CN104530330B - A kind of leather finishing agent and preparation method thereof - Google Patents
A kind of leather finishing agent and preparation method thereof Download PDFInfo
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- CN104530330B CN104530330B CN201410814332.3A CN201410814332A CN104530330B CN 104530330 B CN104530330 B CN 104530330B CN 201410814332 A CN201410814332 A CN 201410814332A CN 104530330 B CN104530330 B CN 104530330B
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- finishing agent
- casein
- leather
- leather finishing
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- 239000010985 leather Substances 0.000 title claims abstract description 160
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 110
- 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 105
- 235000021240 caseins Nutrition 0.000 claims abstract description 77
- 239000005018 casein Substances 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000178 monomer Substances 0.000 claims abstract description 40
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 21
- 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 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 15
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 35
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 1
- 235000010265 sodium sulphite Nutrition 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 33
- -1 amino, carboxyl Chemical group 0.000 abstract description 8
- 150000002118 epoxides Chemical group 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000006482 condensation reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 102000011632 Caseins Human genes 0.000 description 69
- 108010076119 Caseins Proteins 0.000 description 69
- 239000000243 solution Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 23
- 238000012545 processing Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 13
- 239000003643 water by type Substances 0.000 description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000009413 insulation Methods 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
- 238000005498 polishing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 241001272567 Hominoidea Species 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000007654 immersion Methods 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 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
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 150000003951 lactams 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000017854 proteolysis Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 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
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a kind of leather finishing agent, prepared by γ glycidyl ether oxygen propyl trimethoxy silicanes, acrylate monomer, persulfate, casein, organic amine, water and sulphite；The acrylate monomer includes more than three kinds in butyl acrylate, ethyl acrylate, styrene and acrylonitrile.The invention provides a kind of preparation method of leather finishing agent, casein is used into modified with acrylate monomers again using γ glycidyl ether oxygen propyl trimethoxy silicanes are modified, contain epoxide group in γ glycidyl ether oxygen propyl trimethoxy silicanes, pass through modification, epoxide group is grafted in the macromolecular of casein, occur condensation reaction with the polar group on casein side chain such as hydroxyl, amino, carboxyl etc., make the leather finishing agent that the present invention is provided that there is preferable compliance and water resistance；By being modified again for acrylate monomer, the compliance and water resistance for the leather finishing agent that the present invention is provided can be further improved.
Description
Technical field
The present invention relates to leather processing technique field, more particularly to a kind of leather finishing agent and preparation method thereof.
Background technology
Leather finishing agent is mainly used in the modification of leather, particularly in various obverse leathers, the polishing of buff and ironing
During must be indispensable, leather finishing agent can be such that coating is bonded securely with leather surface, improve leather high temperature resistant flatiron property
And polishability, and leather finishing agent can also make leather keep the distinctive sanitation performance of natural leather.
At present, the composition of leather finishing agent is generally modified casein, the material for modified Casein mainly have polyurethane, oneself
Lactams and vinyl monomer etc.；But the polyurethane-modified casein toxicity larger because isocyanate material has,
Modified casein finishing agent is set to bring larger pollution to human body and environment；And the modified casein of acrylic ester monomer
The water resistance or flexible resistance of the finishing agent prepared are poor；Casein is modified using organosilicon, can improve and change
The water resistance and flexible resistance of casein finishing agent after property, such as prior art describe a kind of soap-free polymerization method and prepare acrylic acid
The method of the common modified Casein Leather finishing agent of ester/silane coupler, using double bond containing silane coupler and acrylate to junket
Element progress is double modified, and specific method is：First with triethanolamine and water dissolving casein, casein lysate is obtained；Again to described
Caprolactam solution is added dropwise in casein lysate, the casein emulsion of caprolactam modification is obtained；Then in persulfide initiator
In the presence of, using semi-continuous seed surfactant- free emulsion polymerization, added simultaneously in the casein emulsion being modified to the caprolactam
Methyl methacrylate, butyl acrylate and silane coupler, by Raolical polymerizable, obtain acrylate/silane even
Join agent modified Casein Leather finishing agent altogether.
This leather finishing agent that prior art is provided first uses caprolactam modified Casein, then using acrylate/silicon
The coupling agent modified casein of alkane；Silane coupler is vinyl silicane coupling agent.This leather finishing agent that prior art is provided
Although water resistance has obtained a certain degree of raising, but still poor, limits the extensive use of leather finishing agent.
The content of the invention
In view of this, it is an object of the invention to provide a kind of leather finishing agent, the leather finishing agent tool that the present invention is provided
There are preferable compliance and water resistance.
The invention provides a kind of leather finishing agent, by γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate
Monomer, persulfate, casein, organic amine, water and sulphite are prepared；The acrylate monomer includes acrylic acid fourth
More than three kinds in ester, ethyl acrylate, styrene and acrylonitrile.
It is preferred that, the γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate monomer, persulfate, junket
Element, organic amine, the mass ratio of water and sulphite are (5~10):(45~100):(0.1~1):(100~150):(20~
30):(580~1000):(0.1~1).
It is preferred that, the acrylate monomer in parts by weight, including：
33 parts~50 parts of butyl acrylate；
A parts of ethyl acrylate, 0 ＜ A≤23；
B parts of styrene, 0 ＜ B≤37.5；
C parts of acrylonitrile, 0 ＜ C≤50.
It is preferred that, one or more of the persulfate in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate.
It is preferred that, one or more of the organic amine in triethylamine, diethylamine, triethanolamine and diethanol amine.
It is preferred that, the sulphite is selected from one or both of sodium hydrogensulfite and sodium pyrosulfite.
The leather finishing agent that the present invention is provided, introduces acrylate monomer during modified Casein and γ-shrink is sweet
Contain epoxide group in oily ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, by changing
Property, epoxide group is grafted in the macromolecular of casein, occurred with the polar group on casein side chain such as hydroxyl, amino, carboxyl etc.
Condensation reaction, makes the leather finishing agent that the present invention is provided have preferable compliance and water resistance；And by γ-glycidol ether
The modified casein of oxygen propyl trimethoxy silicane is modified again using acrylate monomer, can further be improved the present invention and be carried
The compliance and water resistance of the leather finishing agent of confession；Therefore, the leather finishing agent that provides of the present invention have preferable compliance and
Water resistance.Test result indicates that, the leather hand feeling after the processing for the leather finishing agent that the present invention is provided is soft, smooth；The present invention
The water resistance of the leather finishing agent of offer is 1.2~1.4.
In addition, the leather finishing agent that provides of the present invention can also improve the glossiness of leather, it is polish retention, plasticity, resistance to
Xerotripsis, wet-rub resistance, resistance to bent rich property, make the leather hand feeling after processing comfortable；And in the leather finishing agent of the invention provided
Without organic solvents, safety and environmental protection such as APES class compounds.Test result indicates that, the leather that the present invention is provided
The resistance to xerotripsis of leather after finishing agent processing is 4.5 grades~5 grades, and wet-rub resistance is 4.5 grades~5 grades；Glossiness is 7.5,7 days
Glossiness afterwards is 6.5~7.5.
The invention provides a kind of preparation method of leather finishing agent, comprise the following steps：
1) reaction, is hydrolyzed in casein and organic amine in water, hydrolyzed casein liquid is obtained；
2), the hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy silicane are reacted, are modified
Casein liquid；
3) carry out polymerizeing instead after, mixing the modified Casein liquid, acrylate monomer, persulfate and sulphite
Should, obtain leather finishing agent；
The acrylate monomer includes more than three kinds in butyl acrylate, ethyl acrylate, styrene and acrylonitrile.
It is preferred that, the step 1) in hydrolysis temperature be 70 DEG C~80 DEG C；
The time of hydrolysis is 1 hour~2 hours.
It is preferred that, the step 2) in reaction temperature be 70 DEG C~80 DEG C；
The time of reaction is 1 hour~2 hours.
It is preferred that, the step 3) in polymerisation temperature be 70 DEG C~90 DEG C；
The time of polymerisation is 2 hours~4 hours.
The present invention is laggard by the way that casein is carried out into proteolysis, γ-glycidyl ether oxygen propyl trimethoxy silicane modification
Row polymerisation prepares leather finishing agent, and the preparation method of this leather finishing agent first uses γ-glycidyl ether oxygen third
Base trimethoxy silane is modified to casein, and modified casein is modified again using acrylate monomer, this
The leather finishing agent that method is prepared has preferable compliance and water resistance.
In addition, the leather finishing agent that the method that the present invention is provided is prepared can also improve the glossiness of leather, gloss
Retentivity, plasticity, resistance to xerotripsis, wet-rub resistance, resistance to bent rich property, make the leather hand feeling after processing comfortable；And the present invention is provided
The leather finishing agent for preparing of method in be free of organic solvent, safety and environmental protection.In addition, the leather finishing agent that the present invention is provided
Preparation method process stabilizing, be adapted to industrialized production.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
The invention provides a kind of leather finishing agent, by γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate
Monomer, persulfate, casein, organic amine, water and sulphite are prepared；The acrylate monomer includes acrylic acid fourth
More than three kinds in ester, ethyl acrylate, styrene and acrylonitrile.
In an embodiment of the present invention, the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane can be with
For 5 parts~10 parts；In other examples, the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane can
Think 6 parts~8 parts.The present invention originates without special limitation to the γ-glycidyl ether oxygen propyl trimethoxy silicane,
It can be bought and obtained by market, such as use KH-570 silane couplers well known to those skilled in the art.
In an embodiment of the present invention, using the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane as
Benchmark, the parts by weight of the acrylate monomer can be 45 parts~100 parts；In other examples, the acrylic acid
The parts by weight of ester monomer can be 60 parts~80 parts.In the present invention, the acrylate monomer includes butyl acrylate, third
The mixture or the mixture of four kinds of materials of three kinds of materials in olefin(e) acid ethyl ester, styrene and acrylonitrile.In the preferred of the present invention
In embodiment, the acrylate monomer in parts by weight, including：
33 parts~50 parts of butyl acrylate；
A parts of ethyl acrylate, 0 ＜ A≤23；
B parts of styrene, 0 ＜ B≤37.5；
C parts of acrylonitrile, 0 ＜ C≤50.
The present invention does not have special limitation to the preparation method of the acrylate monomer, by butyl acrylate, acrylic acid
Three kinds of materials in ethyl ester, styrene and acrylonitrile are mixed；Or by butyl acrylate, ethyl acrylate, styrene and third
Alkene nitrile is mixed.In an embodiment of the present invention, the mixing can be carried out under conditions of stirring.The present invention's
In embodiment, the time of the mixing can be 8 minutes~12 minutes.
In an embodiment of the present invention, using the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane as
Benchmark, the parts by weight of the persulfate can be 0.1 part~1 part；In other examples, the weight of the persulfate
It can be 0.5 part~0.8 part to measure number.In an embodiment of the present invention, the persulfate can be selected from ammonium persulfate, over cure
One or more in sour potassium and sodium peroxydisulfate.In a preferred embodiment of the invention, the persulfate is that persulfate is molten
Liquid；In other preferred embodiments, the persulfate is the persulfate aqueous solution.In an embodiment of the present invention, it is described
The mass concentration of persulfate solution is 0.8%~1.2%；In other examples, the quality of the persulfate solution
Concentration is 1%.
In an embodiment of the present invention, using the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane as
Benchmark, the parts by weight of the casein can be 100 parts~150 parts；In other examples, the parts by weight of the casein
It can be 120 parts~130 parts.The present invention originates without special limitation to the casein, ripe using those skilled in the art
The casein known, can be bought by market and obtained.
In an embodiment of the present invention, using the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane as
Benchmark, the parts by weight of the organic amine can be 20 parts~30 parts；In other examples, the parts by weight of the organic amine
Number can be 24 parts~26 parts.In a preferred embodiment of the invention, the organic amine can be triethylamine, diethylamine, three second
One or more in hydramine and diethanol amine.
In an embodiment of the present invention, using the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane as
Benchmark, the parts by weight of the water can be 580 parts~1000 parts；In other examples, the parts by weight of the water can
Think 650 parts~800 parts.In a preferred embodiment of the invention, the water can be deionized water.
In an embodiment of the present invention, using the parts by weight of the γ-glycidyl ether oxygen propyl trimethoxy silicane as
Benchmark, the parts by weight of the sulphite can be 0.1 part~1 part；In other examples, the weight of the sulphite
It can be 0.4 part~0.8 part to measure number.In a preferred embodiment of the invention, the sulphite can be sodium hydrogensulfite
One or both of with sodium pyrosulfite.In a preferred embodiment of the invention, the sulphite is sulfite solution；
In other preferred embodiments, the sulphite is sulfite solution.In an embodiment of the present invention, the sulfurous
The mass concentration of acid salt solution can be 0.8%~1.2%；In other examples, the quality of the sulfite solution
Concentration can be 1%.
In a preferred embodiment of the invention, the γ-glycidyl ether oxygen propyl trimethoxy silicane, acrylate list
Body, persulfate, casein, organic amine, the mass ratio of water and sulphite are (5~10):(45~100):(0.1~1):(100
~150):(20~30):(580~1000):(0.1~1).The leather finishing agent outward appearance that the present invention is provided is faint yellow translucent
Emulsion, is presented anionic property, and pH value is 7~9, and solid content is 19%~21%.
The leather finishing agent that the present invention is provided has preferable compliance and water resistance.In addition, the leather that the present invention is provided
Finishing agent can also improve glossiness, polish retention, plasticity, resistance to xerotripsis, wet-rub resistance, the resistance to bent rich property of leather, make place
Leather hand feeling after reason is comfortable；And without APES class compound etc. in the leather finishing agent of the invention provided
Organic solvent, safety and environmental protection.
The invention provides a kind of preparation method of leather finishing agent, including：
Reaction is hydrolyzed in casein and organic amine in water, hydrolyzed casein liquid is obtained；
The hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy silicane are reacted, obtain being modified junket
Plain liquid；
Polymerisation is carried out after the modified Casein liquid, acrylate monomer, persulfate and sulphite are mixed, is obtained
To leather finishing agent；
The acrylate monomer includes more than three kinds in butyl acrylate, ethyl acrylate, styrene and acrylonitrile.
Reaction is hydrolyzed in casein and organic amine by the present invention in water, obtains hydrolyzed casein liquid.In the present invention, it is described
Casein, the species of organic amine and water, source and parts by weight and casein described in upper technical scheme, the species of organic amine and water, come
Source is consistent with parts by weight, will not be repeated here.
In an embodiment of the present invention, the time of the hydrolysis can be 1 hour~2 hours.In the reality of the present invention
Apply in example, the temperature of the hydrolysis can be 70 DEG C~80 DEG C；In other examples, the temperature of the hydrolysis
It can be 74 DEG C~78 DEG C.In an embodiment of the present invention, the hydrolysis can be carried out under conditions of stirring.
In a preferred embodiment of the invention, it is incubated after casein heating can be added into water, casein is fully swelled, obtain
To casein solution；Organic amine is added into the casein solution reaction is hydrolyzed, made casein complete hydrolysis, obtain hydrolyzed casein
Liquid.In an embodiment of the present invention, casein can be added into water under conditions of stirring.In an embodiment of the present invention, institute
The temperature for stating heating can be 70 DEG C~80 DEG C.In an embodiment of the present invention, the time of the insulation can for 0.5 hour~
1.5 hour.
Obtain after hydrolyzed casein liquid, it is of the invention by the hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy
Silane is reacted, and obtains modified Casein liquid.In the present invention, the γ-glycidyl ether oxygen propyl trimethoxy silicane
The source and weight of source and parts by weight with γ-glycidyl ether oxygen propyl trimethoxy silicane described in above-mentioned technical proposal
Number is consistent, will not be repeated here.
In an embodiment of the present invention, the temperature of the reaction can be 70 DEG C~80 DEG C；In other examples, institute
The temperature for stating reaction can be 74 DEG C~78 DEG C.In an embodiment of the present invention, the time of the reaction can be 1 hour~2
Hour.In a preferred embodiment of the invention, the reaction can be carried out under conditions of water-bath and insulation.
In an embodiment of the present invention, the hydrolyzed casein liquid can be added to γ-glycidyl ether oxygen propyl front three
Reacted in TMOS, obtain modified Casein liquid.
Obtain after modified Casein liquid, it is of the invention by the modified Casein liquid, acrylate monomer, persulfate and sulfurous acid
Polymerisation is carried out after salt mixing, leather finishing agent is obtained.In an embodiment of the present invention, the acrylate monomer, over cure
Acrylate monomer, persulfate described in species, source and the parts by weight and above-mentioned technical proposal of hydrochlorate and sulphite
Species, source with sulphite is consistent with parts by weight, will not be repeated here.
In an embodiment of the present invention, the temperature of the polymerisation can be 70 DEG C~90 DEG C；In other embodiments
In, the temperature of the polymerisation can be 75 DEG C~80 DEG C.In an embodiment of the present invention, the time of the polymerisation can
Think 2 hours~4 hours；In other examples, the time of the polymerisation can be 3 hours.
In a preferred embodiment of the invention, can be by the persulfate solution of the first mass parts and the Asia of the first mass parts
Sulfate liquor, which is added in acrylate monomer, carries out the first reaction, obtains reaction product；Added into the reaction product
The persulfate solution of second mass parts and the sulfite solution of the second mass parts carry out second and reacted, and obtain leather finish
Agent.
In the present invention, the sulfite solution and persulfate solution and the sulphite described in above-mentioned technical proposal
Solution is consistent with persulfate solution, will not be repeated here.In an embodiment of the present invention, the persulfuric acid of first mass parts
The mass ratio of salting liquid 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 first mass parts and the persulfate solution of the second mass parts can be 1:1.At this
In the embodiment of invention, the mass ratio of the sulfite solution of first mass parts and the sulfite solution of the second mass parts
Can be 1:(0.5~1.5)；In other examples, the sulfite solution and the second mass parts of first mass parts
Sulfite solution mass ratio can be 1:1.
In an embodiment of the present invention, first reaction can be carried out under conditions of stirring.In the implementation of the present invention
In example, the time of the stirring can be 8 minutes~12 minutes.In an embodiment of the present invention, the temperature of first reaction
It can be 70 DEG C~80 DEG C；In other examples, the temperature of first reaction can be 74 DEG C~78 DEG C.In the present invention
Embodiment in, it is described first reaction time can be 0.5 hour~1.5 hours；In other examples, described first
The time of reaction can be 1 hour.
In an embodiment of the present invention, the temperature of second reaction can be 75 DEG C~90 DEG C；In other embodiments
In, the temperature of second reaction can be 80 DEG C~85 DEG C.In an embodiment of the present invention, the time of second reaction can
Think 1 hour~3 hours；In other examples, the time of second reaction can be 2 hours.
In an embodiment of the present invention, after the completion of the polymerisation, obtained polymerizate can be cooled to 35 DEG C
~45 DEG C, obtain leather finishing agent.
The leather finishing agent that the method that the present invention is provided is prepared has preferable compliance and water resistance.In addition, this
The leather finishing agent for preparing of method that invention is provided can also improve the glossiness of leather, polish retention, plasticity, resistance to dry
Wiping property, wet-rub resistance, resistance to bent rich property, make the leather hand feeling after processing comfortable；And the present invention method that provides is prepared
Organic solvent, safety and environmental protection are free of in leather finishing agent.In addition, the preparation method technique for the leather finishing agent that the present invention is provided is steady
It is fixed, it is adapted to industrialized production.
The leather finishing agent that the present invention is provided is mainly used in the covering with paint of leather, both can be used for the primary coat of leather, it is also possible to
Applied in the top coat of leather or face.
The leather finishing agent that the present invention is provided is used to handle cow leather upper, and specific method is：On the surface of cow leather upper
Dried, polished and hot light after the leather finishing agent that the spraying present invention is provided, obtain single treatment leather；The temperature of the drying
Spend for 90 DEG C, the time of the drying is 1h.The present invention does not have special limitation to the method for the polishing and hot light, using this
The technical scheme of polishing and hot light in leather processing procedure known to art personnel.In the present invention, the polishing
Temperature be 90 DEG C；The method of the hot light is the hot pressing carried out in 120 DEG C, 10MPa calender 4 seconds；
Spray the leather finishing agent that provides of the present invention again to the leather surface of the single treatment, carry out secondary drying and
Hot light, the leather after being handled；The temperature of the drying is 90 DEG C, and the time of the drying is 1h；The method of the hot light
To carry out the hot pressing of 4 seconds in 120 DEG C, 10MPa calender.
By the leather after the processing according to QB/T1327《Leather surface colour fastness test method of testing》Standard, adopt
Resistance to xerotripsis test and wet-rub resistance test are carried out with XK-3078 leather surface color fastness experimental machines, test result is, this hair
The resistance to xerotripsis of leather after the leather finishing agent processing of bright offer is 4.5 grades~5 grades, and wet-rub resistance is 4.5 grades~5 grades.
Leather after the processing is tested into its glossiness using surface gloss instrument, test result is that the present invention is provided
Leather finishing agent processing after the glossiness of leather be that 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 processing described in above-mentioned technical proposal.Test knot
Fruit is that 4 volunteers think that the leather after the leather finishing agent processing that the present invention is provided is soft right, smooth.
The water resistance for the leather finishing agent that the present invention is provided is tested, specific method is：
The leather finishing agent that the present invention is provided carries out the drying of 24 hours in 60 DEG C of baking oven, makes the leather finish
Agent film forming；Leather finishing agent after film forming is weighed, record weight is A；
By the leather finishing agent after film forming, immersion is taken out after 24 hours in the beaker of the water equipped with 25 DEG C of constant temperature, uses filter paper
Dry the leather finishing agent film after immersion；The leather finishing agent film for drying water is weighed, record weight is B；According to following
Formula calculates the water resistance for the leather finishing agent that the present invention is provided：
Water resistance=B/A；
Result of calculation is that the water resistance for the leather finishing agent that the present invention is provided is 1.2~1.4.
Raw material used is commercial goods in following examples of the present invention, and the casein is the permanent natural cheese element of New Zealand
The lactic acid method casein 730 (casein) that company provides.
Embodiment 1
550g deionized water is added into reactor, 100g casein is added into the reactor under conditions of stirring
75 DEG C are warming up to, is stirred 1 hour, casein is fully expanded, obtain casein solution；It is molten to the casein under conditions of stirring
The triethanolamine that 20g is added in liquid carries out the hydrolysis of 2 hours, obtains hydrolyzed casein liquid；
Bath temperature is adjusted to 75 DEG C, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is added to above-mentioned water
The insulation reaction carried out in casein liquid 2 hours is solved, modified Casein liquid is obtained；
The mixture that the styrene of 22.5g butyl acrylate, 15g ethyl acrylate and 7.5g is constituted is used as propylene
Acid ester monomer, under conditions of stirring, is added in reactor, added into the reactor by 0.8g ammonium persulfate and
The ammonium persulfate aqueous solution of 25g deionized waters composition, the sodium hydrogensulfite being made up of 0.5g sodium hydrogensulfites and 25g deionized waters
The aqueous solution, is stirred 10 minutes, and first reaction of 1 hour is carried out at 75 DEG C；Added into obtained reaction product by 0.8g's
The ammonium persulfate aqueous solution of ammonium persulfate and 25g deionized waters composition, it is made up of 0.5g sodium hydrogensulfites and 25g deionized waters
Aqueous solution of sodium bisulfite, in the second reaction of 80 DEG C of progress 2 hours；
The second obtained reaction product is cooled to 40 DEG C, leather finishing agent is obtained.
According to the method described in above-mentioned technical proposal, the leather finishing agent prepared using the embodiment of the present invention 1 is to ox
Leather shoe surface is handled, the leather after being handled.
According to the method described in above-mentioned technical proposal, the feel of the leather after the processing that the test embodiment of the present invention 1 is obtained,
Resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, as shown in table 1, table 1 is the embodiment of the present invention and compared test result
The performance test results of leather after the processing that example is obtained.
According to the method described in above-mentioned technical proposal, the resistance to of the leather finishing agent that the embodiment of the present invention 1 is prepared is tested
Aqueous, test result is that the water resistance for the leather finishing agent that the embodiment of the present invention 1 is prepared is 1.4, and water resistance is preferable.
Embodiment 2
730g deionized water is added into reactor, 130g casein is added into the reactor under conditions of stirring
75 DEG C are warming up to, is stirred 1 hour, casein is fully expanded, obtain casein solution；It is molten to the casein under conditions of stirring
The triethanolamine that 26g is added in liquid carries out the hydrolysis of 2 hours, obtains hydrolyzed casein liquid；
Bath temperature is adjusted to 75 DEG C, 7g γ-glycidyl ether oxygen propyl trimethoxy silicane is added to above-mentioned water
The insulation reaction carried out in casein liquid 2 hours is solved, modified Casein liquid is obtained；
The mixture that the styrene of 20g butyl acrylate, 25g acrylonitrile and 20g is constituted is used as acrylate list
Body, under conditions of stirring, is added in reactor, and ammonium persulfate and 25g deionizations by 1g are added into the reactor
The ammonium persulfate aqueous solution of water composition, the aqueous solution of sodium bisulfite being made up of 0.8g sodium hydrogensulfites and 25g deionized waters, are stirred
Mix 10 minutes, first reaction of 1 hour is carried out at 75 DEG C；Added into obtained reaction product by 1g ammonium persulfate and
The ammonium persulfate aqueous solution of 25g deionized waters composition, the sodium hydrogensulfite being made up of 0.8g sodium hydrogensulfites and 25g deionized waters
The aqueous solution, in the second reaction of 80 DEG C of progress 1 hour；
The second obtained reaction product is cooled to 40 DEG C, leather finishing agent is obtained.
According to the method described in above-mentioned technical proposal, the leather finishing agent prepared using the embodiment of the present invention 2 is to ox
Leather shoe surface is handled, the leather after being handled.
According to the method described in above-mentioned technical proposal, the feel of the leather after the processing that the test embodiment of the present invention 2 is obtained,
Resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result are as shown in table 1.
According to the method described in above-mentioned technical proposal, the resistance to of the leather finishing agent that the embodiment of the present invention 2 is prepared is tested
Aqueous, test result is that the water resistance for the leather finishing agent that the embodiment of the present invention 2 is prepared is 1.3, and water resistance is preferable.
Embodiment 3
850g deionized water is added into reactor, 150g casein is added into the reactor under conditions of stirring
75 DEG C are warming up to, is stirred 1 hour, casein is fully expanded, obtain casein solution；It is molten to the casein under conditions of stirring
The triethanolamine that 30g is added in liquid carries out the hydrolysis of 2 hours, obtains hydrolyzed casein liquid；
Bath temperature is adjusted to 75 DEG C, 10g γ-glycidyl ether oxygen propyl trimethoxy silicane is added to above-mentioned water
The insulation reaction carried out in casein liquid 2 hours is solved, modified Casein liquid is obtained；
The mixture that the ethyl acrylate of 30g butyl acrylate, 30g acrylonitrile and 30g is constituted is used as acrylic acid
Ester monomer, under conditions of stirring, is added in reactor, adds and is gone by 1g ammonium persulfate and 25g into the reactor
The ammonium persulfate aqueous solution of ionized water composition, the sodium hydrogensulfite being made up of 0.8g sodium hydrogensulfites and 25g deionized waters are water-soluble
Liquid, is stirred 10 minutes, and first reaction of 1 hour is carried out at 75 DEG C；The persulfuric acid by 1g is added into obtained reaction product
The ammonium persulfate aqueous solution of ammonium and 25g deionized waters composition, the sulfurous acid being made up of 0.8g sodium hydrogensulfites and 25g deionized waters
Hydrogen sodium water solution, in the second reaction of 80 DEG C of progress 2 hours；
The second obtained reaction product is cooled to 40 DEG C, leather finishing agent is obtained.
According to the method described in above-mentioned technical proposal, the leather finishing agent prepared using the embodiment of the present invention 3 is to ox
Leather shoe surface is handled, the leather after being handled.
According to the method described in above-mentioned technical proposal, the feel of the leather after the processing that the test embodiment of the present invention 3 is obtained,
Resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result are as shown in table 1.
According to the method described in above-mentioned technical proposal, the resistance to of the leather finishing agent that the embodiment of the present invention 3 is prepared is tested
Aqueous, test result is that the water resistance for the leather finishing agent that the embodiment of the present invention 3 is prepared is 1.2, and water resistance is preferable.
Comparative example 1
800g deionized water is added into reactor, 150g casein is added into the reactor under conditions of stirring
75 DEG C are warming up to, is stirred 1 hour, casein is fully expanded, obtain casein solution；It is molten to the casein under conditions of stirring
The triethanolamine that 30g is added in liquid carries out the hydrolysis of 2 hours, obtains hydrolyzed casein liquid；
Bath temperature is adjusted to 75 DEG C, 10g caprolactam is dissolved in 50g deionized water to be configured to caprolactam molten
Liquid, the insulation reaction that above-mentioned hydrolyzed casein liquid is carried out 2 hours is added into the caprolactam solution, modified Casein liquid is obtained；
The mixture that the ethyl acrylate of 30g butyl acrylate, 30g acrylonitrile and 30g is constituted is used as acrylic acid
Ester monomer, under conditions of stirring, is added in reactor, adds and is gone by 1g ammonium persulfate and 25g into the reactor
The ammonium persulfate aqueous solution of ionized water composition, the sodium hydrogensulfite being made up of 0.8g sodium hydrogensulfites and 25g deionized waters are water-soluble
Liquid, is stirred 10 minutes, and first reaction of 1 hour is carried out at 75 DEG C；The persulfuric acid by 1g is added into obtained reaction product
The ammonium persulfate aqueous solution of ammonium and 25g deionized waters composition, the sulfurous acid being made up of 0.8g sodium hydrogensulfites and 25g deionized waters
Hydrogen sodium water solution, in the second reaction of 80 DEG C of progress 2 hours；
The second obtained reaction product is cooled to 40 DEG C, leather finishing agent is obtained.
According to the method described in above-mentioned technical proposal, the leather finishing agent prepared using comparative example 1 of the present invention is to ox
Leather shoe surface is handled, the leather after being handled.
According to the method described in above-mentioned technical proposal, the feel for the leather tested after the processing that comparative example 1 of the present invention is obtained,
Resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result are as shown in table 1.
According to the method described in above-mentioned technical proposal, the resistance to of the leather finishing agent that comparative example 1 of the present invention is prepared is tested
Aqueous, test result is that the leather finishing agent that comparative example 1 of the present invention is prepared is steeped rotten completely not water-fast.
Comparative example 2
By 30g DOWESION K 992 (the cation black pigment paste that Sichuan Da Wei companies provide), 80g 1530/T
(the cationic acrylamide yogurt that the new mark scholar of Italy provides), 100g 1521 (the cation caseins that the new mark scholar of Italy provides),
The models of DRIVER 5510 that 120g 1510 (cationic waxes that the new mark scholar of Italy provides), 30g Sichuan Da Wei companies provide
Bleeding agent and 350g water mixing, obtain bottom leather finishing agent coating.
30g DOWESION H 952 (the ion black pigment cream that Sichuan Da Wei companies provide), 30g Sichuan are reached into prestige
The black dyes water of DOWELLDYES BLACK 90R models that company provides, (Sichuan reaches prestige to 80g DOWELLIC RA 1101
The anionic acrylic emulsion that company provides), the 100g DOWELLIC RA 1105 (anion third that Sichuan Da Wei companies provide
Olefin(e) acid emulsion), 100g DOWELLIU RU 2059 (anionic polyurethane emulsion that Sichuan Da Wei companies provide), 60g
DOWELLIU RU 2301 (anionic polyurethane emulsion that Sichuan Da Wei companies provide), 160g Sichuan Da Wei companies provide
The bleeding agents of the types of DRIVER 5510 that the modified Caseins of the models of CASEIN 5833,30g Sichuan Da Wei companies provide, 60g
DOWELLER WAX 5050 (the anion wax emulsion that Sichuan Da Wei companies provide) and 350g water mixing, obtains top layer back cover
Leather finishing agent coating.
Dried, polished and hot light after the above-mentioned bottom leather finishing agent coating of surface spraying of cow leather upper, obtained
Single treatment leather；The temperature of the drying is 90 DEG C, and the time of the drying is 1 hour；The temperature of the polishing is 90 DEG C；
The method of the hot light is the hot pressing carried out in 120 DEG C, 10MPa calender 4 seconds；
Sprayed to the leather surface of the single treatment after above-mentioned top layer back cover leather finishing agent coating, carry out secondary drying
And hot light, the leather after being handled；The temperature of the drying is 90 DEG C, and the time of the drying is 1 hour；The hot light
Method is the hot pressing carried out in 120 DEG C, 10MPa calender 4 seconds.
According to the method described in above-mentioned technical proposal, the feel for the leather tested after the processing that comparative example 2 of the present invention is obtained,
Resistance to xerotripsis, wet-rub resistance, glossiness, 7 days glossiness, test result are as shown in table 1.
According to the method described in above-mentioned technical proposal, the bottom leather finishing agent that comparative example 2 of the present invention is prepared is tested
The water resistance of coating, test result is that the bottom leather finishing agent coating that comparative example 2 of the present invention is prepared is steeped rotten completely,
Water resistance is poor.
According to the method described in above-mentioned technical proposal, the top layer back cover leather painting that comparative example 2 of the present invention is prepared is tested
The water resistance of agent coating is adornd, test result is that the top layer back cover leather finishing agent coating that comparative example 2 of the present invention is prepared is complete
Steep rotten entirely, water resistance is poor.
The performance test results of leather after the processing that the embodiment of the present invention of table 1 and comparative example are obtained
As shown in Table 1, leather hand feeling softness, glossiness and gloss after the leather finishing agent processing that the present invention is provided are protected
Holding property is preferable, resistance to xerotripsis and wet-rub resistance are preferable.
As seen from the above embodiment, the invention provides a kind of leather finishing agent, by γ-glycidyl ether oxygen propyl front three
TMOS, acrylate monomer, persulfate, casein, organic amine, water and sulphite are prepared；The acrylate
Monomer includes more than three kinds in butyl acrylate, ethyl acrylate, styrene and acrylonitrile.The invention provides a kind of leather
The preparation method of finishing agent, acrylic acid is used by casein again using γ-glycidyl ether oxygen propyl trimethoxy silicane is modified
Ester monomer is modified, and contains epoxide group in γ-glycidyl ether oxygen propyl trimethoxy silicane, by modification, epoxide group connects
To in the macromolecular of casein with the polar group on casein side chain such as hydroxyl, amino, carboxyl etc. condensation reaction occurs for branch, makes
The leather finishing agent that invention is provided has preferable compliance and water resistance；, can by being modified again for acrylate monomer
Further improve the compliance and water resistance for the leather finishing agent that the present invention is provided.Therefore, the leather finishing agent that the present invention is provided
With preferable compliance and water resistance.In addition, the leather finishing agent that the present invention is provided can also improve the glossiness of leather, light
Damp retentivity, plasticity, resistance to xerotripsis, wet-rub resistance, resistance to bent rich property, make the leather hand feeling after processing comfortable；And the present invention is carried
Without organic solvents, safety and environmental protection such as APES class compounds in the leather finishing agent of confession.
Claims (9)
1. a kind of leather finishing agent, by γ-glycidyl ether oxygen propyl trimethoxy silicane, monomer, persulfate, casein, have
Machine amine, water and sulphite are prepared；The monomer is in butyl acrylate, ethyl acrylate, styrene and acrylonitrile
Three kinds.
2. leather finishing agent according to claim 1, it is characterised in that the γ-glycidyl ether oxygen propyl trimethoxy
Base silane, monomer, persulfate, casein, organic amine, the mass ratio of water and sulphite are (5~10):(45~100):(0.1
~1):(100~150):(20~30):(580~1000):(0.1~1).
3. leather finishing agent according to claim 1, it is characterised in that the persulfate is selected from ammonium persulfate, over cure
One or more in sour potassium and sodium peroxydisulfate.
4. leather finishing agent according to claim 1, it is characterised in that the organic amine is selected from triethylamine, diethylamine, three
One or more in monoethanolamine and diethanol amine.
5. leather finishing agent according to claim 1, it is characterised in that the sulphite is selected from sodium hydrogensulfite and Jiao
One or both of sodium sulfite.
6. a kind of preparation method of the leather finishing agent described in claim 1, comprises the following steps：
1) reaction, is hydrolyzed in casein and organic amine in water, hydrolyzed casein liquid is obtained；
2), the hydrolyzed casein liquid and γ-glycidyl ether oxygen propyl trimethoxy silicane are reacted, modified Casein is obtained
Liquid；
3) polymerisation is carried out after, mixing the modified Casein liquid, monomer, persulfate and sulphite, leather painting is obtained
Adorn agent；
The monomer is three kinds in butyl acrylate, ethyl acrylate, styrene and acrylonitrile.
7. method according to claim 6, it is characterised in that the step 1) in the temperature of hydrolysis be 70 DEG C~80
℃；
The time of hydrolysis is 1 hour~2 hours.
8. method according to claim 6, it is characterised in that the step 2) in the temperature of reaction be 70 DEG C~80 DEG C；
The time of reaction is 1 hour~2 hours.
9. method according to claim 6, it is characterised in that the step 3) in the temperature of polymerisation be 70 DEG C~90
℃；
The time of polymerisation is 2 hours~4 hours.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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| CN102532561B (en) * | 2011-12-19 | 2013-12-04 | 四川达威科技股份有限公司 | Modified casein, leather finishing agent and preparation method thereof |
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| 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 |
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