CN102532561A - Modified casein, leather finishing agent and preparation method thereof - Google Patents
Modified casein, leather finishing agent and preparation method thereof Download PDFInfo
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- CN102532561A CN102532561A CN201110427243XA CN201110427243A CN102532561A CN 102532561 A CN102532561 A CN 102532561A CN 201110427243X A CN201110427243X A CN 201110427243XA CN 201110427243 A CN201110427243 A CN 201110427243A CN 102532561 A CN102532561 A CN 102532561A
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- casein
- leather
- preparation
- cationic
- hide finishes
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical class 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 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010985 leather Substances 0.000 title abstract description 51
- 239000003795 chemical substances by application Substances 0.000 title abstract description 13
- 235000021240 caseins Nutrition 0.000 claims abstract description 92
- 239000005018 casein Substances 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 125000002091 cationic group Chemical group 0.000 claims abstract description 67
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000007524 organic acids Chemical class 0.000 claims abstract description 33
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 30
- 239000003995 emulsifying agent Substances 0.000 claims description 27
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 16
- 235000019260 propionic acid Nutrition 0.000 claims description 15
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 14
- 239000004310 lactic acid Substances 0.000 claims description 13
- 235000014655 lactic acid Nutrition 0.000 claims description 13
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001409 amidines Chemical class 0.000 claims description 8
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 8
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 29
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000003755 preservative agent Substances 0.000 abstract description 25
- 239000007787 solid Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 9
- 125000000129 anionic group Chemical group 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 2
- 206010063409 Acarodermatitis Diseases 0.000 abstract 1
- 241000447727 Scabies Species 0.000 abstract 1
- 208000005687 scabies Diseases 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 83
- 102000011632 Caseins Human genes 0.000 description 81
- 108010076119 Caseins Proteins 0.000 description 81
- 238000009835 boiling Methods 0.000 description 44
- 230000002335 preservative effect Effects 0.000 description 24
- 230000000845 anti-microbial effect Effects 0.000 description 20
- AWSFEOSAIZJXLG-UHFFFAOYSA-N azepan-2-one;hydrate Chemical compound O.O=C1CCCCCN1 AWSFEOSAIZJXLG-UHFFFAOYSA-N 0.000 description 20
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 16
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 10
- -1 imino- Chemical class 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004922 lacquer Substances 0.000 description 8
- 235000013305 food Nutrition 0.000 description 7
- 229940021722 caseins Drugs 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 201000002266 mite infestation Diseases 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000018102 proteins Nutrition 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- 241001125620 Dermochelys coriacea Species 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000549 coloured material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Cosmetics (AREA)
Abstract
The invention provides modified casein, which is prepared via grafting polycondensation of caprolactam and casein in organic acid. The invention also provides a leather finishing agent and a preparation method thereof. Since the modified casein is prepared via modification of the casein through the caprolactam with the presence of the organic acid, the defects of the casein material such as hard film, no extension and easy breaking are overcome. Moreover, the modified casein is cationic and has good affinity to an anionic leather surface when being used as the leather finishing agent to form a coating. Therefore, the coating has strong adhesion to the leather surface and cannot easily fall off, and the finishing quality of leather cannot be affected. The leather finishing agent with the solid content higher than 15 percent is prepared via mixing of the modified casein, preservatives and water. When the leather finishing agent is coated on the leather, the leather becomes soft, plump and natural, the defects of stitches and scabies can be overcome effectively, the rate of utilization of the leather can be increased, and the level of the leather can be improved.
Description
Technical field
The invention belongs to the hide finishes technical field, relate in particular to a kind of modified Casein, hide finishes and preparation method thereof.
Background technology
Hide finishes is mainly to comprise filmogen, coloured material, solvent and auxiliary agent through wiping, brush, spray or mode such as pouring forming a kind of material of film or coating at leather surface.Hide finishes can increase the attractive in appearance and durability of leather, improves the leather class, increases the leather assortment and enlarges the leather use range.
Prior art discloses multiple hide finishes; Mainly comprise modified polyurethane hide finishes, modified acroleic acid hide finishes, protein binder and nitrocotton etc.; Wherein, The modified polyurethane hide finishes has the excellent properties of urethane and epoxy resin, has excellent waterproof and wear resisting property, can make that product is attractive in appearance, smooth, prolong work-ing life; The modified acroleic acid hide finishes is the maximum hide finishes of present usage quantity, have fast light, ageing-resistant, moisture resistance properties, but it has the shortcoming of hot sticky cold crisp, receives the restriction of weather condition in the use; Nitrocotton has light, attractive in appearance, acidproof, oil resistant, advantage such as water-fast, but it is not ageing-resistant, winter hardiness is poor, ventilation property is poor after the film forming; The staple of protein binder is a casein, have coating gloss soft natural, cohesive force is strong, high temperature resistant flatiron, the corium sense of touch is arranged, can keep the good advantages such as permeable gas property of leather, becomes one of hide finishes research focus gradually.
Casein is a phosphor protein matter, contains multiple hydrophilic radicals such as amido, imino-, carboxyl, must carry out can being used as hide finishes after modification improves performances such as its extensibility, flexible resistance, wet fastness to casein.Like application number is that 200910036061.2 Chinese patent document discloses a kind of leather finish with the plain preparation method of modified casein; It is under the condition of ammonia solvent casein; With the ammonium persulphate is initiator; Make hexanolactam and casein generation grafting condensation reaction, obtain modified Casein, this modified Casein has coating light, high temperature resistant flatiron, suitable polishing when the hide finishes, can present plentiful soft hand feeling, good springiness, cold-resistant, advantage such as cohesive force is strong, water repelling property is good.But this modified Casein is an initiator in ammonia environment, with the ammonium persulphate of anionic, and itself shows anionic property; And adopt the leather after the retanning of reinforcing yin essence ionic material also mainly to show anionic property, therefore, when adopting this hide finishes that leather is covered with paint, lacquer, colour wash, etc.; Do not have avidity between coating and the leather surface; It is bonding mainly to be the adhesive effect that leans on membrane-forming agent, occurs bonding insecure, phenomenon such as coating comes off easily easily, thereby influences the coating quality of leather.
Summary of the invention
In view of this; The technical problem that the present invention will solve is to provide a kind of modified Casein, hide finishes and preparation method thereof; Coating and leather-surface bonding power that hide finishes provided by the invention forms are strong, and the coating difficult drop-off can not influence the coating quality of leather.
The invention provides a kind of modified Casein, said modified Casein prepares according to following method:
The grafting polycondensation takes place in hexanolactam and casein under the organic acid condition, obtain modified Casein.
Preferably, the grafting polycondensation is taking place in said hexanolactam and casein under the initiation of cationic initiator, under the organic acid condition.
Preferably, said cationic initiator is an azo diisobutyl amidine hydrochloride.
Preferably, said organic acid is one or more in Hydrocerol A, lactic acid and the propionic acid.
The present invention also provides a kind of hide finishes, comprising:
The described modified Casein of the technique scheme of 10wt%～40wt%;
The sanitas of 0.1wt%～1wt%;
The water of surplus.
Preferably, said sanitas is not for containing the sanitas of phenyl ring.
Preferably, the cationic emulsifier that also comprises 0.2wt%～1wt%.
Preferably, said cationic emulsifier is one or more in dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, DTAC, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride and the cetyl trimethylammonium bromide.
The present invention also provides a kind of preparation method of hide finishes, may further comprise the steps:
A) casein and organic acid are dissolved in the water, obtain the casein aqueous solution;
B) in the casein aqueous solution that said step a) obtains, add hexanolactam, obtain intermediate product after the reaction;
C) in the intermediate product that said step b) obtains, add sanitas, obtain hide finishes after the stirring.
Preferably, also comprise before the said step b):
In the casein aqueous solution that said step a) obtains, add cationic emulsifier.
Preferably, said step b) specifically comprises:
In the casein aqueous solution that said adding cationic emulsifier obtains, add cationic initiator and hexanolactam, obtain intermediate product after the reaction.
Preferably, said organic acid is one or more in Hydrocerol A, lactic acid and the propionic acid.
Preferably, said cationic emulsifier is one or more in dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, DTAC, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride and the cetyl trimethylammonium bromide.
Preferably, said cationic initiator is an azo diisobutyl amidine hydrochloride.
Preferably, the mass ratio of said casein, cationic initiator and hexanolactam is (10～15): (0.1～0.3): (5～10).
Preferably, in the said step b), the temperature of said reaction is 80 ℃～100 ℃, and the time of said reaction is 1h～5h.
Compared with prior art, the present invention carries out modification with hexanolactam to casein and obtains modified Casein under the condition that organic acid exists; This modified Casein has not only been improved shortcomings such as the casein material filming is hard, inextensibility, easy fracture, and its demonstration cationic, after hide finishes formation coating; And avidity is better between the leather surface of demonstration anionic property; Therefore the bonding force of coating and leather surface is stronger, and difficult drop-off can not influence the coating quality of leather.The present invention is the hide finishes more than 15% with said modified Casein, with obtaining solid content after sanitas and water mix; Cover with paint, lacquer, colour wash, etc. after leather forms coating; Soft and full, the nature of leather body can effectively hide defectives such as pinprick, mange, increases utilization ratio, the raising leather grade of leather.The present invention is a dispersion medium with water, need not with an organic solvent, can not work the mischief to environment and HUMAN HEALTH.In addition, hide finishes preparation method provided by the invention is simple, convenient, is easy to produce constant product quality in batches.Experiment shows that hide finishes provided by the invention is covered with paint, lacquer, colour wash, etc. the brightness and the smooth degree that after leather, can improve leather, and the positively charged ion casein 1521 of result of use and asterisk scholar company is suitable.
Embodiment
The invention provides a kind of modified Casein, said modified Casein prepares according to following method:
The grafting polycondensation takes place in hexanolactam and casein under the organic acid condition, obtain modified Casein.
Modified Casein provided by the invention is under the organic acid existence condition; With hexanolactam as properties-correcting agent; Hexanolactam and casein generation grafting condensation reaction are obtained; It is shown as cationic, when the hide finishes and leather surface have avidity preferably, can improve the cohesive force between leather surface and the coating.
Said modified Casein is preferably according to following method preparation:
Casein and organic acid are dissolved in the water, obtain the casein aqueous solution;
In the said casein aqueous solution, add hexanolactam, take place to obtain modified Casein after the grafting polycondensation.
The present invention preferably at first is dissolved in the water casein under 70 ℃～75 ℃ conditions, add organic acid again, fully stirs 1.5h～2h casein is fully dissolved, and obtains the casein aqueous solution.Said organic acid is preferably one or more in Hydrocerol A, propionic acid and the lactic acid, more preferably propionic acid or lactic acid.Among the present invention, said casein and said organic acid mass ratio are preferably (5～20): (2～5), more preferably (10～15): (2～5).
After obtaining the casein aqueous solution, in the said casein aqueous solution, add hexanolactam, casein and hexanolactam generation grafting polycondensation obtain modified Casein.The present invention preferably adds cationic initiator when adding hexanolactam, make casein and hexanolactam that the grafting polycondensation take place under the effect of cationic initiator, and strengthen the cationic of said modified Casein.In the present invention, said cationic initiator is cationic initiator, includes but not limited to the cationic initiator that Lewis acid and complex compound are formed, like ceric ammonium nitrate etc.; Two imidazoles like azo diisobutyl amidine hydrochloride, comprise V40, V50 etc., are preferably azo diisobutyl amidine hydrochloride, more preferably V50.
The temperature of said casein and hexanolactam generation grafting polycondensation is preferably 80 ℃～100 ℃, and more preferably 85 ℃～95 ℃, the time is preferably 1h～5h, more preferably 2h～4h.When reacting, the mass ratio of said casein, cationic initiator and hexanolactam is preferably (10～15): (0.1～0.3): (5～10), more preferably (12～14): (0.15～0.25): (7～9).
After reaction finishes, obtain modified Casein, said modified Casein shows cationic.
In said modified Casein, except modified Casein, also comprise the material such as organic acid, cationic initiator of complete reaction not, the present invention can not separate it and directly be used to prepare hide finishes.
The present invention also provides a kind of hide finishes, comprising:
The described modified Casein of the technique scheme of 10wt%～40wt%;
The sanitas of 0.1wt%～1wt%;
The water of surplus.Hide finishes provided by the invention shows cationic; Cover with paint, lacquer, colour wash, etc. after leather forms coating; Avidity is better not only and between the leather surface, and bonding force is stronger, difficult drop-off and make soft and full, the nature of leather body; Can effectively hide defectives such as pinprick, mange, increase utilization ratio, the raising leather grade of leather.
In the hide finishes provided by the invention, said modified Casein is a membrane-forming agent, is the essential substance that forms coating, and its content is 10wt%～40wt%, is preferably 15wt%～35wt%.Said modified Casein forms with the hexanolactam modified Casein under the organic acid condition according to the technique scheme preparation, perhaps under the condition of organic acid dissolving casein, causes hexanolactam and casein generation grafting polycondensation formation with cationic initiator.
Hide finishes provided by the invention also comprises sanitas, and said sanitas is preferably the sanitas that does not contain phenyl ring, like BIOBAN
TMI-20 Antimicrobial, BIOBAN
TMULTRA BIT 20Antimicrobial etc.The content of said sanitas is 0.1wt%～1wt%, is preferably 0.2wt%～0.7wt%.
Hide finishes provided by the invention is dispersion agent with water, does not contain organic solvent, and is nontoxic, helps environment protection and HUMAN HEALTH.
Hide finishes provided by the invention preferably also comprises cationic emulsifier; Said cationic emulsifier is preferably one or more in dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, DTAC, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride and the cetyl trimethylammonium bromide; More preferably one or more in dodecyl benzyl dimethyl ammonium chloride, Trimethyllaurylammonium bromide and the cetyl trimethylammonium bromide most preferably are Trimethyllaurylammonium bromide and cetyl trimethylammonium bromide.The content of said cationic emulsifier is preferably 0.2wt%～1wt%, more preferably 0.3wt%～0.8wt%.
The solid content of hide finishes provided by the invention is higher, is more than 15%, to be preferably 15%～20%; The pH value is 3～5, is preferably 3.5～4.5; Viscosity is 500mPa.s～800mPa.s, is preferably 500mPa.s～600mPa.s.
The invention provides a kind of preparation method of hide finishes, may further comprise the steps:
A) casein and organic acid are dissolved in the water, obtain the casein aqueous solution;
B) in the casein aqueous solution that said step a) obtains, add hexanolactam, obtain intermediate product after the reaction;
C) in the intermediate product that said step b) obtains, add sanitas, obtain hide finishes after the stirring.
The present invention is properties-correcting agent and casein generation grafting polycondensation with the hexanolactam under the condition of organic acid acid dissolving casein, directly obtains cationic Casein Leather finish.Preparing method provided by the invention is simple, convenient, is easy to produce constant product quality in batches.
The present invention at first is dissolved in the water casein and organic acid, and casein all is dissolved in the water under the organic acid condition, specifically may further comprise the steps:
A1) casein is mixed heated and stirred with water;
A2) to said step a1) add organic acid in the mixing solutions that obtains, continue to stir and obtain the casein aqueous solution.
Said step a1) in, the temperature of said heated and stirred is preferably 65 ℃～80 ℃, more preferably 70 ℃～75 ℃; The time of said heated and stirred is preferably 0.5h～1.5h, more preferably 0.8h～1.1h; Said step a2) in, preferred 65 ℃～80 ℃ of the temperature that said continuation is stirred, more preferably 70 ℃～75 ℃; The time that said continuation is stirred is preferably 1h～2.5h, more preferably 1.5h～2h.Casein can all be dissolved in the water under the condition that organic acid exists, and obtains the casein aqueous solution.
In the present invention, said casein is a casein food grade well known to those skilled in the art, and the commercially available prod gets final product.Said organic acid is preferably one or more in Hydrocerol A, lactic acid and the propionic acid, more preferably lactic acid or propionic acid; Said water is preferably boiling water.Said casein and said organic acid mass ratio are preferably (5～20): (2～5), more preferably (10～15): (2～5); The mass ratio of said casein and water is preferably (10～15): (30～60), more preferably (10～15): (40～50).
After obtaining the casein aqueous solution, the present invention preferably adds cationic emulsifier in the said casein aqueous solution, obtain mixing solutions after the stirring.In the present invention; Said cationic emulsifier is preferably one or more in dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, DTAC, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride and the cetyl trimethylammonium bromide; More preferably one or more in dodecyl benzyl dimethyl ammonium chloride, Trimethyllaurylammonium bromide and the cetyl trimethylammonium bromide most preferably are Trimethyllaurylammonium bromide and cetyl trimethylammonium bromide.
The present invention preferably adds cation emulsified agent solution in the said casein aqueous solution, said cation emulsified agent solution is preferably according to following method preparation:
1) cationic emulsifier is joined in the hot water, fully stirring and dissolving.
In the said step 1), the temperature of said hot water is preferably 40 ℃～70 ℃, more preferably 50 ℃～60 ℃; The mass ratio of said cationic emulsifier and said hot water is preferably (0.2～1): (1.5～3), more preferably (0.4～0.7): (2～2.5).
Said cation emulsified agent solution is joined in the casein aqueous solution, obtain mixing solutions after fully stirring.The mass ratio of said cationic emulsifier and said casein is preferably (0.2～1): (5～20), more preferably (0.2～1): (10～15); The temperature of said stirring is preferably 75 ℃～90 ℃, more preferably 80 ℃～85 ℃; The time of said stirring is preferably 5min～15min, more preferably 8min～12min.
After obtaining mixing solutions, to wherein adding hexanolactam, hexanolactam and casein generation grafting polycondensation obtain modified Casein.The present invention preferably adds cationic initiator and hexanolactam simultaneously, makes hexanolactam and casein that the grafting polycondensation take place under the initiation of cationic initiator.In the present invention, said cationic initiator is cationic initiator, and the cationic initiator that Lewis acid and complex compound are formed is like ceric ammonium nitrate etc.; Two imidazoles like azo diisobutyl amidine hydrochloride, comprise V40, V50 etc., are preferably azo diisobutyl amidine hydrochloride, more preferably V50.The modified Casein cationic that said cationic initiator obtains is stronger, has stronger avidity with the leather surface that presents anionic property, thereby improves the bonding force between coating and the leather surface.
The present invention preferably adds the cationic initiator aqueous solution and caprolactam water solution in said mixing solutions, the said cationic initiator aqueous solution and said caprolactam water solution are preferably according to following method preparation:
B1) cationic initiator is joined in the hot water, fully stirring and dissolving;
B2) hexanolactam is joined in the hot water, fully stirring and dissolving;
Said step b1) and said step b2) between do not have step restriction.
Said step b1) in, the temperature of said hot water is preferably 40 ℃～70 ℃, more preferably 50 ℃～60 ℃; The mass ratio of said cationic initiator and said hot water is preferably (0.1～0.3): (15～30), more preferably (0.1～0.3): (20～25).Said step b2) in, the temperature of said hot water is preferably 40 ℃～70 ℃, more preferably 50 ℃～60 ℃; The mass ratio of said hexanolactam and said hot water is preferably (5～10): (6～9), more preferably (5～10): (6.5～8.5).
In order to make reaction more fully, fully, the present invention preferably joins said cationic initiator solution and said caprolactam solution in the said mixing solutions in batches, as preferably includes following steps:
Cationic initiator solution with 20%～30% and 20%～30% caprolactam solution join in the said mixing solutions, stir the back and drip residue cationic initiator solution and caprolactam solution, obtain intermediate product after the reaction.
In the present invention, the temperature that stirs after cationic initiator solution with 20%～30% and 20%～30% caprolactam solution join in the said mixing solutions is preferably 80 ℃～100 ℃, more preferably 85 ℃～95 ℃; Time is preferably 5min～15min, more preferably 7min～12min; The present invention preferably in 1h, will remain cationic initiator solution and caprolactam solution dropwises; After dropwising, the temperature of said reaction is preferably 80 ℃～100 ℃, and more preferably 85 ℃～95 ℃, the time of said reaction is preferably 1h～5h, more preferably 2h～4h.
When reacting, the mass ratio of said casein, cationic initiator and hexanolactam is preferably (10～15): (0.1～0.3): (5～10), more preferably (12～14): (0.15～0.25): (7～9).
After reaction finishes, obtain intermediate product, said intermediate product comprises modified Casein, cationic emulsifier and water, also comprises a small amount of unreacted organic acid and/or cationic initiator completely.After obtaining intermediate product, after wherein adding sanitas, stirring, obtain hide finishes.In the present invention, said sanitas is preferably the sanitas that does not contain phenyl ring, like BIOBAN
TMI-20 Antimicrobial, BIOBAN
TMULTRA BIT 20 Antimicrobial etc.
The present invention preferably adds antiseptic solution in said intermediate product, said antiseptic solution is preferably according to following method preparation:
C1) sanitas is joined in the hot water, fully stirring and dissolving.
Said step c1) in, the temperature of said hot water is preferably 40 ℃～70 ℃, more preferably 50 ℃～60 ℃; The mass ratio of said sanitas and said hot water is preferably (0.1～1): (1～2), more preferably (0.2～0.7): (1.2～1.8).In the present invention, said sanitas can be for multiple, when sanitas when being multiple, preferably prepares each antiseptic solution respectively.
In said intermediate product, add antiseptic solution, obtain hide finishes after fully stirring, the temperature of said stirring is preferably 35 ℃～50 ℃, and more preferably 40 ℃～45 ℃, the time is preferably 20min～40min, more preferably 25min～35min; The mass ratio of said sanitas and said casein is preferably (0.1～1): (10～15), more preferably (0.2～0.7): (10～15).
In the present invention; Can confirm the usage quantity of water according to the content of water in the product that finally obtains; Thereby need not the hide finishes that aftertreatment can directly be met requirement; As the massfraction of water is 65%～85% in the hide finishes that finally obtains, and can confirm the consumption of water according to following method:
60% water is used to dissolve casein and organic acid; 3% water is used to dissolve cationic emulsifier; 25% water is used to dissolve cationic initiator; 10% water is used to dissolve hexanolactam; 2% water is used to dissolve sanitas etc.
After obtaining hide finishes, it is detected, the result shows that the solid content of the hide finishes that method provided by the invention prepares is more than 15%, to be preferably 15%～20%; The pH value is 3～5, is preferably 3.5～4.5; Viscosity is 500mPa.s～800mPa.s, is preferably 500mPa.s～600mPa.s.
After obtaining hide finishes; It is covered with paint, lacquer, colour wash, etc. in leather surface formation coating, and carry out brightness and the isoparametric investigation of feel, the result shows; The mill base that the positively charged ion casein 1521 of itself and asterisk scholar company forms has suitable brightness peace fineness, and feel is more smooth.
The present invention carries out modification with hexanolactam to casein and obtains modified Casein under the condition that organic acid exists, and this modified Casein has not only been improved shortcomings such as the casein material filming is hard, inextensibility, easy fracture; And it shows cationic; After hide finishes formation coating, and avidity is better between the leather surface of demonstration anionic property, so the bonding force of coating and leather surface is stronger; Difficult drop-off can not influence the coating quality of leather.The present invention is the hide finishes more than 15% with said modified Casein with obtaining solid content after sanitas and water mix; Cover with paint, lacquer, colour wash, etc. after leather forms coating; Soft and full, the nature of leather body can effectively hide defectives such as pinprick, mange, increases utilization ratio, the raising leather grade of leather.The present invention is a dispersion medium with water, need not with an organic solvent, can not work the mischief to environment and HUMAN HEALTH.In addition, hide finishes preparation method provided by the invention is simple, convenient, is easy to produce constant product quality in batches.
In order to further specify the present invention, modified Casein provided by the invention, hide finishes and preparation method thereof are described in detail below in conjunction with embodiment.
Embodiment 1
Take by weighing following raw materials according respectively:
300g boiling water, 50g casein food grade, 8g propionic acid, 30g hexanolactam, 0.48gBIOBAN
TMI-20Antimicrobial and 0.64gBIOBAN
TMULTRA BIT 20 Antimicrobial;
20% of boiling water total amount is cooled to 60 ℃, adds whole hexanolactams and make its whole dissolvings, obtain caprolactam water solution;
5% of boiling water total amount is cooled to 60 ℃, adds whole BIOBAN
TMI-20 Antimicrobial makes its whole dissolvings, obtains first aqueous preservative solution;
5% of boiling water total amount is cooled to 60 ℃, adds whole BIOBAN
TMULTRA BIT 20Antimicrobial makes its whole dissolvings, obtains second aqueous preservative solution;
70% of boiling water total amount is added in the reaction kettle, open and stir, add whole caseins, and be heated to 70 ℃～75 ℃, stirred 1 hour; In said reaction kettle, add whole propionic acid, stirred 2 hours, casein is all dissolved, and be warmed up to 80 ℃～85 ℃; In reaction kettle, add 25% of caprolactam water solution respectively, stir and drip the residue caprolactam water solution after 10 minutes, dripped off in 1 hour, be warmed up to 95 ℃, insulation reaction cools to 45 ℃ after 3 hours; Continuation adds first aqueous preservative solution and second aqueous preservative solution in said reaction kettle, stir discharging after 30 minutes, obtains hide finishes.
Said hide finishes is detected, and its solid content is 17 ± 1%, the pH value is 3～4, viscosity is 500mPa.s.
Embodiment 2
Take by weighing following raw materials according respectively:
300g boiling water, 50g casein food grade, 8g lactic acid, 0.45gV50,32g hexanolactam, 0.48gBIOBAN
TMI-20 Antimicrobial and 0.64gBIOBAN
TMULTRA BIT 20 Antimicrobial;
25% of boiling water total amount is cooled to 55 ℃, adds whole V50 and make its whole dissolvings, obtain initiator solution;
10% of boiling water total amount is cooled to 55 ℃, adds whole hexanolactams and make its whole dissolvings, obtain caprolactam water solution;
2% of boiling water total amount is cooled to 55 ℃, adds whole BIOBAN
TMI-20 Antimicrobial makes its whole dissolvings, obtains first aqueous preservative solution;
3% of boiling water total amount is cooled to 55 ℃, adds whole BIOBAN
TMULTRA BIT 20Antimicrobial makes its whole dissolvings, obtains second aqueous preservative solution;
60% of boiling water total amount is added in the reaction kettle, open and stir, add whole caseins, and be heated to 70 ℃～75 ℃, stirred 1 hour; In said reaction kettle, add whole propionic acid, stirred 2 hours, casein is all dissolved, and be warmed up to 80 ℃～85 ℃; In reaction kettle, add 25% of caprolactam water solution and initiator solution respectively, stir and drip residue caprolactam water solution and initiator solution after 10 minutes, dripped off in 1 hour, be warmed up to 95 ℃, insulation reaction cools to 45 ℃ after 3 hours; Continuation adds first aqueous preservative solution and second aqueous preservative solution in said reaction kettle, stir discharging after 30 minutes, obtains hide finishes.
Said hide finishes is detected, and its solid content is 17 ± 1%, the pH value is 3～4, viscosity is 500mPa.s.
Embodiment 3
Take by weighing following raw materials according respectively:
310g boiling water, 50g casein food grade, 9g propionic acid, 1.5g cetyl trimethylammonium bromide, 32g hexanolactam, 0.48gBIOBAN
TMI-20 Antimicrobial and 0.64gBIOBAN
TMULTRA BIT20 Antimicrobial;
3% of boiling water total amount is cooled to 60 ℃, adds whole cetyl trimethylammonium bromides and make its whole dissolvings, obtain emulsifier aqueous solution;
20% of boiling water total amount is cooled to 60 ℃, adds whole hexanolactams and make its whole dissolvings, obtain caprolactam water solution;
1% of boiling water total amount is cooled to 60 ℃, adds whole BIOBAN
TMI-20 Antimicrobial makes its whole dissolvings, obtains first aqueous preservative solution;
1% of boiling water total amount is cooled to 60 ℃, adds whole BIOBAN
TMULTRA BIT 20Antimicrobial makes its whole dissolvings, obtains second aqueous preservative solution;
75% of boiling water total amount is added in the reaction kettle, open and stir, add whole caseins, and be heated to 70 ℃～75 ℃, stirred 1 hour; In said reaction kettle, add whole propionic acid, stirred 2 hours, casein is all dissolved, and be warmed up to 80 ℃～85 ℃; In reaction kettle, add 25% of caprolactam water solution and initiator solution respectively, stir and drip residue caprolactam water solution and initiator solution after 10 minutes, dripped off in 1 hour, be warmed up to 95 ℃, insulation reaction cools to 45 ℃ after 3 hours; Continuation adds first aqueous preservative solution and second aqueous preservative solution in said reaction kettle, stir discharging after 30 minutes, obtains hide finishes.
Said hide finishes is detected, and its solid content is 17 ± 1%, the pH value is 3～4, viscosity is 500mPa.s.
Embodiment 4
Take by weighing following raw materials according respectively:
320.9g boiling water, 50g casein food grade, 9g propionic acid, 1.5g cetyl trimethylammonium bromide, 0.48gV50,32g hexanolactam, 0.48gBIOBAN
TMI-20 Antimicrobial and 0.64gBIOBAN
TMULTRABIT 20 Antimicrobial;
3% of boiling water total amount is cooled to 60 ℃, adds whole cetyl trimethylammonium bromides and make its whole dissolvings, obtain emulsifier aqueous solution;
25% of boiling water total amount is cooled to 60 ℃, adds whole V50 and make its whole dissolvings, obtain initiator solution;
10% of boiling water total amount is cooled to 60 ℃, adds whole hexanolactams and make its whole dissolvings, obtain caprolactam water solution;
1% of boiling water total amount is cooled to 60 ℃, adds whole BIOBAN
TMI-20 Antimicrobial makes its whole dissolvings, obtains first aqueous preservative solution;
1% of boiling water total amount is cooled to 60 ℃, adds whole BIOBAN
TMULTRA BIT 20Antimicrobial makes its whole dissolvings, obtains second aqueous preservative solution;
60% of boiling water total amount is added in the reaction kettle, open and stir, add whole caseins, and be heated to 70 ℃～75 ℃, stirred 1 hour; In said reaction kettle, add whole propionic acid, stirred 2 hours, casein is all dissolved, and be warmed up to 80 ℃～85 ℃; In said reaction kettle, add emulsifier aqueous solution, stirred 10 minutes; Continuation adds 25% of caprolactam water solution and initiator solution respectively in reaction kettle, stir to drip residue caprolactam water solution and initiator solution after 10 minutes, drips off in 1 hour, is warmed up to 95 ℃, and insulation reaction cools to 45 ℃ after 3 hours; Continuation adds first aqueous preservative solution and second aqueous preservative solution in said reaction kettle, stir discharging after 30 minutes, obtains hide finishes.
Said hide finishes is detected, and its solid content is 17 ± 1%, the pH value is 3～4, viscosity is 500mPa.s.
Embodiment 5
Take by weighing following raw materials according respectively:
265.9g boiling water, 50g casein food grade, 9g lactic acid, 1.5g cetyl trimethylammonium bromide, 0.48gV50,32g hexanolactam, 0.48gBIOBAN
TMI-20 Antimicrobial and 0.64gBIOBAN
TMULTRABIT 20 Antimicrobial;
3% of boiling water total amount is cooled to 50 ℃, adds whole cetyl trimethylammonium bromides and make its whole dissolvings, obtain emulsifier aqueous solution;
25% of boiling water total amount is cooled to 50 ℃, adds whole V50 and make its whole dissolvings, obtain initiator solution;
10% of boiling water total amount is cooled to 50 ℃, adds whole hexanolactams and make its whole dissolvings, obtain caprolactam water solution;
1% of boiling water total amount is cooled to 50 ℃, adds whole BIOBAN
TMI-20 Antimicrobial makes its whole dissolvings, obtains first aqueous preservative solution;
1% of boiling water total amount is cooled to 50 ℃, adds whole BIOBAN
TMULTRA BIT 20Antimicrobial makes its whole dissolvings, obtains second aqueous preservative solution;
60% of boiling water total amount is added in the reaction kettle, open and stir, add whole caseins, and be heated to 70 ℃～75 ℃, stirred 1 hour; In said reaction kettle, add whole lactic acid, stirred 1.5 hours, casein is all dissolved, and be warmed up to 80 ℃～85 ℃; In said reaction kettle, add emulsifier aqueous solution, stirred 10 minutes; Continuation adds 25% of caprolactam water solution and initiator solution respectively in reaction kettle, stir to drip residue caprolactam water solution and initiator solution after 10 minutes, drips off in 1 hour, is warmed up to 90 ℃, and insulation reaction cools to 45 ℃ after 3 hours; Continuation adds first aqueous preservative solution and second aqueous preservative solution in said reaction kettle, stir discharging after 30 minutes, obtains hide finishes.
Said hide finishes is detected, and its solid content is 17 ± 1%, the pH value is 3～4, viscosity is 600mPa.s.
Embodiment 6
Take by weighing following raw materials according respectively:
245.9g boiling water, 50g casein food grade, 9g lactic acid, 1.5g Trimethyllaurylammonium bromide, 0.48gV50,32g hexanolactam, 0.48gBIOBAN
TMI-20 Antimicrobial and 0.64gBIOBAN
TMULTRABIT 20 Antimicrobial;
3% of boiling water total amount is cooled to 55 ℃, adds whole Trimethyllaurylammonium bromides and make its whole dissolvings, obtain emulsifier aqueous solution;
25% of boiling water total amount is cooled to 55 ℃, adds whole V50 and make its whole dissolvings, obtain initiator solution;
10% of boiling water total amount is cooled to 55 ℃, adds whole hexanolactams and make its whole dissolvings, obtain caprolactam water solution;
1% of boiling water total amount is cooled to 55 ℃, adds whole BIOBAN
TMI-20 Antimicrobial makes its whole dissolvings, obtains first aqueous preservative solution;
1% of boiling water total amount is cooled to 55 ℃, adds whole BIOBAN
TMULTRA BIT 20Antimicrobial makes its whole dissolvings, obtains second aqueous preservative solution;
60% of boiling water total amount is added in the reaction kettle, open and stir, add whole caseins, and be heated to 70 ℃～75 ℃, stirred 1 hour; In said reaction kettle, add whole lactic acid, stirred 2 hours, casein is all dissolved, and be warmed up to 80 ℃～85 ℃; In said reaction kettle, add emulsifier aqueous solution, stirred 10 minutes; Continuation adds 25% of caprolactam water solution and initiator solution respectively in reaction kettle, stir to drip residue caprolactam water solution and initiator solution after 10 minutes, drips off in 1 hour, is warmed up to 95 ℃, and insulation reaction cools to 45 ℃ after 3 hours; Continuation adds first aqueous preservative solution and second aqueous preservative solution in said reaction kettle, stir discharging after 30 minutes, obtains hide finishes.
Said hide finishes is detected, and its solid content is 17 ± 1%, the pH value is 3～4, viscosity is 600mPa.s.
Embodiment 7
According to following method the hide finishes that the embodiment of the invention 1～6 provides is carried out performance test:
With the said hide finishes of 100g, 100g model is that cation polyurethane, the model of 1530/T is that 1512 cationic wax and 300g water mix, and obtains mill base, and said mill base is little thick milky white liquid;
Choosing 6 piece sizes respectively is the sheepskin vamp of 20cm * 15cm, covers with paint, lacquer, colour wash, etc. according to following flow process, the above-mentioned mill base of employing, forms the upper leather back cover:
Middle spray 1 time, leave standstill 2h after the middle spray---wipe 1 time, wipe the back hold over night, second day boiling hot light of oven dry---polishing---, boiling hot optical parameter is: 90 °, 50 kilograms, 2s;
After the covering with paint, detect the gloss and the feel of coating, the result is referring to table 1, the The performance test results of the hide finishes that table 1 provides for the embodiment of the invention and comparative example.
Comparative example 1
According to following method said hide finishes is carried out performance test:
With 100g available from the asterisk scholar, model is that hide finishes, the 100g model of positively charged ion casein 1521 is 991 cationic pigment paste, the 100g model is 1530/T cation polyurethane, model are that 1512 cationic wax and 300g water mix; Obtain mill base, said mill base is little thick yellow liquid;
Choosing 6 piece sizes respectively is the sheepskin vamp of 20cm * 15cm, covers with paint, lacquer, colour wash, etc. according to following flow process, the above-mentioned mill base of employing, forms the upper leather back cover:
Middle spray 1 time, leave standstill 2h after the middle spray---wipe 1 time, wipe the back hold over night, second day boiling hot light of oven dry---polishing---, boiling hot optical parameter is: 90 °, 50 kilograms, 2s;
After the covering with paint, detect the gloss and the feel of coating, the result is referring to table 1, the The performance test results of the hide finishes that table 1 provides for the embodiment of the invention and comparative example.
The The performance test results of the hide finishes that table 1 embodiment of the invention and comparative example provide
In table 1, fine and smooth, comfort index is high more, smooth degree is good more;
Can be known that by table 1 hide finishes that the embodiment of the invention provides is more smooth, and the hide finishes that comparative example 1 provides is more puckery, the wax sense is heavier; After scalding light, the brightness of the coating that the hide finishes that the embodiment of the invention provides forms and the brightness that comparative example 1 provides are more or less the same.
In addition, behind the boiling hot light, the flat fineness of the coating that the hide finishes that the embodiment of the invention provides forms and the flat fineness that comparative example 1 provides are more or less the same.
Can know that by the foregoing description and comparative example hide finishes provided by the invention has good coating effect.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (16)
1. a modified Casein is characterized in that, said modified Casein prepares according to following method:
The grafting polycondensation takes place in hexanolactam and casein under the organic acid condition, obtain modified Casein.
2. modified Casein according to claim 1 is characterized in that, the grafting polycondensation is taking place under the initiation of cationic initiator, under the organic acid condition for said hexanolactam and casein.
3. modified Casein according to claim 2 is characterized in that, said cationic initiator is an azo diisobutyl amidine hydrochloride.
4. modified Casein according to claim 1 is characterized in that, said organic acid is one or more in Hydrocerol A, lactic acid and the propionic acid.
5. hide finishes comprises:
Any described modified Casein of the claim 1～4 of 10wt%～40wt%;
The sanitas of 0.1wt%～1wt%;
The water of surplus.
6. hide finishes according to claim 5 is characterized in that, said sanitas is not for containing the sanitas of phenyl ring.
7. hide finishes according to claim 5 is characterized in that, also comprises the cationic emulsifier of 0.2wt%～1wt%.
8. hide finishes according to claim 7; It is characterized in that said cationic emulsifier is one or more in dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, DTAC, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride and the cetyl trimethylammonium bromide.
9. the preparation method of a hide finishes may further comprise the steps:
A) casein and organic acid are dissolved in the water, obtain the casein aqueous solution;
B) in the casein aqueous solution that said step a) obtains, add hexanolactam, obtain intermediate product after the reaction;
C) in the intermediate product that said step b) obtains, add sanitas, obtain hide finishes after the stirring.
10. preparation method according to claim 9 is characterized in that, also comprises before the said step b):
In the casein aqueous solution that said step a) obtains, add cationic emulsifier.
11. preparation method according to claim 10 is characterized in that, said step b) specifically comprises:
In the casein aqueous solution that said adding cationic emulsifier obtains, add cationic initiator and hexanolactam, obtain intermediate product after the reaction.
12. preparation method according to claim 11 is characterized in that, said organic acid is one or more in Hydrocerol A, lactic acid and the propionic acid.
13. preparation method according to claim 12; It is characterized in that said cationic emulsifier is one or more in dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, DTAC, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride and the cetyl trimethylammonium bromide.
14. preparation method according to claim 13 is characterized in that, said cationic initiator is an azo diisobutyl amidine hydrochloride.
15. preparation method according to claim 14 is characterized in that, the mass ratio of said casein, cationic initiator and hexanolactam is (10～15): (0.1～0.3): (5～10).
16., it is characterized in that in the said step b), the temperature of said reaction is 80 ℃～100 ℃ according to any described preparation method of claim 9～15, the time of said reaction is 1h～5h.
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| CN103061129A (en) * | 2012-12-28 | 2013-04-24 | 苏州鼎润复合材料有限公司 | Synthetic leather finishing agent, preparation method of the synthetic leather finishing agent, and synthetic leather surface treatment method |
| CN104530330A (en) * | 2014-12-24 | 2015-04-22 | 四川达威科技股份有限公司 | Leather finishing agent and preparation method thereof |
| CN105384883A (en) * | 2015-12-25 | 2016-03-09 | 上海金狮化工有限公司 | Method for preparing amphoteric retanning agent |
| CN105384883B (en) * | 2015-12-25 | 2018-04-27 | 上海金狮化工有限公司 | A kind of preparation method of amphoteric retanning agent |
| DE112017000374B4 (en) * | 2016-01-14 | 2021-04-29 | Shaanxi University Of Science And Technology | A slow release, mold protecting and casein-based microsphere coating material and a process for its manufacture |
| 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 |
| CN106221558A (en) * | 2016-08-22 | 2016-12-14 | 中国皮革和制鞋工业研究院（晋江）有限公司 | A kind of preparation method of leather casein class gloss oil |
| 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 |
| CN109252365A (en) * | 2018-08-10 | 2019-01-22 | 陕西科技大学 | Anti-electrostatic fire retardant type casein base graphene compound fabric and preparation method thereof |
| CN109252365B (en) * | 2018-08-10 | 2021-07-27 | 陕西科技大学 | Antistatic flame-retardant casein-based graphene composite fabric and preparation method thereof |
| IT202200010043A1 (en) | 2022-05-16 | 2023-11-16 | Fgl Int S P A | FORMULATION FOR COATING PRODUCT |
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| CN102532561B (en) | 2013-12-04 |
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