylformic acid 3 gram (account for total amount 0.6%), 7,0%1,631 18 grams (account for total amount 2.4%), dimethylaminoethyl acrylate methyl base amido ethyl ester 10 gram (account for total amount 1.9%), stir and to add butyl acrylate 40 grams (account for total amount 7.5%) after half an hour more successively, dodecylacrylate 6 gram (account for total amount 1.1%), N hydroxymethyl acrylamide 5 gram (account for total amount 0.9%), water 280 grams, in 60 ℃ of stirring and emulsifying 2 hours, add persulphate 0.8 gram and sulphite 0.4 gram then, reacted 3 hours down at 60 ℃, be warming up to 90 ℃ of reactions 1 hour again, add glycerol 5 gram (account for total amount 0.9%) reaction 0.5 hour at last, cooling discharge, finished product 530 grams.
Embodiment three
Get sericin 25 gram (account for total amount 4.8%), add reaction flask and add water 180 grams again, be heated to 70 ℃, stir and to add 85% formic acid, 8 grams (account for gross weight 1.3%) down successively, acrylamide 10 gram (account for total amount 1.9%), (methacryloxyethyl-trimethylammonium) ammonium halide 37 gram (account for total amount 7.1%), stir after 1 hour, add Isooctyl acrylate monomer 60 gram (account for total amount 11.5%) more successively, Hydroxyethyl acrylate 10 grams (account for total amount 1.9%), water 175 grams, in 70 ℃ of stirring and emulsifying 2 hours, add persulphate 1.0 grams and sulphite 0.5 gram then, reacted 2 hours down at 70 ℃, be warming up to 85 ℃ again, reacted 3 hours, and added polyoxyethylene glycol (M=800) 18 gram (account for total amount 3.5%) at last, reacted 0.5 hour, cooling discharge gets finished product 520 grams.
Embodiment four
Get sericin 18 gram (account for total amount 2.9%), add reaction flask, add water 200 grams again, be heated to 60 ℃, stir and to add 85% formic acid, 20 grams (account for total amount 2.7%), 5,0%1,231 10 grams (account for total amount 0.8%) down successively, acrylamide 14 gram (account for total amount 2.2%), (methacryloxyethyl-butyl-dimethyl) ammonium halide 20 gram (account for total amount 3.2%), stirred 1 hour, add butyl acrylate 80 gram (account for total amount 12.7%) more successively, dodecylacrylate 22 gram (account for total amount 3.5%), water 240 gram in 60 ℃ of following stirring and emulsifying 2 hours, adds persulphate 1.2 grams and sulphite 0.6 then and restrains, reacted 3 hours down at 60 ℃, be warming up to 90 ℃ of reactions 1 hour again, add polyoxyethylene glycol (M=400) 10 gram (account for total amount 1.6%) at last, reacted 0.5 hour, cooling discharge gets finished product 630 grams.
Embodiment five
Get sericin 12 gram (account for total amount 1.8%), add reaction flask, add water 180 grams again, be heated to 50 ℃, stir and to add 36% hydrochloric acid, 2 grams (account for total amount 0.1%) down successively, 7,0%1,831 40 grams (account for total amount 4.1%), (methacryloxyethyl-dimethyl-ethyl) ammonium halide 12 gram (account for total amount 1.8%), stirred 2 hours, add ethyl propenoate 40 gram (account for total amount 5.9%) more successively, butyl acrylate 110 grams (account for total amount 16.3%), water 285 grams, in 60 ℃ of following stirring and emulsifying 2 hours, add people's persulphate 1.5 grams and sulphite 0.7 gram then,, be warming up to 80 ℃ of reactions 3 hours again 60 ℃ of reactions 1 hour, cooling discharge gets finished product 675 grams.
Embodiment six
Get silk gum 10 gram (account for total amount 2.2%), add reaction flask, add water 150 grams again, be heated to and add 85% phosphoric acid 5 gram (account for total amount 0.9%) under 70 ℃ of stirrings successively, dimethylaminoethyl acrylate methyl base amido ethyl ester 6 gram (account for total amount 1.3%), (methacryloxyethyl-trimethylammonium) ammonium halide 14 gram (account for total amount 3.2%), stirred 0.5 hour, add vinylformic acid cetyl ester 25 gram (account for total amount 5.6%) more successively, N hydroxymethyl acrylamide 8 gram (account for total amount 1.8%), hydroxyethyl methylacrylate 18 gram (account for total amount 4.0%), water 205 gram in 70 ℃ of following stirring and emulsifying 1 hour, adds persulphate 0.9 gram and sulphite 0.4 then and restrains, 70 ℃ of reactions 2 hours, be warming up to 90 ℃ of reactions 0.5 hour again, add ethylene glycol 8 gram (account for total amount 1.8%) at last, reacted 0.5 hour, cooling discharge gets finished product 445 grams.
Embodiment seven
Get sericin 4 gram (account for total amount 0.7%), add reaction flask and add water 160 grams again, be heated to 50 ℃, stir and to add 85% formic acid, 8 grams (account for total amount 1.1) down successively, 5,0%1,231 16 grams (account for total amount 1.3%), (methacryloxyethyl-dimethyl-ethyl) ammonium halide 4 gram (account for total amount 0.7%), stir after 2 hours, add butyl acrylate 60 gram (account for total amount 9.8%) more successively, Propylene glycol monoacrylate 8 grams (account for total amount 1.3%), water 345 grams, in 50 ℃ of stirring and emulsifying 2 hours, add persulphate 0.9 gram and sulphite 0.4 gram then, reacted 4 hours down, be warming up to 80 ℃ of reactions 2 hours again at 50 ℃, add propylene glycol 14 gram (account for total amount 2.3%) at last, reacted 0.5 hour, cooling discharge gets finished product 615 grams.
Embodiment eight
Get sericin 24 gram (account for total amount 3.4%), add reaction flask and add water 180 grams again, be heated to 60 ℃, stir and to add 85% phosphoric acid, 8 grams (account for total amount 1.0%) down successively, methacrylic acid 5 gram (account for total amount 0.7%), 5,0%1,231 45 grams (account for total amount 3.2%), (methacryloxyethyl-trimethylammonium) ammonium halide 25 gram (account for total amount 3.5%), acrylamide 12 gram (account for total amount 1.7%), stir after 0.5 hour, add ethyl propenoate 50 gram (account for total amount 7.1%) more successively, vinylformic acid cetyl ester 10 grams (account for total amount 1.4%), Hydroxyethyl acrylate 21 gram (account for total amount 3.0%), water 310 gram in 70 ℃ of following stirring and emulsifying 1 hour, adds persulphate 1.2 grams and sulphite 0.6 then and restrains, reacted 2 hours down at 70 ℃, be warming up to 85 ℃ of reactions 2 hours again, add polyoxyethylene glycol (M=1000) 20 gram (account for total amount 2.8%) at last, reacted 0.5 hour, cooling discharge gets finished product 705 grams.
Claims (9)
1, a kind of leather bottom-closing coating and decorating agent preparation method, it is characterized in that forming: silk sericin 0.4%～6.0% by the weight percentage of following prescription, cats product 0～5.0%, small molecules acid 0.04%～3.0%, acrylate monomer 5.0%～25%, nitrogen containing monomer 0.5%～10%, hydroxyl monomer 0～6.0%, surplus is a water, under persulphate and the effect of sulphite initiator, gets leather bottom-closing coating and decorating agent in 50～95 ℃ of reactions 4～12 hours.
2, preparation method according to claim 1 is characterized in that adding in the prescription alcohol compound 0～3.6%, 70～95 ℃ of reactions 0.5 hour, and gets leather bottom-closing coating and decorating agent.
3,, it is characterized in that sericin is to refine and get from by product silk material or wastewater from silk reeling according to the preparation method of claim 1 or 2.
4, according to the preparation method of claim 1 or 2, it is characterized in that tensio-active agent is a dodecyl dimethyl benzyl ammonium halide (1227), dodecyl trimethyl-ammonium halide (1231), cetyl trimethyl ammonium halide (1631), octadecyl trimethyl-ammonium halide (1831); Wherein halogen is Cl, Br.
5,, it is characterized in that small molecules acid is hydrochloric acid, phosphoric acid, (methyl) vinylformic acid, formic acid according to the preparation method of claim 1 or 2.
6,, it is characterized in that ester group is C in the acrylate monomer according to the preparation method of claim 1 or 2
2～C
20Esters monomer.
7, according to the preparation method of claim 1 or 2, it is characterized in that nitrogen containing monomer is an acrylamide, dimethylaminoethyl acrylate methyl base amido ethyl ester, (methacryloxy-trimethylammonium) ammonium halide, (methacryloxy-dimethyl-butyl) ammonium halide, (methacryloxy-dimethyl-ethyl) ammonium halide; Wherein halogen is Cl, Br.
8,, it is characterized in that the hydroxyl monomer is (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, N hydroxymethyl acrylamide according to the preparation method of claim 1 or 2.
9,, it is characterized in that alcohol compound is that ethylene glycol, propylene glycol, glycerol, molecular weight are 90～1200 polyoxyethylene glycol according to the preparation method of claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991150902A CN1183215C (en) | 1999-08-20 | 1999-08-20 | Process for preparation of leather bottom-closing coating and decorating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991150902A CN1183215C (en) | 1999-08-20 | 1999-08-20 | Process for preparation of leather bottom-closing coating and decorating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1285379A CN1285379A (en) | 2001-02-28 |
| CN1183215C true CN1183215C (en) | 2005-01-05 |
Family
ID=5278106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991150902A Expired - Fee Related CN1183215C (en) | 1999-08-20 | 1999-08-20 | Process for preparation of leather bottom-closing coating and decorating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1183215C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016573B (en) * | 2007-02-15 | 2012-12-05 | 陈晓鹏 | Leather nursing liquid for eliminating formaldehyde pollution and peculiar smell, and preparing method thereof |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102138641B (en) * | 2011-01-20 | 2013-04-03 | 江南大学 | Application of perylenequinone compound to preparation of feed for preventing and controlling virus of aquatic animals |
| CN103103765B (en) * | 2013-01-14 | 2013-10-09 | 山东轻工业学院 | Self-emulsifying wet-scratch-resistant leather top coat finishing agent and preparation method thereof |
| CN103755986B (en) * | 2014-01-14 | 2016-05-18 | 陕西科技大学 | The preparation method of the crosslinked heteropolymer film of a kind of casein keratinase |
| EP3226835B1 (en) | 2014-12-02 | 2024-11-13 | Evolved by Nature, Inc. | Silk performance apparel |
| BR112018000699B1 (en) | 2015-07-14 | 2023-10-17 | Silk Therapeutics, Inc | ARTICLE AND METHOD FOR COATING A MATERIAL |
| CN105694649A (en) * | 2016-03-25 | 2016-06-22 | 陕西科技大学 | Preparation method of antibacterial bottom sealing type cation modified casein leather finishing agent |
| CN106046887A (en) * | 2016-06-29 | 2016-10-26 | 沈敏华 | Leather finishing cream |
| CN106009825A (en) * | 2016-06-29 | 2016-10-12 | 宋雁群 | Leather-care finishing agent |
| CN108504797A (en) * | 2018-04-18 | 2018-09-07 | 海宁玖洲家具有限公司 | The Coating technology of sofa leather |
| CN108997942A (en) * | 2018-07-26 | 2018-12-14 | 苏州华龙化工有限公司 | A kind of preparation method of sericin grape pip polysaccharide composite leather gloss agent |
-
1999
- 1999-08-20 CN CNB991150902A patent/CN1183215C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016573B (en) * | 2007-02-15 | 2012-12-05 | 陈晓鹏 | Leather nursing liquid for eliminating formaldehyde pollution and peculiar smell, and preparing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1285379A (en) | 2001-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1183215C (en) | Process for preparation of leather bottom-closing coating and decorating agent | |
| IE840800L (en) | Copolymer | |
| JPH0160080B2 (en) | ||
| CN114641512B (en) | multistage polymer | |
| CN101037558A (en) | Aqueous compositions comprising polymeric duller particle | |
| JP7536014B2 (en) | Multi-stage polymer | |
| JPH03170517A (en) | Copolymer based on ethylenic unsaturated monomer and containing urethane group and its preparation and use | |
| CN1165864A (en) | Method of treating leather with amphoteric polymers | |
| CA1264280A (en) | Aqueous adhesive compositions for use with wall coverings and the like, having improved adhesion and rheology properties | |
| JP3689131B2 (en) | Aqueous polymer dispersions as binders for tack-free, scratch-resistant and chemical-resistant coatings | |
| CN1229456C (en) | Binder for leather coatings and coated leather with good embossability and wet flex resistance | |
| US5723182A (en) | Method for coating leather | |
| US4631063A (en) | Process for finish dressing minerally dressed leathers or those dressed by a combined method, using polymer dressings | |
| US4345006A (en) | Method of treating leather | |
| JP2002294561A (en) | Synthetic resin emulsion for nonwoven fabric antifouling agent, antifouling agent for nonwoven wallpaper and nonwoven wallpaper | |
| US4840991A (en) | Aqueous dispersions of partially cross-linked emulsion copolymers | |
| US2511695A (en) | Copolymer liquid polish | |
| CN1118356A (en) | Improved method for forming (meth)acrolein-containing polymers | |
| AU717402B2 (en) | Method for coating leather | |
| JPH08245912A (en) | Matte electrodeposition coating material | |
| JPH0123310Y2 (en) | ||
| JPS6015759B2 (en) | Strengthening treatment liquid for paper, etc. | |
| SU1673598A1 (en) | Manufacturing fur plates | |
| BR0013850A (en) | Process for preparing adhesives with better adhesion | |
| KR850000161B1 (en) | Process for treating pelts and leather with polymer products in the form of aqueous dispersions |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |