CN106947382B - A kind of polyurethane finishing agent - Google Patents
A kind of polyurethane finishing agent Download PDFInfo
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- CN106947382B CN106947382B CN201710287200.3A CN201710287200A CN106947382B CN 106947382 B CN106947382 B CN 106947382B CN 201710287200 A CN201710287200 A CN 201710287200A CN 106947382 B CN106947382 B CN 106947382B
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- hide
- polyurethane
- finishing agent
- diisocyanate
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 81
- 239000004814 polyurethane Substances 0.000 title claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 73
- 239000010985 leather Substances 0.000 claims abstract description 24
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 11
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 11
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract 2
- 238000010409 ironing Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 230000010358 mechanical oscillation Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- -1 hydroxyalkyl silicon Chemical compound 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 108010035532 Collagen Proteins 0.000 abstract description 18
- 102000008186 Collagen Human genes 0.000 abstract description 18
- 229920001436 collagen Polymers 0.000 abstract description 18
- 239000004744 fabric Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000003672 processing method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 229920001864 tannin Polymers 0.000 description 12
- 235000018553 tannin Nutrition 0.000 description 12
- 239000001648 tannin Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 108010077465 Tropocollagen Proteins 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 102000008946 Fibrinogen Human genes 0.000 description 1
- 108010049003 Fibrinogen Proteins 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229940012952 fibrinogen Drugs 0.000 description 1
- 244000309465 heifer Species 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000037303 wrinkles Effects 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of polyurethane finishing agents, including alcohols solvent and polyurethane solute, the polyurethane prepolymer and sodium hydrogensulfite end-capping reagent that wherein the polyurethane is formed by oligomer polyol with diisocyanate are prepared as a raw material, and the molar ratio of the oligomer polyol, diisocyanate and sodium hydrogensulfite is 1:2~3:2~3.Elastic construction can be formed in the collagen fabric of leather using polyurethane finishing agent provided by the invention, improve leather elasticity.And polyurethane finishing agent provided by the invention is conducive to industrialized production in the preparation without using toxic organic solvent.
Description
Technical field
The present invention relates to a kind of leather treatment, especially a kind of polyurethane finishing agent.
Background technique
In leather manufacture, especially handbag product manufacturing industry, the elastic recovery of ox-hide is particularly significant, the property
The appearance that product can not only be influenced more influences the function of product.
In existing leather processing, using organic silicone finishing agent or wax, grease-filled leather, make its softening, and
Improve its elastic recovery.But the elastic recovery of the leather of these processing methods acquisition cannot be lasting.As shown in Figure 1, ox
Skin is full of filler 12 after the filling of existing leather processing between the collagen fabric 11 of ox-hide；However, making
With in the process, ox-hide is caused the filler 12 between collagen fabric 11 by different degrees of extrusion by external force F extruding, simultaneously
New chemical bond 13 is formed between collagen fabric 11, causes ox-hide thinning and elastic recovery reduces.Therefore, how
The elasticity and elastic stability for improving ox-hide become research hotspot.
Polyurethane correlation finishing agent early has record, for example, a kind of Publication No. CN102070759A " aqueous polyurethane skin
The preparation method of leather retanning agent ", Publication No. CN103030769A " a kind of polyurethane retanning agent ", notification number
CN104073575B " fur tanning agent and preparation method thereof based on isocyanates " discloses polyurethane finishing agent with good
Filling effect, however, fillibility polyurethane is not crosslinked with ox-hide and is reacted, after long-time use, ox-hide impaired performance.In addition
During the preparation process, it is related to the use of toxic organic solvent, such as tetrahydrofuran, benzene, toluene, is unfavorable for industrialized production.
In the U.S. Patent application of United States Patent (USP) US2923594, US2523326 and Publication No. 20060080784A1
It discloses isocyanates and its related polymer is used as the relevant information of tanning finishing agent.The wherein molecular mass of isocyanates
It is relatively low, and can be effectively crosslinked with collagen molecules, to improve the shrinkage temperature of leather, but leather can not be improved
Elasticity.
Summary of the invention
In order to overcome the drawbacks of the prior art, the present invention propose it is a kind of can improve leather elasticity and prepare when without using poison
The polyurethane finishing agent of property organic solvent.
For this purpose, a kind of polyurethane finishing agent provided by the invention, comprising: alcohols solvent and polyurethane solute,
The polyurethane prepolymer and sodium hydrogensulfite that wherein the polyurethane is formed by oligomer polyol and diisocyanate block
Agent is prepared as a raw material, and the molar ratio of the oligomer polyol, diisocyanate and sodium hydrogensulfite is 1:2~3:2
~3.
Preferably, the alcohols solvent is ethyl alcohol or isopropanol.
Preferably, the solid content of the polyurethane finishing agent is 45~49%.
Preferably, the molecular weight of the oligomer polyol is 1000~8000, and degree of functionality is 2~3.
Preferably, the oligomer polyol is selected from the one or more of polyether polyol or hydroxyalkyl silicone oil.
Preferably, the diisocyanate is selected from isophorone diisocyanate, 4,4- dicyclohexyl methyl hydride, two isocyanide
Acid esters, cyclohexanedimethyl diisocyanate and toluene di-isocyanate(TDI).
Preferably, dibutyl tin dilaurate is used when the oligomer polyol and diisocyanate form prepolymerization reaction
As catalyst.
Preferably, dosage of the dibutyl tin dilaurate in the prepolymerization reaction is 20~100ppm.
Preferably, the pH value of the polyurethane finishing agent is 3~5.
Preferably, sulfuric acid, hydrochloric acid, acetic acid or the formic acid that the pH value of the polyurethane finishing agent uses are adjusted.
The invention has the benefit that the polyurethane finishing agent in the present invention is that have multi-functional molecule flexible
The crosslinking of multidigit point can occur with the collagenous fibres in leather for chain.Polyurethane finishing agent of the invention has two to three active officials
It can roll into a ball, can be bonded simultaneously with different collagenous fibres, similar to " bridge " is costed between tropocollagen molecule, play effective friendship
Connection effect；Meanwhile will not be excessive because of crosslinking points, so as to cause collagenous fibres are bonded excessively, it is unfavorable for leather elasticity instead
Enhancing.In addition, isocyanates hard section assigns molecule chain rigidity, polyalcohol in polyurethane molecular chain in the polyurethane finishing agent
Soft segment assigns Chain Flexibility, and the polyalcohol that soft segment is macromolecular is chosen in the polyurethane, make polyurethane finishing agent have compared with
High-flexibility.After being applied to leather arrangement using polyurethane finishing agent of the present invention, when leather is by bending external force, between collagen
Polyurethane molecular chain play the role of support, after external force is removed, polyurethane molecular chain can play the effect of " spring ", side
Its rebound is helped, the elasticity of leather is improved.
Detailed description of the invention
Fig. 1 is the schematic diagram that the collagen fabric structure of prior art heifer is deformed in use；
Fig. 2 is the chemical reaction schematic diagram of step S12 in embodiment 1；
Fig. 3 is the chemical reaction schematic diagram of step S14 in embodiment 1；
Fig. 4 is the cross-linking reaction schematic diagram of step A11 in embodiment 1；
Fig. 5 is the schematic diagram for the ox-hide wet blue that step A11 is used in embodiment 1；
Fig. 6 is that the collagen fabric structure change before and after being handled ox-hide using the processing method provided by the present invention is illustrated
Figure；
Fig. 7 is the schematic diagram that the collagen fabric structure of treated ox-hide in Fig. 6 is deformed in use.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.
Embodiment one
A kind of polyurethane finishing agent S1 provided in this embodiment and preparation method thereof and using the polyurethane finishing agent
Ox-hide processing method.
The preparation method of the polyurethane finishing agent S1 the following steps are included:
S11: by the polypropylene oxide triol (abbreviation of 0.1mol degree of functionality Fn=3, number-average molecular weight Mn=1000g/mol
For two laurels of reactant and 20ppm that the isophorone diisocyanate (english abbreviation IPDI) of PPG) and 0.3mol forms
Sour dibutyl tin (english abbreviation DBTDL) catalyst is added in the three-necked flask of a 1000ml；
S12: under conditions of 85 DEG C of oil baths, mechanical stirring is carried out to the reactant in the three-necked flask, is reacted 2 hours
Afterwards, the polyurethane prepolymer that reaction is formed is down to room temperature, chemically reacts schematic diagram as shown in Fig. 2, the polyurethane prepolymer
PPG and IPDI interconnection in object forms the chain-like molecular structure of PPG-IPDI-PPG-IPDI ...；
S13: the polyurethane prepolymer is diluted to the solution that solidification amount is 50% using ethyl alcohol；
S14: the sodium hydrogensulfite (NaHSO for the use of mass percent being 30%3) aqueous solution is added into the solution
0.3mol sodium hydrogensulfite carries out end capping reaction to the polyurethane prepolymer, reacts 1 hour at room temperature, and chemical reaction is shown
It is intended to as shown in Figure 3；
S15: the dilute sulfuric acid (H for the use of mass percent being 20%2SO4) adjust the pH value of the solution to 5, that is, it is formed
The polyurethane finishing agent S1 that solid content is about 45%.
Using polyurethane finishing agent S1 ox-hide processing method the following steps are included:
A11: ox-hide wet blue 50 is used to be put into rotary drum as raw material when tanning arranges referring to Fig. 5, with ox-hide indigo plant
The quality of wet skin 50 is benchmark quality, and the water of 100% Reference mass is first added, then 6%, 5% and 5% benchmark matter is added in three times
Weight polyurethane finishing agent S1, every minor tick 15 minutes, as shown in figure 4, after the polyurethane finishing agent S1 is soluble in water, polyurethane
Sodium hydrogensulfite block be detached from, expose end NCO group 21 and the ox-hide in collagen fabric NH2Group 31
It is bonded, formation crosslinking points 35, by 30 elastic connection of strand of the polyurethane between each crosslinking points 35, wherein poly- ammonia
The NCO group 21 of ester end and the NH of the collagen fabric2The reaction equation that group 31 is crosslinked is as follows:
-NCO+-NH2→-NH-CO-NH-；
A12: being added the pigment of 1% Reference mass, handles 1 hour；
A13: draining is added the Synthetic Oil of 8% Reference mass, handles 1 hour at 50 DEG C；
A14: taking out treated ox-hide, using vacuum ironing machine, ox-hide 3~4 minutes described in ironing at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
A15: being sprayed at the ox-hide inner surface after drying for moisture again, make the moisture content of the ox-hide reach 10%~
15%；
A16: the soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface applies ox-hide surface rubbing to ox-hide
Color/color spray processing presses the ox-hide by rotary ironing machine, and ironing temperature is 100~150 DEG C, this implementation is obtained after ironing
The ox-hide A1 of example ox-hide processing method processing.
In step A11, the polyurethane finishing agent S1 is spaced addition in three times, is conducive to slowly permeate, and avoids primary
Property be added excessive concentration the ox-hide surface react it is too fast, hinder the polyurethane finishing agent S1 it is further infiltration and instead
It answers.In step A14, using vacuum ironing machine ironing, the adhesion strength of pigment, grease and ox-hide is increased, ox-hide is dyed
Securely, the hydrophobicity and elasticity of ox-hide are improved.The pliability of soft adjustable ox-hide is drawn in mechanical oscillation in step A16, keeps ox-hide fine
Dimension becomes loose, thus the softness for becoming ox-hide；The flaw that ox-hide surface can be covered is modified ox-hide surface；It tints/sprays
Color can protect ox-hide surface property and ox-hide surface color is made to become uniform；Ox-hide is pressed by rotary ironing machine, reduces ox-hide
Moisture makes ox-hide become smooth.In various embodiments, can according to the demand of ox-hide product, repeat it is described draw it is soft, apply
Color/color spray, ironing process.
In order to compare the ox-hide A1 of prior art tannin ox-hide and the ox-hide processing method processing using the present embodiment, use
Common tanning agent handles same batch with the ox-hide wet blue at position, makes conventional kraft B1, comprising the following steps:
B11: when tanning arranges, ox-hide wet blue 50 is used to be put into rotary drum as raw material, with ox-hide wet blue 50
Quality is benchmark quality, is first added the water of 100% Reference mass, then (english abbreviation is by the resin tannin of 2% Reference mass
Relugan D) and the composite filled tannin of synthesis (english abbreviation the be Basyntan HL) mixing of 5.5% Reference mass after points three
2.5% Reference mass, every minor tick 10~15 minutes is added in secondary addition every time；
B12: by the acrylate resin tanning of the neutralization tannin (english abbreviation NTL) of 4% Reference mass and 8% Reference mass
It is added in three times after agent mixing, 4% Reference mass, every minor tick 10~15 minutes is added every time；
B13: by the resin retaning agent (english abbreviation is Retingan R7) of 3% Reference mass, the grain of 4% Reference mass
Wood, the neutralization tannin (english abbreviation is Tamol M) of 1.5% Reference mass, polymer tannin (the English contracting of 2% Reference mass
Be written as Relugan FR-RV) and 1% Reference mass pigment be added after, handle 2 hours；
B14: draining is added the Synthetic Oil of 8% Reference mass, handles 1 hour at 50 DEG C；
B15: taking out treated ox-hide, using vacuum ironing machine, ox-hide 3~4 minutes described in ironing at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
B16: being sprayed at the ox-hide inner surface after drying for moisture again, make the moisture content of the ox-hide reach 10%~
15%；
B17: the soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface applies ox-hide surface rubbing to ox-hide
Color/color spray processing after ironing, obtains the ox-hide B1 of common tanning agent processing.
Referring to Fig. 5, the direction along the ridge line 51 of ox-hide wet blue 50 is Y-direction, and the direction perpendicular to ridge line 51 is X
To.Using AATCC 66-2008Wrinkle Recovery of Woven Fabrics:RecoveryAngle (AATCC 66-
2008 woven fabric wrinkle recoveries: recovery angle test) testing standard carries out recovery angle test to ox-hide A1 and ox-hide B1, fold 15 points
Recovery angle testing result after clock is as shown in table 1.
Table 1
Embodiment two
A kind of polyurethane finishing agent S2 provided in this embodiment and preparation method thereof and using the polyurethane finishing agent
Ox-hide processing method.
The preparation method of the polyurethane finishing agent S2 the following steps are included:
S21: by 0.1mol degree of functionality Fn=3, number-average molecular weight Mn=4000g/mol polyoxyethylene ether trihydroxylic alcohol and
The reactant of cyclohexanedimethyl diisocyanate composition and the dibutyltin dilaurate catalyst of 50ppm of 0.3mol is added
Into the three-necked flask of a 1000ml；
S22: under conditions of 90 DEG C of oil baths, mechanical stirring is carried out to the reactant in the three-necked flask, is reacted 3 hours
Afterwards, the polyurethane prepolymer that reaction is formed is down to room temperature, the polyoxyethylene ether trihydroxylic alcohol and ring in the polyurethane prepolymer
Hexane diformazan group diisocyanate interconnection；
S23: the polyurethane prepolymer is diluted to the solution that solidification amount is 50% using ethyl alcohol；
S24: 0.2mol sulfurous is added into the solution using the aqueous solution of sodium bisulfite that mass percent is 30%
Sour hydrogen sodium carries out end capping reaction to the polyurethane prepolymer, reacts 1.5 hours at room temperature；
S25: the pH value of the solution is adjusted to 3 using the dilute sulfuric acid that mass percent is 20%, that is, forms solid content
About 48.5% polyurethane finishing agent S2.
Using polyurethane finishing agent S2 ox-hide processing method the following steps are included:
A21: when tanning arranges, ox-hide wet blue is used to be put into rotary drum as raw material, with the quality of ox-hide wet blue
For benchmark quality, the water of 150% Reference mass is first added, then presses the acrylic resin of 3%, 3%, 2% Reference mass in three times
Tanning agent is added, every minor tick 10~15 minutes；
A22: by the resin retaning agent of 9% Reference mass, divide three after the polyurethane finishing agent S2 mixing of 15% Reference mass
8% Reference mass, every minor tick 15 minutes is added in secondary addition every time；
A23: being added the pigment of 1% Reference mass, handles 1.5 hours；
A24: draining is added the natural oil of 15% Reference mass, handles 1.5 hours at 50 DEG C；
A25: taking out treated ox-hide, using vacuum ironing machine, ox-hide 3~4 minutes described in ironing at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
A26: being sprayed at the ox-hide inner surface after drying for moisture again, make the moisture content of the ox-hide reach 10%~
15%；
A27: the soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface applies ox-hide surface rubbing to ox-hide
Color/color spray processing presses the ox-hide by rotary ironing machine, and ironing temperature is 100~150 DEG C, this implementation is obtained after ironing
The ox-hide A2 of example ox-hide processing method processing.
In step A22, it is spaced addition in three times after the polyurethane finishing agent S2 and resin retaning agent mixing, has
It is slowly permeated conducive to the polyurethane finishing agent S2, avoids being added at one time excessive concentration on the ox-hide surface and react too fast,
Hinder the further infiltration and reaction of the polyurethane finishing agent S2.In alternative embodiments, the resin in step A22 is multiple
Tanning agent dosage is also possible to the 6% of Reference mass.
In order to compare the ox-hide A2 that the ox-hide processing method of prior art tannin ox-hide and the present embodiment is handled, by embodiment
Step B11 to B17 in one handles the ox-hide wet blue that step A21 is used with batch with the ox-hide wet blue at position,
It is wherein consistent in the amount of water of step B11 and step A21, step B14 with and step A24 it is consistent, ox-hide B2 is obtained after processing.
To the recovery angle test that ox-hide A2 and ox-hide B2 are the same as example 1, test data is as shown in table 2.
Table 2
Embodiment three
A kind of polyurethane finishing agent S3 provided in this embodiment and preparation method thereof and using the polyurethane finishing agent
Ox-hide processing method.
The preparation method of the polyurethane finishing agent S3 the following steps are included:
S31: by the polyoxypropyleneglycol (English of 0.1mol degree of functionality Fn=2, number-average molecular weight Mn=8000g/mol
Be abbreviated as PEG), the dibutyl tin dilaurate of the toluene di-isocyanate(TDI) (english abbreviation TDI) of 0.2mol and 100ppm urges
The reactant of agent composition is added in the three-necked flask of a 1000ml；
S32: under conditions of 90 DEG C of oil baths, mechanical stirring is carried out to the reactant in the three-necked flask, is reacted 4 hours
Afterwards, the polyurethane prepolymer that reaction is formed is down to room temperature, PEG the and TDI interconnection in the polyurethane prepolymer；
S33: the polyurethane prepolymer is diluted to the solution that solidification amount is 50% using isopropanol；
S34: 0.3mol sulfurous is added into the solution using the aqueous solution of sodium bisulfite that mass percent is 30%
Sour hydrogen sodium carries out end capping reaction to the polyurethane prepolymer, reacts 4 hours at room temperature；
S35: the pH value of the solution is adjusted to 3 using the dilute sulfuric acid that mass percent is 10%, that is, forms solid content
About 49% polyurethane finishing agent S3.
Using polyurethane finishing agent S3 ox-hide processing method the following steps are included:
A31: when tanning arranges, ox-hide wet blue is used to be put into rotary drum as raw material, with the quality of ox-hide wet blue
For benchmark quality, first it is added the water of 200% Reference mass, then by the resin tannin of 2% Reference mass, 5.5% Reference mass
It is added in three times after synthesizing composite filled tannin mixing, 2.5% Reference mass, every minor tick 10~15 minutes is added every time；
A32: by after the acrylate resin tanning agent mixing for neutralizing tannin and 8% Reference mass of 4% Reference mass points three
4% Reference mass, every minor tick 10~15 minutes is added in secondary addition every time；
A33: by the resin retaning agent of 3% Reference mass, the grain wood of 4% Reference mass, the neutralization list of 1.5% Reference mass
Rather, the pigment of the polymer tannin of 2% Reference mass, 6% Reference mass polyurethane finishing agent S3 and 1% Reference mass mixes
It is added, handles 2 hours；
A34: the Synthetic Oil of 6% Reference mass and the natural oil of 4% Reference mass is added, at 50 DEG C in draining
Reason 1.2 hours；
A35: taking out treated ox-hide, using vacuum ironing machine, ox-hide 3~4 minutes described in ironing at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
A36: being sprayed at the ox-hide inner surface after drying for moisture again, make the moisture content of the ox-hide reach 10%~
15%；
A37: the soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface applies ox-hide surface rubbing to ox-hide
Color/color spray processing presses the ox-hide by rotary ironing machine, and ironing temperature is 100~150 DEG C, this implementation is obtained after ironing
The ox-hide A3 of example ox-hide processing method processing.
In order to compare the ox-hide A3 that the ox-hide processing method of prior art tannin ox-hide and the present embodiment is handled, by embodiment
Step B11 to B17 in one handles the ox-hide wet blue that step A31 is used with batch with the ox-hide wet blue at position,
It is wherein consistent in the amount of water of step B11 and step A31, step B14 with and step A34 it is consistent, ox-hide B3 is obtained after processing.
To the recovery angle test that ox-hide A3 and ox-hide B3 are the same as example 1, test data is as shown in table 3.
Table 3
Certainly, in the polyurethane finishing agent that other alternate embodiments of the invention provide, it is pre- to form the polyurethane
In the reactant of polymers, the oligomer polyol is also possible to one kind or more of other polyether polyol or hydroxyalkyl silicone oil
Kind, the diisocyanate can also select 4,4- dicyclohexyl methyl hydride diisocyanate.In alternative embodiments, step
Hydrochloric acid, acetic acid or formic acid can also be used to carry out pH value adjusting to the solution in S15, S25 or S25.To sum up, the present invention provides
Polyurethane finishing agent preparation method without using toxic organic solvent, it is harmless to environment and operating personnel, be conducive to industry
Metaplasia produces.
Referring to Fig. 6, formed using the ox-hide that polyurethane finishing agent of the invention is handled in original collagen fabric 41
It in structure, is crosslinked by polyurethane and collagen fabric 41, collagen fabric 41 is passed through into flexible polyurethane molecular
Chain 42 connect it is stronger while, so that filler 43 is more fully filled in the collagen fabric 41 and polyurethane
In the space that strand 42 is formed.After polyurethane finishing agent processing of the invention, shape between the collagen fabric of the ox-hide
At elastic construction, the elasticity of the ox-hide can be effectively improved.Referring to Fig. 7, when the ox-hide is when by external force, the glue
Although former azelon 41 deforms, but not forms new molecular link.Therefore, after losing external force, polyurethane point
The elastic construction that subchain 42 and the collagen fabric 41 are formed can make the ox-hide be returned to original shape as far as possible
State.
In conclusion the polyurethane in the present invention is that have multi-functional strand flexible, it can be with the glue in leather
The crosslinking of multidigit point occurs for fibrinogen.Polyurethane finishing agent of the invention have two to three active function groups, can simultaneously with difference
Collagenous fibres be bonded, similar to " bridge " is costed between tropocollagen molecule, play effective crosslinked action；Meanwhile it will not
Because crosslinking points are excessive, so as to cause collagenous fibres are bonded excessively, it is unfavorable for the enhancing of leather elasticity instead.In addition, described
Isocyanates hard section assigns molecule chain rigidity in polyurethane molecular chain in polyurethane finishing agent, and it is soft that polyalcohol soft segment assigns strand
Property, the polyalcohol that soft segment is macromolecular is chosen in the polyurethane, and there is polyurethane finishing agent compared with high-flexibility.Using this hair
After bright polyurethane finishing agent is applied to leather arrangement, when leather is by bending external force, the polyurethane molecular chain between collagen is risen
To the effect of support, after external force is removed, polyurethane molecular chain can play the effect of " spring ", help its rebound, improve skin
The elasticity of leather.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (1)
1. a kind of polyurethane finishing agent for leather, it is characterised in that: including alcohols solvent and polyurethane solute, wherein institute
It is former for stating polyurethane prepolymer that polyurethane is formed by oligomer polyol and diisocyanate and sodium hydrogensulfite end-capping reagent
Material is prepared, and the molar ratio of the oligomer polyol, diisocyanate and sodium hydrogensulfite is 1:2~3:2~3；Institute
The alcohols solvent stated is ethyl alcohol or isopropanol；The solid content of the polyurethane finishing agent is 45~49%；The oligomer is polynary
The molecular weight of alcohol is 1000~8000, and degree of functionality is 2~3；The oligomer polyol is selected from polyether polyol or hydroxyalkyl silicon
Oily is one or more；The diisocyanate is selected from isophorone diisocyanate, two isocyanide of 4,4- dicyclohexyl methyl hydride
Acid esters, cyclohexanedimethyl diisocyanate and toluene di-isocyanate(TDI)；The oligomer polyol is formed with diisocyanate
Use dibutyl tin dilaurate as catalyst when prepolymerization reaction；The dibutyl tin dilaurate is in the prepolymerization reaction
Dosage be 20~100ppm, the pH value of the polyurethane finishing agent is 3~5；Its pH value using sulfuric acid, hydrochloric acid, acetic acid or
Formic acid is adjusted；
Include the following: using a kind of technique of the polyurethane finishing agent processing ox-hide for leather
A11: when tanning arranges, ox-hide wet blue is used to be put into rotary drum as raw material, using the quality of ox-hide wet blue as base
The water of 150% Reference mass is first added in quasi- quality, then 6%, 5% and 5% Reference mass polyurethane finishing agent is added in three times,
The each interval time being added three times is 15 minutes；
A12: being added the pigment of 1% Reference mass, handles 1 hour；
A13: draining is added the Synthetic Oil of 8% Reference mass, handles 1 hour at 50 DEG C；
A14: treated ox-hide is taken out, using vacuum ironing machine, ox-hide 3~4 minutes described in ironing, are then taken at 40 DEG C
Ox-hide out, by ox-hide hang airing 2~3 days；
A15: moisture is sprayed at the ox-hide inner surface after drying again, the moisture content of the ox-hide is made to reach 10%~15%；
A16: drawing the soft ox-hide using mechanical oscillation, modify ox-hide surface, by ox-hide surface rubbing, ox-hide tint/
Color spray processing presses the ox-hide by rotary ironing machine, and ironing temperature is 100~150 DEG C, and described one is utilized after ironing
Kind of polyurethane finishing agent treated ox-hide.
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