CN105385280A - Leather finishing agent and preparation method thereof - Google Patents
Leather finishing agent and preparation method thereof Download PDFInfo
- Publication number
- CN105385280A CN105385280A CN201510998295.0A CN201510998295A CN105385280A CN 105385280 A CN105385280 A CN 105385280A CN 201510998295 A CN201510998295 A CN 201510998295A CN 105385280 A CN105385280 A CN 105385280A
- Authority
- CN
- China
- Prior art keywords
- weight part
- hide finishes
- water
- initiator
- leather
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010985 leather Substances 0.000 title abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003999 initiator Substances 0.000 claims abstract description 45
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 33
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 22
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 21
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- 239000013067 intermediate product Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004945 emulsification Methods 0.000 claims description 13
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical group OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 12
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 12
- 239000012874 anionic emulsifier Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- HKLVLWGHCHJEIK-UHFFFAOYSA-N n-hydroxy-2-methylidenehexanamide Chemical compound CCCCC(=C)C(=O)NO HKLVLWGHCHJEIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 48
- 239000000243 solution Substances 0.000 description 44
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000009413 insulation Methods 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 18
- 229910052939 potassium sulfate Inorganic materials 0.000 description 18
- 235000011151 potassium sulphates Nutrition 0.000 description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 10
- 238000005452 bending Methods 0.000 description 10
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 10
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 10
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 210000000988 bone and bone Anatomy 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000006071 cream Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- SUOFREPYJDSUTJ-UHFFFAOYSA-N iron sulfurous acid Chemical compound [Fe].S(O)(O)=O SUOFREPYJDSUTJ-UHFFFAOYSA-N 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 235000010265 sodium sulphite Nutrition 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- -1 propylene amide Chemical class 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- 239000004159 Potassium persulphate Substances 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a leather finishing agent and a preparation method thereof. The leather finishing agent is prepared from, by weight, 7-28 parts of ethyl acrylate, 0-25 parts of butyl acrylate, 0-5 parts of methyl methacrylate, 0.2-2 parts of crylic acid and/or alkyl acrylate, 0.1-0.6 part of acrylamide derivative, 0.2-2 parts of emulgator, 0.01-2 parts of initiator and 50-70 parts of water. Compared with the prior art, crylic acid, alkyl acrylate and the acrylamide derivative in the leather finishing agent achieve the function of a cross-linking agent, the leather finishing agent is subjected to film forming, meanwhile, the ductility and cold tolerance of a film can be improved through ethyl acrylate and butyl acrylate, methyl methacrylate is a hard monomer, and the cohesion of the film can be improved. The ingredients act together, so that the leather finishing agent has high ductility and cold tolerance.
Description
Technical field
The invention belongs to leather processing technique field, particularly relate to a kind of hide finishes and preparation method thereof.
Background technology
Hide finishes is mainly used in the modification of leather, particularly must be indispensable in the polishing of various obverse leather, buffed leather and the process of ironing, hide finishes can make coating and leather surface bond securely, improve high temperature resistant flatiron and the polishability of leather, and hide finishes can also make leather keep the distinctive sanitation performance of natural leather.
High elastic clothes leather is the New-type leather product of domestic development, and it has the advantage such as good-extensibility, folding.The class improving domestic leatherware that appears as of high elastic clothes leather has made contribution, but due to the performance of its uniqueness, it is also proposed higher requirement for working the finishing agent acted on of making something perfect even more perfect, extensibility and winter hardiness are exactly wherein most important performance.Improve extensibility and the winter hardiness of finishing agent, can ensure to avoid occurring coating cracking in leather stretching and bending process, and then ensure good coating effect.
Acrylic resin is a most widely used class filmogen in coating material for leather, have cohesive force strong, smear smooth, bright, warping strength, extensibility is large and constitutionally stable feature, but there is the shortcomings such as winter hardiness is poor in it.For the leather with general elongation at break, require that the elongation at break of the membrane-forming agent of excellent property can reach about 1200%, and just higher for the elongation at break of the required membrane-forming agent of high elastic clothes leather.Although traditional leather finish can improve quality, the performance of leather products, change the outward appearance of leather, there is leather surface attractive in appearance, improve use properties and improve the effect of assortment, but in unit elongation and winter hardiness, all can not meet the requirement of high elastic clothes leather.
Application number is that the Chinese patent of CN201410480413 discloses a kind of cold resistant paint, comprises urethane and water, also adds propylene glycol n-butyl ether 5 ~ 10 parts, PSI 1 ~ 5 part, nano titanium oxide, polyamide resin 10 ~ 15 parts.This cold resistant paint has good cold-resistant advantage, but its unit elongation is not high, and it adopts urethane resin, and cost is higher.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of has hide finishes of good unit elongation and winter hardiness and preparation method thereof.
The invention provides a kind of hide finishes, it is characterized in that, prepared by following composition:
Preferably, in described alkyl acrylic, the carbonatoms of alkyl is 1 ~ 5.
Preferably, described acrylamide derivative is the acrylamide derivative comprising hydroxyl.
Preferably, described acrylamide derivative is n-methylolacrylamide and/or hydroxyl butylacrylamide.
Preferably, described emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent.
Preferably, the mass ratio of described anionic emulsifier and nonionic emulsifying agent is (1.5 ~ 2.5): 1.
Preferably, described anionic emulsifier is one or more in sodium lauryl sulphate, sodium laurylsulfonate and Sodium dodecylbenzene sulfonate.
Preferably, described nonionic emulsifying agent is one or more in emulsifying agent SA-9, emulsifying agent DIPONILA-4056, EmulsogenLCN407 and paregal O.
Present invention also offers a kind of preparation method of hide finishes, comprise the following steps:
A) acrylamide derivative of the methyl methacrylate of the butyl acrylate of the ethyl propenoate of 7 ~ 28 weight parts, 0 ~ 25 weight part, 0 ~ 5 weight part, the vinylformic acid of 0.1 ~ 2 weight part and/or alkyl acrylic, 0.1 ~ 0.6 weight part, the emulsifying agent of 0.2 ~ 2 weight part, the initiator of 0.01 ~ 2 weight part are mixed with the water of 50 ~ 70 weight parts, reacting by heating, obtains hide finishes.
Preferably, described steps A) comprising:
A1) butyl acrylate of the ethyl propenoate of 7 ~ 28 weight parts, 0 ~ 25 weight part, the vinylformic acid of 0.1 ~ 2 weight part and/or alkyl acrylic, the emulsifying agent of 0.2 ~ 2 weight part, the acrylamide derivative of 0.1 ~ 0.6 weight part are mixed with water, carry out pre-emulsification, obtain pre-emulsion;
A2) described pre-emulsion, initiator are mixed with water, heating is reacted, and obtains the first intermediate product;
A3) described first intermediate product, the methyl methacrylate of 0 ~ 5 weight part, initiator are mixed with water, heating is reacted, and obtains the second intermediate product;
A4) described second intermediate product, initiator are mixed with water, heating is reacted, and obtains hide finishes;
Described steps A 1), steps A 2), steps A 3) with steps A 4) in water be total up to 50 ~ 70 weight parts; Described steps A 2), steps A 3) with steps A 4) in initiator be total up to 0.01 ~ 2 weight part.
The invention provides a kind of hide finishes and preparation method thereof, prepared by following composition: 7 ~ 28 parts by weight propylene acetoacetic esters, 0 ~ 25 parts by weight propylene acid butyl ester, 0 ~ 5 parts by weight of methylmethacrylate, 0.2 ~ 2 parts by weight of acrylic acid and/or alkyl acrylic, 0.1 ~ 0.6 parts by weight propylene amide derivatives, 0.2 ~ 2 parts by weight Emulsifier, 0.01 ~ 2 weight part initiator and 50 ~ 70 weight parts waters.Compared with prior art, in hide finishes of the present invention, vinylformic acid, alkyl acrylic and acrylamide derivative play the effect of linking agent, make hide finishes film forming, simultaneously, ethyl propenoate and butyl acrylate can improve unit elongation and the winter hardiness of film, methyl methacrylate is the force of cohesion that hard monomer can improve film, mentioned component acting in conjunction, makes hide finishes of the present invention have higher unit elongation and winter hardiness.
Embodiment
Below in conjunction with the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of hide finishes, prepared by following composition:
Wherein, the restriction that the present invention is not special to the source of all raw materials, for commercially available.
The content of described ethyl propenoate is preferably 10 ~ 25 weight parts, is more preferably 10 ~ 20 weight parts, then is preferably 10 ~ 16 weight parts.Ethyl propenoate can improve extensibility and the winter hardiness of the film that hide finishes is formed.
The content of described butyl acrylate is preferably 5 ~ 25 weight parts, is more preferably 8 ~ 20 weight parts, then is preferably 10 ~ 16 weight parts.Butyl acrylate can improve extensibility and the winter hardiness of the film that hide finishes is formed.
The content of described methyl methacrylate is preferably 1 ~ 5 weight part, is more preferably 2 ~ 4 weight parts.Methyl methacrylate is hard monomer, can improve the force of cohesion of film.
The content of described vinylformic acid and/or alkyl acrylic is preferably 0.5 ~ 2 weight part, is more preferably 0.7 ~ 1.2 weight part; In described alkyl acrylic, the carbonatoms of alkyl is preferably 1 ~ 5, is more preferably 1 ~ 3, then is preferably 1 ~ 1, and most preferably be 1, now alkyl acrylic is methacrylic acid.
The content of described acrylamide derivative is preferably 0.2 ~ 0.5 weight part, is more preferably 0.2 ~ 0.4 weight part; Described acrylamide derivative preferably comprises the acrylamide derivative of hydroxyl, is more preferably n-methylolacrylamide and/or hydroxyethyl acrylamide.Vinylformic acid and/or alkyl acrylic and acrylamide derivative play the effect of linking agent.
The content of described emulsifying agent is preferably 0.4 ~ 2 weight part, is more preferably 0.6 ~ 2 weight part, then is preferably 0.6 ~ 1.5 weight part; Described emulsifying agent is preferably the mixture of anionic emulsifier and nonionic emulsifying agent; The mass ratio of described anionic emulsifier and nonionic emulsifying agent is preferably (1.5 ~ 2.5): 1, is more preferably (1.8 ~ 2.2): 1; Described anionic emulsifier is emulsifying agent well known to those skilled in the art, there is no special restriction, is preferably one or more in sodium lauryl sulphate, sodium laurylsulfonate and Sodium dodecylbenzene sulfonate in the present invention; Described nonionic emulsifying agent is nonionic emulsifying agent well known to those skilled in the art, there is no special restriction, is preferably one or more in emulsifying agent SA-9, emulsifying agent DIPONILA-4056, EmulsogenLCN407 and paregal O in the present invention.
The content of described initiator is preferably 0.02 ~ 2 weight part, is more preferably 0.05 ~ 1.5 weight part, then is preferably 0.1 ~ 1.5 weight part; The kind of described initiator is water soluble starter well known to those skilled in the art and redox initiator, there is no special restriction; Wherein said water soluble starter is preferably persulphate, is more preferably one or more in ammonium persulphate, Sodium Persulfate and Potassium Persulphate; Described redox initiator is preferably the one in Potassium Persulphate and sodium hydrogen sulfite system, ammonium persulphate and vat powder system, tert-butyl peroxide and rongalite, more preferably also adds and helps reductive agent; The described reductive agent that helps is preferably metal-salt, is more preferably ferrous sulfate and/or cuprous sulfate.
The content of described water is preferably 50 ~ 67 weight parts, more preferably makes above-mentioned hide finishes composition and water be total up to 100 weight parts.
In hide finishes of the present invention, vinylformic acid, alkyl acrylic and acrylamide derivative play the effect of linking agent, make hide finishes film forming, simultaneously, ethyl propenoate and butyl acrylate can improve unit elongation and the winter hardiness of film, methyl methacrylate is the force of cohesion that hard monomer can improve film, mentioned component acting in conjunction, makes hide finishes of the present invention have higher unit elongation and winter hardiness.
Present invention also offers a kind of preparation method of above-mentioned hide finishes, comprise the following steps: A) acrylamide derivative of the methyl methacrylate of the butyl acrylate of the ethyl propenoate of 7 ~ 28 weight parts, 0 ~ 25 weight part, 0 ~ 5 weight part, the vinylformic acid of 0.1 ~ 2 weight part and/or alkyl acrylic, 0.1 ~ 0.6 weight part, the emulsifying agent of 0.2 ~ 2 weight part, the initiator of 0.01 ~ 2 weight part are mixed with the water of 50 ~ 70 weight parts, reacting by heating, obtains hide finishes.
Wherein, described ethyl propenoate, butyl acrylate, methyl methacrylate, vinylformic acid and/or alkyl acrylic, acrylamide derivative, emulsifying agent, initiator and water are all same as above, do not repeat them here.
According to the present invention, described steps A) preferably carry out according to following steps:
A1) butyl acrylate of the ethyl propenoate of 7 ~ 28 weight parts, 0 ~ 25 weight part, the vinylformic acid of 0.1 ~ 2 weight part and/or alkyl acrylic, the emulsifying agent of 0.2 ~ 2 weight part, the acrylamide derivative of 0.1 ~ 0.6 weight part are mixed with water, carry out pre-emulsification, obtain pre-emulsion;
A2) described pre-emulsion, initiator are mixed with water, heating is reacted, and obtains the first intermediate product;
A3) described first intermediate product, the methyl methacrylate of 0 ~ 5 weight part, initiator are mixed with water, heating is reacted, and obtains the second intermediate product;
A4) described second intermediate product, initiator are mixed with water, heating is reacted, and obtains hide finishes;
Described steps A 1), steps A 2), steps A 3) with steps A 4) in water be total up to 50 ~ 70 weight parts; Described steps A 2), steps A 3) with steps A 4) in initiator be total up to 0.01 ~ 2 weight part, preferred described steps A 2), steps A 3) with steps A 4) in the mass ratio of initiator be (0.3 ~ 1): (1 ~ 2): (1 ~ 4).
The butyl acrylate of the ethyl propenoate of 7 ~ 28 weight parts, 0 ~ 25 weight part, the vinylformic acid of 0.1 ~ 1.2 weight part and/or alkyl acrylic, the emulsifying agent of 0.2 ~ 2 weight part, the acrylamide derivative of 0.1 ~ 0.6 weight part are mixed with water, carry out pre-emulsification, obtain pre-emulsion.
Then in pre-emulsion, add initiator and water, preferably first mixed with water by initiator, and then mix with pre-emulsion in the present invention, heating is reacted, and the temperature of described heating is preferably 70 DEG C ~ 90 DEG C; Then preferably lower the temperature, be more preferably cooled to 50 DEG C ~ 60 DEG C, then add the methyl methacrylate of 0 ~ 5 weight part, initiator and water, add again in reaction system after preferably first initiator being mixed with water, insulation is reacted, and preferred reaction 10 ~ 20min, obtains the second intermediate product.Finally described second intermediate product, initiator are mixed with water, preferably first initiator is mixed with water, then be added in the second intermediate product, more preferably being mixed with water by initiator is added in the second intermediate product at twice, each insulation reaction 10 ~ 20min, finally lowers the temperature, preferably near 30 DEG C ~ 45 DEG C, the pH value of regulation system is 7.0 ~ 8.0, obtains hide finishes.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of hide finishes provided by the invention and preparation method thereof is described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
By 120g deionized water, 2.5g sodium lauryl sulphate, 32g ethyl propenoate, 54g butyl acrylate, 3g vinylformic acid and 1g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 10g methyl methacrylate is added in reaction flask, add 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite) again, insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the embodiment 1 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in embodiment 1, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g embodiment 1 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Embodiment 2
By 120g deionized water, 2.5g sodium lauryl sulphate, 31.5g ethyl propenoate, 53.5g butyl acrylate, 3g vinylformic acid and 2g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 10g methyl methacrylate is added in reaction flask, add 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite) again), insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the embodiment 2 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in embodiment 2, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g embodiment 2 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Embodiment 3
By 150g deionized water, 2.5g sodium lauryl sulphate, 1g emulsifying agent SA-9, 31.5g ethyl propenoate, 3g vinylformic acid and 2g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 10g methyl methacrylate is added in reaction flask, add 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite) again), insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the embodiment 2 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in embodiment 2, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g embodiment 2 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Embodiment 4
By 100g deionized water, 2.25g sodium lauryl sulphate, 1.25g emulsifying agent DIPONILA-4056, 31.5g ethyl propenoate, 3g vinylformic acid and 2g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, add 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite) again), insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the embodiment 2 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in embodiment 2, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g embodiment 2 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Embodiment 5
By 120g deionized water, 2.5g sodium lauryl sulphate, 32g ethyl propenoate, 54g butyl acrylate, 3g vinylformic acid and 1g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 10g methyl methacrylate is added in reaction flask, add 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.1g70% tert-butyl peroxide and 4g contain 0.1g rongalite) again), insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the embodiment 2 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in embodiment 2, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g embodiment 2 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Comparative example 1
By 120g deionized water, 2.5g sodium lauryl sulphate, 96g ethyl propenoate, 3g vinylformic acid and 1g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite) is added, insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the comparative example 1 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in comparative example 1, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g comparative example 1 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Comparative example 2
By 120g deionized water, 2.5g sodium lauryl sulphate, 96g butyl acrylate, 3g vinylformic acid and 1g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite) is added, insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the comparative example 2 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in comparative example 2, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g comparative example 2 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Comparative example 3
By 120g deionized water, 2.5g sodium lauryl sulphate, 86g ethyl propenoate, 3g vinylformic acid and 1g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 10g methyl methacrylate is added in reaction flask, add 8g initiator solution (4g contains the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite) again, insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the comparative example 3 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in comparative example 3, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g comparative example 3 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Comparative example 4
By 120g deionized water, 2.5g sodium lauryl sulphate, 86g butyl acrylate, 3g vinylformic acid and 1g n-methylolacrylamide load in flask to mix carries out pre-emulsification, then 1g monsel solution (containing 0.003g seven water sulfurous acid iron) is added, 5g potassium sulfate solution (containing 0.1g potassium sulfate) and 10g sodium sulfite solution (containing 0.5g sodium bisulfite) initiated polymerization, after temperature is raised to 90 DEG C, be cooled to 60 DEG C again, then 10g methyl methacrylate is added in reaction flask, add 8g initiator solution (containing the aqueous solution that the aqueous solution of 0.8g70% tert-butyl peroxide and 4g contain 0.6g rongalite containing 4g) again, insulation 15min, add the initiator solution twice of same components same amount again, each insulation 15min, finally, be cooled to 40 DEG C, adding ammoniacal liquor adjust ph is 7.0 ~ 8.0, obtain hide finishes.
According to GB/T508-1998, employing thickness is the film of hide finishes formation prepared by the comparative example 4 of 1mm (± 0.4mm), use standard dog bone stage property, preparation standard examination bar, and measure its thickness with screw micrometer, and be minimum entrance power with 0.01N, the draw speed of 100mm/min, tension test test is carried out to the hide finishes obtained in comparative example 4, obtains the results are shown in Table 1.
The cold-resistant flexibility testing method of hide finishes coating leather: the resistance to bend(ing) under wet or dry condition is based on leather chemistry man international federation IUF20 method, use Bally flexometer, bending dry or wet leather sample (65mm × 40mm), then-15 DEG C check the level of breakage after recorded number of bends.Tested by following concrete grammar in the present invention: the hide finishes obtained in 350g comparative example 4 is mixed with 100g black pigment cream (Sichuan reaches prestige H952), and be supplemented to 500g with water and prepare leather coating.First brush one deck (6g/ square feet) on buffed leather, dry rear dull and stereotyped 90 DEG C ,/5 kilograms press down 2s, more two-layer according to the spraying of 3g/ square feet, drying, place one day afterwards test (-15 DEG C) deflect performance, test result is in table 2.
Table 1 tension test test result
Table 2 resists cold flexibility test result
Wherein PA is the SB300 polyacrylic acid hide finishes of LANXESS.
As shown in Table 1, embodiment 1 has more excellent elongation at break with hide finishes in embodiment 2 than comparative example 1 ~ 4 and PA, is more suitable for the covering with paint of highly elastic leather.
As shown in Table 2, be coated with embodiment 1 to have respectively obviously than scribbling the more excellent performance of comparative example 1 ~ 4 with embodiment 2 and the leather of PA, covering with paint for highly elastic leather can improve its cold-resistant flexibility, although the cold-resistant flexibility of PA is good, but its elongation at break is lower, be not suitable for the covering with paint of highly elastic leather.
Claims (10)
1. a hide finishes, is characterized in that, is prepared by following composition:
2. hide finishes according to claim 1, is characterized in that, in described alkyl acrylic, the carbonatoms of alkyl is 1 ~ 5.
3. hide finishes according to claim 1, is characterized in that, described acrylamide derivative is the acrylamide derivative comprising hydroxyl.
4. hide finishes according to claim 1, is characterized in that, described acrylamide derivative is n-methylolacrylamide and/or hydroxyl butylacrylamide.
5. hide finishes according to claim 1, is characterized in that, described emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent.
6. hide finishes according to claim 5, is characterized in that, the mass ratio of described anionic emulsifier and nonionic emulsifying agent is (1.5 ~ 2.5): 1.
7. hide finishes according to claim 5, is characterized in that, described anionic emulsifier is one or more in sodium lauryl sulphate, sodium laurylsulfonate and Sodium dodecylbenzene sulfonate.
8. hide finishes according to claim 5, is characterized in that, described nonionic emulsifying agent is one or more in emulsifying agent SA-9, emulsifying agent DIPONILA-4056, EmulsogenLCN407 and paregal O.
9. a preparation method for hide finishes, is characterized in that, comprises the following steps:
A) acrylamide derivative of the methyl methacrylate of the butyl acrylate of the ethyl propenoate of 7 ~ 28 weight parts, 0 ~ 25 weight part, 0 ~ 5 weight part, the vinylformic acid of 0.1 ~ 2 weight part and/or alkyl acrylic, 0.1 ~ 0.6 weight part, the emulsifying agent of 0.2 ~ 2 weight part, the initiator of 0.01 ~ 2 weight part are mixed with the water of 50 ~ 70 weight parts, reacting by heating, obtains hide finishes.
10. preparation method according to claim 9, is characterized in that, described steps A) comprising:
A1) butyl acrylate of the ethyl propenoate of 7 ~ 28 weight parts, 0 ~ 25 weight part, the vinylformic acid of 0.1 ~ 2 weight part and/or alkyl acrylic, the emulsifying agent of 0.2 ~ 2 weight part, the acrylamide derivative of 0.1 ~ 0.6 weight part are mixed with water, carry out pre-emulsification, obtain pre-emulsion;
A2) described pre-emulsion, initiator are mixed with water, heating is reacted, and obtains the first intermediate product;
A3) described first intermediate product, the methyl methacrylate of 0 ~ 5 weight part, initiator are mixed with water, heating is reacted, and obtains the second intermediate product;
A4) described second intermediate product, initiator are mixed with water, heating is reacted, and obtains hide finishes;
Described steps A 1), steps A 2), steps A 3) with steps A 4) in water be total up to 50 ~ 70 weight parts; Described steps A 2), steps A 3) with steps A 4) in initiator be total up to 0.01 ~ 2 weight part.
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| CN109135480A (en) * | 2018-08-16 | 2019-01-04 | 广州市麦吉高分子材料有限公司 | A kind of cold-resistant acrylic emulsion leather agent and preparation method thereof |
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Application publication date: 20160309 |