CN104530330A - Leather finishing agent and preparation method thereof - Google Patents
Leather finishing agent and preparation method thereof Download PDFInfo
- Publication number
- CN104530330A CN104530330A CN201410814332.3A CN201410814332A CN104530330A CN 104530330 A CN104530330 A CN 104530330A CN 201410814332 A CN201410814332 A CN 201410814332A CN 104530330 A CN104530330 A CN 104530330A
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- China
- Prior art keywords
- casein
- hide finishes
- acrylate monomer
- parts
- leather
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- Granted
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010985 leather Substances 0.000 title abstract description 65
- 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 claims abstract description 108
- 235000021240 caseins Nutrition 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000005018 casein Substances 0.000 claims abstract description 80
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 43
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 33
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 36
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 27
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 20
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 19
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000004160 Ammonium persulphate Substances 0.000 claims description 11
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 229960004418 trolamine Drugs 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 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 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000012986 modification Methods 0.000 abstract description 14
- 230000004048 modification Effects 0.000 abstract description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- -1 by modification Chemical group 0.000 abstract description 9
- 238000006482 condensation reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 abstract 3
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- 229920002521 macromolecule Polymers 0.000 abstract 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 102000011632 Caseins Human genes 0.000 description 72
- 108010076119 Caseins Proteins 0.000 description 72
- 239000000243 solution Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 150000002118 epoxides Chemical group 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000011221 initial treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229940021722 caseins Drugs 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000017854 proteolysis Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Abstract
The invention provides a leather finishing agent. The leather finishing agent is prepared from gamma-glycidoxy propyl trimethoxy silane, acrylate monomer, persulfate, casein, organic amine, water and sulfite, wherein the acrylate monomer comprises more than three of butyl acrylate, ethyl acrylate, styrene and acrylonitrile. The invention provides a preparation method of the leather finishing agent. The preparation method comprises the following step of modifying casein with gamma-glycidoxy propyl trimethoxy silane and the acrylate monomer. Since gamma-glycidoxy propyl trimethoxy silane contains epoxy groups, by modification, epoxy groups are grafted onto macromolecules of casein, the macromolecules and polar groups such as hydroxyl, amino and carboxyl on branched chains of casein are subjected to condensation reaction so that the leather finishing agent provided by the invention has good flexibility and water resistance; and by the further modification of the acrylate monomer, the flexibility and water resistance of the leather finishing agent provided by the invention can be further increased.
Description
Technical field
The present invention relates to leather processing technique field, particularly relate to a kind of hide finishes and preparation method thereof.
Background technology
Hide finishes is mainly used in the modification of leather, particularly must be indispensable in the polishing of various obverse leather, buffed leather and the process of ironing, hide finishes can make coating and leather surface bond securely, improve high temperature resistant flatiron and the polishability of leather, and hide finishes can also make leather keep the distinctive sanitation performance of natural leather.
At present, the composition of hide finishes mostly is the casein of modification, and the material for modified Casein mainly contains urethane, hexanolactam and vinyl monomer etc.; But the toxicity that polyurethane-modified casein is larger because isocyanate material has, makes modified casein finishing agent bring larger pollution to human body and environment; And the water tolerance of finishing agent for preparing of the modified casein of acrylic ester monomer or flexible resistance poor; Organosilicon is adopted to carry out modification to casein, water tolerance and the flexible resistance of modified casein finishing agent can be improved, as prior art describes the method for a kind of soap-free polymerization legal system for the common modified Casein Leather finishing agent of acrylate/silane coupling agent, double bond containing silane coupling agent and acrylate is adopted to carry out two modification to casein, concrete grammar is: first use trolamine and water dissolution casein food grade, obtain casein lysate; In described casein lysate, drip caprolactam solution again, obtain the casein emulsion of hexanolactam modification; Then under the effect of persulfide initiator, adopt semi-continuous seed surfactant-free emulsion polymerization, add methyl methacrylate, butyl acrylate and silane coupling agent in the casein emulsion of described hexanolactam modification simultaneously, by Raolical polymerizable, obtain acrylate/silane coupling agent modified Casein Leather finishing agent altogether.
This hide finishes that prior art provides first adopts hexanolactam modified Casein, then adopts acrylate/silane coupler modified casein; Silane coupling agent is vinyl silicane coupling agent.Although the water tolerance of this hide finishes that prior art provides obtains raising to a certain degree, still poor, limit the widespread use of hide finishes.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of hide finishes, hide finishes provided by the invention has good kindliness and water tolerance.
The invention provides a kind of hide finishes, prepared by γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulphate, casein, organic amine, water and sulphite; Described acrylate monomer comprises more than three kinds in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide.
Preferably, the mass ratio of described γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulphate, casein, organic amine, water and sulphite is (5 ~ 10): (45 ~ 100): (0.1 ~ 1): (100 ~ 150): (20 ~ 30): (580 ~ 1000): (0.1 ~ 1).
Preferably, described acrylate monomer, with parts by weight, comprising:
The butyl acrylate of 33 parts ~ 50 parts;
The ethyl propenoate of A part, 0 < A≤23;
The vinylbenzene of B part, 0 < B≤37.5;
The vinyl cyanide of C part, 0 < C≤50.
Preferably, described persulphate is selected from one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
Preferably, described organic amine is selected from one or more in triethylamine, diethylamine, trolamine and diethanolamine.
Preferably, described sulphite is selected from one or both in sodium bisulfite and Sodium Pyrosulfite.
Hide finishes provided by the invention, acrylate monomer and γ-glycidyl ether oxygen propyl trimethoxy silicane is introduced in the process of modified Casein, containing epoxide group in γ-glycidyl ether oxygen propyl trimethoxy silicane, pass through modification, epoxide group is grafted on the macromole of casein, there is condensation reaction with the polar group on casein side chain as hydroxyl, amino, carboxyl etc., make hide finishes provided by the invention have good kindliness and water tolerance; And casein modified for γ-glycidyl ether oxygen propyl trimethoxy silicane is adopted acrylate monomer modification again, kindliness and the water tolerance of hide finishes provided by the invention can be improved further; Therefore, hide finishes provided by the invention has good kindliness and water tolerance.Experimental result shows, the leather hand feeling after the process of hide finishes provided by the invention is soft, smooth; The water tolerance of hide finishes provided by the invention is 1.2 ~ 1.4.
In addition, hide finishes provided by the invention can also improve the glossiness of leather, polish retention, plasticity, resistance to xerotripsis, wet-rub resistance, resistance to having mercy on property of song, makes the leather hand feeling after process comfortable; And not containing organic solvents such as alkylphenol polyoxyethylene compounds in hide finishes provided by the invention, safety and environmental protection.Experimental result shows, the resistance to xerotripsis of the leather after hide finishes process provided by the invention is 4.5 grades ~ 5 grades, and wet-rub resistance is 4.5 grades ~ 5 grades; Glossiness is the glossiness after 7.5,7 days is 6.5 ~ 7.5.
The invention provides a kind of preparation method of hide finishes, comprise the following steps:
1), by casein and organic amine be hydrolyzed reaction in water, obtains hydrolyzed casein liquid;
2), by described hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy silicane react, obtain modified Casein liquid;
3), by after the mixing of described modified Casein liquid, acrylate monomer, persulphate and sulphite carry out polyreaction, obtain hide finishes;
Described acrylate monomer comprises more than three kinds in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide.
Preferably, described step 1) in the temperature of hydrolysis reaction be 70 DEG C ~ 80 DEG C;
The time of hydrolysis reaction is 1 hour ~ 2 hours.
Preferably, described step 2) in reaction temperature be 70 DEG C ~ 80 DEG C;
The time of reaction is 1 hour ~ 2 hours.
Preferably, described step 3) in the temperature of polyreaction be 70 DEG C ~ 90 DEG C;
The time of polyreaction is 2 hours ~ 4 hours.
The present invention by casein being carried out proteolysis, the modified polyreaction of carrying out of γ-glycidyl ether oxygen propyl trimethoxy silicane prepares hide finishes, the preparation method of this hide finishes first adopts γ-glycidyl ether oxygen propyl trimethoxy silicane to carry out modification to casein, adopt acrylate monomer to carry out modification again modified casein, the hide finishes that this method prepares has good kindliness and water tolerance.
In addition, the hide finishes that method provided by the invention prepares can also improve the glossiness of leather, polish retention, plasticity, resistance to xerotripsis, wet-rub resistance, resistance to having mercy on property of song, makes the leather hand feeling after process comfortable; And not containing organic solvent in the hide finishes for preparing of method provided by the invention, safety and environmental protection.In addition, preparation method's process stabilizing of hide finishes provided by the invention, is applicable to suitability for industrialized production.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of hide finishes, prepared by γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulphate, casein, organic amine, water and sulphite; Described acrylate monomer comprises more than three kinds in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide.
In an embodiment of the present invention, the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane can be 5 parts ~ 10 parts; In other examples, the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane can be 6 parts ~ 8 parts.The source of the present invention to described γ-glycidyl ether oxygen propyl trimethoxy silicane does not have special restriction, can be bought obtain, as adopted KH-570 silane coupling agent well known to those skilled in the art by market.
In an embodiment of the present invention, with the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane for benchmark, the parts by weight of described acrylate monomer can be 45 parts ~ 100 parts; In other examples, the parts by weight of described acrylate monomer can be 60 parts ~ 80 parts.In the present invention, described acrylate monomer comprises the mixture of three kinds of materials in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide or the mixture of four kinds of materials.In a preferred embodiment of the invention, described acrylate monomer, with parts by weight, comprising:
The butyl acrylate of 33 parts ~ 50 parts;
The ethyl propenoate of A part, 0 < A≤23;
The vinylbenzene of B part, 0 < B≤37.5;
The vinyl cyanide of C part, 0 < C≤50.
The preparation method of the present invention to described acrylate monomer does not have special restriction, is mixed by kind of the material of three in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide; Or butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide are carried out mixing.In an embodiment of the present invention, described mixing can be carried out under the condition stirred.In an embodiment of the present invention, the time of described mixing can be 8 minutes ~ 12 minutes.
In an embodiment of the present invention, with the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane for benchmark, the parts by weight of described persulphate can be 0.1 part ~ 1 part; In other examples, the parts by weight of described persulphate can be 0.5 part ~ 0.8 part.In an embodiment of the present invention, described persulphate can be selected from one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.In a preferred embodiment of the invention, described persulphate is persulfate solution; In other preferred embodiment, described persulphate is the persulphate aqueous solution.In an embodiment of the present invention, the mass concentration of described persulfate solution is 0.8% ~ 1.2%; In other examples, the mass concentration of described persulfate solution is 1%.
In an embodiment of the present invention, with the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane for benchmark, the parts by weight of described casein can be 100 parts ~ 150 parts; In other examples, the parts by weight of described casein can be 120 parts ~ 130 parts.The source of the present invention to described casein does not have special restriction, adopts casein well known to those skilled in the art, can be bought obtain by market.
In an embodiment of the present invention, with the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane for benchmark, the parts by weight of described organic amine can be 20 parts ~ 30 parts; In other examples, the parts by weight of described organic amine can be 24 parts ~ 26 parts.In a preferred embodiment of the invention, described organic amine can be one or more in triethylamine, diethylamine, trolamine and diethanolamine.
In an embodiment of the present invention, with the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane for benchmark, the parts by weight of described water can be 580 parts ~ 1000 parts; In other examples, the parts by weight of described water can be 650 parts ~ 800 parts.In a preferred embodiment of the invention, described water can be deionized water.
In an embodiment of the present invention, with the parts by weight of described γ-glycidyl ether oxygen propyl trimethoxy silicane for benchmark, the parts by weight of described sulphite can be 0.1 part ~ 1 part; In other examples, the parts by weight of described sulphite can be 0.4 part ~ 0.8 part.In a preferred embodiment of the invention, described sulphite can be one or both in sodium bisulfite and Sodium Pyrosulfite.In a preferred embodiment of the invention, described sulphite is sulfite solution; In other preferred embodiment, described sulphite is sulfite solution.In an embodiment of the present invention, the mass concentration of described sulfite solution can be 0.8% ~ 1.2%; In other examples, the mass concentration of described sulfite solution can be 1%.
In a preferred embodiment of the invention, the mass ratio of described γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulphate, casein, organic amine, water and sulphite is (5 ~ 10): (45 ~ 100): (0.1 ~ 1): (100 ~ 150): (20 ~ 30): (580 ~ 1000): (0.1 ~ 1).Hide finishes outward appearance provided by the invention is faint yellow translucent emulsion, presents anionic property, and pH value is 7 ~ 9, and solid content is 19% ~ 21%.
Hide finishes provided by the invention has good kindliness and water tolerance.In addition, hide finishes provided by the invention can also improve the glossiness of leather, polish retention, plasticity, resistance to xerotripsis, wet-rub resistance, resistance to having mercy on property of song, makes the leather hand feeling after process comfortable; And not containing organic solvents such as alkylphenol polyoxyethylene compounds in hide finishes provided by the invention, safety and environmental protection.
The invention provides a kind of preparation method of hide finishes, comprising:
Be hydrolyzed casein and organic amine in water reaction, obtains hydrolyzed casein liquid;
Described hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy silicane are reacted, obtains modified Casein liquid;
Carry out polyreaction after described modified Casein liquid, acrylate monomer, persulphate and sulphite being mixed, obtain hide finishes;
Described acrylate monomer comprises more than three kinds in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide.
Casein and organic amine are hydrolyzed reaction by the present invention in water, obtain hydrolyzed casein liquid.In the present invention, the kind of the kind of described casein, organic amine and water, source and parts by weight and casein, organic amine and water described in upper technical scheme, source and parts by weight are consistent, do not repeat them here.
In an embodiment of the present invention, the time of described hydrolysis reaction can be 1 hour ~ 2 hours.In an embodiment of the present invention, the temperature of described hydrolysis reaction can be 70 DEG C ~ 80 DEG C; In other examples, the temperature of described hydrolysis reaction can be 74 DEG C ~ 78 DEG C.In an embodiment of the present invention, described hydrolysis reaction can be carried out under the condition stirred.
In a preferred embodiment of the invention, can add in water after casein heats up and be incubated, make casein fully swelling, obtain casein solution; In described casein solution, add organic amine to be hydrolyzed reaction, make casein complete hydrolysis, obtain hydrolyzed casein liquid.In an embodiment of the present invention, under the condition stirred, casein can be added in water.In an embodiment of the present invention, the temperature of described intensification can be 70 DEG C ~ 80 DEG C.In an embodiment of the present invention, the time of described insulation can be 0.5 hour ~ 1.5 hours.
After obtaining hydrolyzed casein liquid, described hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy silicane react by the present invention, obtain modified Casein liquid.In the present invention, source and the parts by weight of the source of described γ-glycidyl ether oxygen propyl trimethoxy silicane and parts by weight and the γ-glycidyl ether oxygen propyl trimethoxy silicane described in technique scheme are consistent, do not repeat them here.
In an embodiment of the present invention, the temperature of described reaction can be 70 DEG C ~ 80 DEG C; In other examples, the temperature of described reaction can be 74 DEG C ~ 78 DEG C.In an embodiment of the present invention, the time of described reaction can be 1 hour ~ 2 hours.In a preferred embodiment of the invention, described reaction can be carried out under the condition of water-bath and insulation.
In an embodiment of the present invention, described hydrolyzed casein liquid can be joined in γ-glycidyl ether oxygen propyl trimethoxy silicane and react, obtain modified Casein liquid.
After obtaining modified Casein liquid, the present invention carries out polyreaction after described modified Casein liquid, acrylate monomer, persulphate and sulphite being mixed, and obtains hide finishes.In an embodiment of the present invention, the kind of the kind of described acrylate monomer, persulphate and sulphite, source and parts by weight and the acrylate monomer described in technique scheme, persulphate and sulphite, source and parts by weight are consistent, do not repeat them here.
In an embodiment of the present invention, the temperature of described polyreaction can be 70 DEG C ~ 90 DEG C; In other examples, the temperature of described polyreaction can be 75 DEG C ~ 80 DEG C.In an embodiment of the present invention, the time of described polyreaction can be 2 hours ~ 4 hours; In other examples, the time of described polyreaction can be 3 hours.
In a preferred embodiment of the invention, the sulfite solution of the persulfate solution of the first mass parts and the first mass parts can be joined in acrylate monomer and carry out the first reaction, obtain reaction product; The sulfite solution of the persulfate solution and the second mass parts that add the second mass parts in described reaction product carries out the second reaction, obtains hide finishes.
In the present invention, described sulfite solution is consistent with persulfate solution with the sulfite solution described in technique scheme with persulfate solution, does not repeat them here.In an embodiment of the present invention, the mass ratio of the persulfate solution of described first mass parts and the persulfate solution of the second mass parts can be 1:(0.5 ~ 1.5); In other examples, the mass ratio of the persulfate solution of described first mass parts and the persulfate solution of the second mass parts can be 1:1.In an embodiment of the present invention, the mass ratio of the sulfite solution of described first mass parts and the sulfite solution of the second mass parts can be 1:(0.5 ~ 1.5); In other examples, the mass ratio of the sulfite solution of described first mass parts and the sulfite solution of the second mass parts can be 1:1.
In an embodiment of the present invention, described first reaction can be carried out under the condition stirred.In an embodiment of the present invention, the time of described stirring can be 8 minutes ~ 12 minutes.In an embodiment of the present invention, the temperature of described first reaction can be 70 DEG C ~ 80 DEG C; In other examples, the temperature of described first reaction can be 74 DEG C ~ 78 DEG C.In an embodiment of the present invention, the time of described first reaction can be 0.5 hour ~ 1.5 hours; In other examples, the time of described first reaction can be 1 hour.
In an embodiment of the present invention, the temperature of described second reaction can be 75 DEG C ~ 90 DEG C; In other examples, the temperature of described second reaction can be 80 DEG C ~ 85 DEG C.In an embodiment of the present invention, the time of described second reaction can be 1 hour ~ 3 hours; In other examples, the time of described second reaction can be 2 hours.
In an embodiment of the present invention, after described polyreaction completes, the polymerisate obtained can be cooled to 35 DEG C ~ 45 DEG C, obtain hide finishes.
The hide finishes that method provided by the invention prepares has good kindliness and water tolerance.In addition, the hide finishes that method provided by the invention prepares can also improve the glossiness of leather, polish retention, plasticity, resistance to xerotripsis, wet-rub resistance, resistance to having mercy on property of song, makes the leather hand feeling after process comfortable; And not containing organic solvent in the hide finishes for preparing of method provided by the invention, safety and environmental protection.In addition, preparation method's process stabilizing of hide finishes provided by the invention, is applicable to suitability for industrialized production.
Hide finishes provided by the invention is mainly used in the covering with paint of leather, both may be used for the primary coat of leather, and the top that also can be used for leather is coated with or face painting.
By hide finishes provided by the invention for the treatment of cow leather upper, concrete grammar is: carry out drying after the surface spraying of cow leather upper hide finishes provided by the invention, polishing and hot light, obtains primary treatment leather; The temperature of described oven dry is 90 DEG C, and the time of described oven dry is 1h.The method of the present invention to described polishing and hot light does not have special restriction, adopts the technical scheme of polishing and hot light in leather treating processes well known to those skilled in the art.In the present invention, the temperature of described polishing is 90 DEG C; The method of described hot light be 120 DEG C, carry out the hot pressing of 4 seconds in the rolling press of 10MPa;
Leather surface to described primary treatment sprays hide finishes provided by the invention again, carries out secondary drying and hot light, obtains the leather after processing; The temperature of described oven dry is 90 DEG C, and the time of described oven dry is 1h; The method of described hot light be 120 DEG C, carry out the hot pressing of 4 seconds in the rolling press of 10MPa.
By the standard of the leather after described process according to QB/T1327 " leather surface colour fastness test testing method ", XK-3078 leather surface color fastness experimental machine is adopted to carry out resistance to xerotripsis test and wet-rub resistance test, test result is, the resistance to xerotripsis of the leather after hide finishes process provided by the invention is 4.5 grades ~ 5 grades, and wet-rub resistance is 4.5 grades ~ 5 grades.
Adopt surface gloss instrument to test its glossiness the leather after described process, test result is, the glossiness of the leather after hide finishes process provided by the invention is the glossiness after 7.5,7 days is 6.5 ~ 7.5.
Choose 5 volunteers and sensory testing is carried out to the leather hand feeling after the process described in technique scheme.Test result is, 4 volunteers think that the leather after hide finishes process provided by the invention is soft right, smooth.
Test the water tolerance of hide finishes provided by the invention, concrete grammar is:
Hide finishes provided by the invention is carried out in the baking oven of 60 DEG C the drying of 24 hours, make described hide finishes film forming; Weighed by hide finishes after film forming, record weight is A;
Hide finishes after film forming is soaked in the beaker of water that constant temperature 25 DEG C is housed after 24 hours and take out, dry the hide finishes film after immersion with filter paper; Weighed by the hide finishes film drying water, record weight is B; Calculate the water tolerance of hide finishes provided by the invention according to the following equation:
Water tolerance=B/A;
Calculation result is, the water tolerance of hide finishes provided by the invention is 1.2 ~ 1.4.
Raw material used in following examples of the present invention is commercial goods, the lactic acid method casein 730 (casein food grade) that described casein provides for permanent natural cheese element company of New Zealand.
Embodiment 1
The deionized water of 550g is added reactor, and the casein adding 100g under the condition stirred in described reactor is warming up to 75 DEG C, stirs 1 hour, casein is fully expanded, obtains casein solution; Under the condition stirred, the trolamine adding 20g in described casein solution carries out the hydrolysis reaction of 2 hours, obtains hydrolyzed casein liquid;
Bath temperature is adjusted to 75 DEG C, the γ-glycidyl ether oxygen propyl trimethoxy silicane of 5g is joined in said hydrolyzed casein liquid the insulation reaction of carrying out 2 hours, obtain modified Casein liquid;
The mixture formed by the vinylbenzene of the butyl acrylate of 22.5g, the ethyl propenoate of 15g and 7.5g is as acrylate monomer, under the condition stirred, join in reactor, the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 0.8g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.5g sodium bisulfite and 25g deionized water is added in described reactor, stir 10 minutes, at 75 DEG C, carry out first reaction of 1 hour; In the reaction product obtained, add the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 0.8g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.5g sodium bisulfite and 25g deionized water, carry out second reaction of 2 hours at 80 DEG C;
The second reaction product obtained is cooled to 40 DEG C, obtains hide finishes.
According to the method described in technique scheme, the hide finishes adopting the embodiment of the present invention 1 to prepare processes cow leather upper, obtains the leather after processing.
According to the method described in technique scheme, the feel of the leather after the process that the test embodiment of the present invention 1 obtains, resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result is as shown in table 1, and table 1 is the performance test results of the leather after the process that obtains of the embodiment of the present invention and comparative example.
According to the method described in technique scheme, the water tolerance of the hide finishes that the test embodiment of the present invention 1 prepares, test result is, the water tolerance of the hide finishes that the embodiment of the present invention 1 prepares is 1.4, and water tolerance is better.
Embodiment 2
The deionized water of 730g is added reactor, and the casein adding 130g under the condition stirred in described reactor is warming up to 75 DEG C, stirs 1 hour, casein is fully expanded, obtains casein solution; Under the condition stirred, the trolamine adding 26g in described casein solution carries out the hydrolysis reaction of 2 hours, obtains hydrolyzed casein liquid;
Bath temperature is adjusted to 75 DEG C, the γ-glycidyl ether oxygen propyl trimethoxy silicane of 7g is joined in said hydrolyzed casein liquid the insulation reaction of carrying out 2 hours, obtain modified Casein liquid;
The mixture formed by the vinylbenzene of the butyl acrylate of 20g, the vinyl cyanide of 25g and 20g is as acrylate monomer, under the condition stirred, join in reactor, the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 1g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.8g sodium bisulfite and 25g deionized water is added in described reactor, stir 10 minutes, at 75 DEG C, carry out first reaction of 1 hour; In the reaction product obtained, add the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 1g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.8g sodium bisulfite and 25g deionized water, carry out second reaction of 1 hour at 80 DEG C;
The second reaction product obtained is cooled to 40 DEG C, obtains hide finishes.
According to the method described in technique scheme, the hide finishes adopting the embodiment of the present invention 2 to prepare processes cow leather upper, obtains the leather after processing.
According to the method described in technique scheme, the feel of the leather after the process that the test embodiment of the present invention 2 obtains, resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result is as shown in table 1.
According to the method described in technique scheme, the water tolerance of the hide finishes that the test embodiment of the present invention 2 prepares, test result is, the water tolerance of the hide finishes that the embodiment of the present invention 2 prepares is 1.3, and water tolerance is better.
Embodiment 3
The deionized water of 850g is added reactor, and the casein adding 150g under the condition stirred in described reactor is warming up to 75 DEG C, stirs 1 hour, casein is fully expanded, obtains casein solution; Under the condition stirred, the trolamine adding 30g in described casein solution carries out the hydrolysis reaction of 2 hours, obtains hydrolyzed casein liquid;
Bath temperature is adjusted to 75 DEG C, the γ-glycidyl ether oxygen propyl trimethoxy silicane of 10g is joined in said hydrolyzed casein liquid the insulation reaction of carrying out 2 hours, obtain modified Casein liquid;
The mixture formed by the ethyl propenoate of the butyl acrylate of 30g, the vinyl cyanide of 30g and 30g is as acrylate monomer, under the condition stirred, join in reactor, the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 1g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.8g sodium bisulfite and 25g deionized water is added in described reactor, stir 10 minutes, at 75 DEG C, carry out first reaction of 1 hour; In the reaction product obtained, add the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 1g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.8g sodium bisulfite and 25g deionized water, carry out second reaction of 2 hours at 80 DEG C;
The second reaction product obtained is cooled to 40 DEG C, obtains hide finishes.
According to the method described in technique scheme, the hide finishes adopting the embodiment of the present invention 3 to prepare processes cow leather upper, obtains the leather after processing.
According to the method described in technique scheme, the feel of the leather after the process that the test embodiment of the present invention 3 obtains, resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result is as shown in table 1.
According to the method described in technique scheme, the water tolerance of the hide finishes that the test embodiment of the present invention 3 prepares, test result is, the water tolerance of the hide finishes that the embodiment of the present invention 3 prepares is 1.2, and water tolerance is better.
Comparative example 1
The deionized water of 800g is added reactor, and the casein adding 150g under the condition stirred in described reactor is warming up to 75 DEG C, stirs 1 hour, casein is fully expanded, obtains casein solution; Under the condition stirred, the trolamine adding 30g in described casein solution carries out the hydrolysis reaction of 2 hours, obtains hydrolyzed casein liquid;
Bath temperature is adjusted to 75 DEG C, the hexanolactam of 10g is dissolved in the deionized water of 50g and is mixed with caprolactam solution, in described caprolactam solution, add the insulation reaction that said hydrolyzed casein liquid carries out 2 hours, obtain modified Casein liquid;
The mixture formed by the ethyl propenoate of the butyl acrylate of 30g, the vinyl cyanide of 30g and 30g is as acrylate monomer, under the condition stirred, join in reactor, the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 1g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.8g sodium bisulfite and 25g deionized water is added in described reactor, stir 10 minutes, at 75 DEG C, carry out first reaction of 1 hour; In the reaction product obtained, add the ammonium persulfate aqueous solution be made up of the ammonium persulphate of 1g and 25g deionized water, the aqueous solution of sodium bisulfite be made up of 0.8g sodium bisulfite and 25g deionized water, carry out second reaction of 2 hours at 80 DEG C;
The second reaction product obtained is cooled to 40 DEG C, obtains hide finishes.
According to the method described in technique scheme, the hide finishes adopting comparative example 1 of the present invention to prepare processes cow leather upper, obtains the leather after processing.
According to the method described in technique scheme, test the feel of the leather after the process that comparative example 1 of the present invention obtains, resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result is as shown in table 1.
According to the method described in technique scheme, test the water tolerance of the hide finishes that comparative example 1 of the present invention prepares, test result is, the hide finishes that comparative example 1 of the present invention prepares is steeped rotten completely not water-fast.
Comparative example 2
The permeate agent of DRIVER 5510 model provide 1510 (cationic waxes that Italy new mark scholar provides) of 1521 (the positively charged ion caseins that Italy new mark scholar provides) of the 1530/T (the cationic acrylamide yogurt that Italy new mark scholar provides) of the DOWESION K 992 (the positively charged ion black pigment paste that Sichuan Da Wei company provides) of 30g, 80g, 100g, 120g, the Sichuan Da Wei company of 30g and the water mixing of 350g, obtain bottom hide finishes coating.
By the DOWESION H 952 (the ion black pigment cream that Sichuan Da Wei company provides) of 30g, the black dyes water of the DOWELLDYES BLACK 90R model that the Sichuan Da Wei company of 30g provides, the DOWELLIC RA 1101 (the anionic acrylic emulsion that Sichuan Da Wei company provides) of 80g, the DOWELLIC RA 1105 (the anionic acrylic emulsion that Sichuan Da Wei company provides) of 100g, the DOWELLIU RU 2059 (anionic polyurethane emulsion that Sichuan Da Wei company provides) of 100g, the DOWELLIU RU 2301 (anionic polyurethane emulsion that Sichuan Da Wei company provides) of 60g, the modified Casein of CASEIN 5833 model that the Sichuan Da Wei company of 160g provides, the permeate agent of DRIVER 5510 type that the Sichuan Da Wei company of 30g provides, the DOWELLER WAX 5050 (the negatively charged ion wax emulsion that Sichuan Da Wei company provides) of 60g and the water mixing of 350g, obtain top layer back cover hide finishes coating.
Carry out drying after the surface spraying of cow leather upper above-mentioned bottom hide finishes coating, polishing and hot light, obtain primary treatment leather; The temperature of described oven dry is 90 DEG C, and the time of described oven dry is 1 hour; The temperature of described polishing is 90 DEG C; The method of described hot light be 120 DEG C, carry out the hot pressing of 4 seconds in the rolling press of 10MPa;
After spraying above-mentioned top layer back cover hide finishes coating to the leather surface of described primary treatment, carry out secondary drying and hot light, obtain the leather after processing; The temperature of described oven dry is 90 DEG C, and the time of described oven dry is 1 hour; The method of described hot light be 120 DEG C, carry out the hot pressing of 4 seconds in the rolling press of 10MPa.
According to the method described in technique scheme, test the feel of the leather after the process that comparative example 2 of the present invention obtains, resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result is as shown in table 1.
According to the method described in technique scheme, test the water tolerance of the bottom hide finishes coating that comparative example 2 of the present invention prepares, test result is, the bottom hide finishes coating that comparative example 2 of the present invention prepares is steeped rotten completely, and water tolerance is poor.
According to the method described in technique scheme, test the water tolerance of the top layer back cover hide finishes coating that comparative example 2 of the present invention prepares, test result is, the top layer back cover hide finishes coating that comparative example 2 of the present invention prepares is steeped rotten completely, and water tolerance is poor.
The performance test results of the leather after the process that table 1 embodiment of the present invention and comparative example obtain
As shown in Table 1, leather hand feeling after hide finishes process provided by the invention is soft, glossiness and better, the resistance to xerotripsis of polish retention and wet-rub resistance better.
As seen from the above embodiment, the invention provides a kind of hide finishes, prepared by γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulphate, casein, organic amine, water and sulphite; Described acrylate monomer comprises more than three kinds in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide.The invention provides a kind of preparation method of hide finishes, casein is adopted γ-glycidyl ether oxygen propyl trimethoxy silicane is modified adopts modified with acrylate monomers again, containing epoxide group in γ-glycidyl ether oxygen propyl trimethoxy silicane, pass through modification, epoxide group is grafted on the macromole of casein, there is condensation reaction with the polar group on casein side chain as hydroxyl, amino, carboxyl etc., make hide finishes provided by the invention have good kindliness and water tolerance; By the modification again of acrylate monomer, kindliness and the water tolerance of hide finishes provided by the invention can be improved further.Therefore, hide finishes provided by the invention has good kindliness and water tolerance.In addition, hide finishes provided by the invention can also improve the glossiness of leather, polish retention, plasticity, resistance to xerotripsis, wet-rub resistance, resistance to having mercy on property of song, makes the leather hand feeling after process comfortable; And not containing organic solvents such as alkylphenol polyoxyethylene compounds in hide finishes provided by the invention, safety and environmental protection.
Claims (10)
1. a hide finishes, is prepared by γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulphate, casein, organic amine, water and sulphite; Described acrylate monomer comprises more than three kinds in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide.
2. hide finishes according to claim 1, it is characterized in that, the mass ratio of described γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulphate, casein, organic amine, water and sulphite is (5 ~ 10): (45 ~ 100): (0.1 ~ 1): (100 ~ 150): (20 ~ 30): (580 ~ 1000): (0.1 ~ 1).
3. hide finishes according to claim 1, is characterized in that, described acrylate monomer, with parts by weight, comprising:
The butyl acrylate of 33 parts ~ 50 parts;
The ethyl propenoate of A part, 0 < A≤23;
The vinylbenzene of B part, 0 < B≤37.5;
The vinyl cyanide of C part, 0 < C≤50.
4. hide finishes according to claim 1, is characterized in that, described persulphate is selected from one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
5. hide finishes according to claim 1, is characterized in that, described organic amine is selected from one or more in triethylamine, diethylamine, trolamine and diethanolamine.
6. hide finishes according to claim 1, is characterized in that, described sulphite be selected from sodium bisulfite and Sodium Pyrosulfite one or both.
7. a preparation method for hide finishes, comprises the following steps:
1), by casein and organic amine be hydrolyzed reaction in water, obtains hydrolyzed casein liquid;
2), by described hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy silicane react, obtain modified Casein liquid;
3), by after the mixing of described modified Casein liquid, acrylate monomer, persulphate and sulphite carry out polyreaction, obtain hide finishes;
Described acrylate monomer comprises more than three kinds in butyl acrylate, ethyl propenoate, vinylbenzene and vinyl cyanide.
8. method according to claim 7, is characterized in that, described step 1) in the temperature of hydrolysis reaction be 70 DEG C ~ 80 DEG C;
The time of hydrolysis reaction is 1 hour ~ 2 hours.
9. method according to claim 7, is characterized in that, described step 2) in reaction temperature be 70 DEG C ~ 80 DEG C;
The time of reaction is 1 hour ~ 2 hours.
10. method according to claim 7, is characterized in that, described step 3) in the temperature of polyreaction be 70 DEG C ~ 90 DEG C;
The time of polyreaction is 2 hours ~ 4 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433458A (en) * | 2016-11-01 | 2017-02-22 | 南宁马瑞娜装饰工程有限公司 | Color modified waterproof coating |
| CN106497419A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of heat-proof combustion-resistant water-repellent paint |
| CN106496501A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of preparation method of water-repellent paint with modified film former |
| CN106497418A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of heat-insulated water-repellent paint of colour |
| CN106497180A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of water-repellent paint of high viscosity environment-friendly type |
| CN106497420A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of water-repellent paint |
| CN106497417A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of weather-proof water-repellent paint of anti-corrosion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532561A (en) * | 2011-12-19 | 2012-07-04 | 四川达威科技股份有限公司 | Modified casein, leather finishing agent and preparation method thereof |
| CN103059233A (en) * | 2012-12-24 | 2013-04-24 | 陕西科技大学 | Method for preparing acrylate/ silane coupling agent shared modified casein leather finishing agent by adopting soap-free polymerization method |
| CN103468084A (en) * | 2013-09-18 | 2013-12-25 | 辽宁恒星精细化工有限公司 | Polyacrylate modified casein leather finishing agent and preparation method thereof |
-
2014
- 2014-12-24 CN CN201410814332.3A patent/CN104530330B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532561A (en) * | 2011-12-19 | 2012-07-04 | 四川达威科技股份有限公司 | Modified casein, leather finishing agent and preparation method thereof |
| CN103059233A (en) * | 2012-12-24 | 2013-04-24 | 陕西科技大学 | Method for preparing acrylate/ silane coupling agent shared modified casein leather finishing agent by adopting soap-free polymerization method |
| CN103468084A (en) * | 2013-09-18 | 2013-12-25 | 辽宁恒星精细化工有限公司 | Polyacrylate modified casein leather finishing agent and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433458A (en) * | 2016-11-01 | 2017-02-22 | 南宁马瑞娜装饰工程有限公司 | Color modified waterproof coating |
| CN106497419A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of heat-proof combustion-resistant water-repellent paint |
| CN106496501A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of preparation method of water-repellent paint with modified film former |
| CN106497418A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of heat-insulated water-repellent paint of colour |
| CN106497180A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of water-repellent paint of high viscosity environment-friendly type |
| CN106497420A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of water-repellent paint |
| CN106497417A (en) * | 2016-11-01 | 2017-03-15 | 南宁马瑞娜装饰工程有限公司 | A kind of weather-proof water-repellent paint of anti-corrosion |
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