CN106947382A - A kind of polyurethane finishing agent - Google Patents
A kind of polyurethane finishing agent Download PDFInfo
- Publication number
- CN106947382A CN106947382A CN201710287200.3A CN201710287200A CN106947382A CN 106947382 A CN106947382 A CN 106947382A CN 201710287200 A CN201710287200 A CN 201710287200A CN 106947382 A CN106947382 A CN 106947382A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- finishing agent
- hide
- polyurethane finishing
- diisocyanate
- 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.)
- Granted
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 88
- 239000004814 polyurethane Substances 0.000 title claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 80
- 229920001730 Moisture cure polyurethane Polymers 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 12
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 11
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims abstract description 8
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 239000003054 catalyst Substances 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
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 22
- 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
- 238000010409 ironing Methods 0.000 description 12
- 235000018553 tannin Nutrition 0.000 description 12
- 229920001864 tannin Polymers 0.000 description 12
- 239000001648 tannin Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000003672 processing method 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
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 230000010358 mechanical oscillation Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229920000642 polymer 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
- 238000013019 agitation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 239000000203 mixture Substances 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 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
- 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 1
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002600 fibrillogenic effect Effects 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 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 agent, including alcohols solvent and polyurethane solute, the polyurethane prepolymer and sodium hydrogensulfite end-capping reagent that wherein described polyurethane is formed by oligomer polyol and diisocyanate are prepared from for raw material, and the mol ratio of the oligomer polyol, diisocyanate and sodium hydrogensulfite is 1：2~3：2~3.The polyurethane finishing agent provided using the present invention can form elastic construction in the collagen fabric of leather, improve leather elasticity.And the polyurethane finishing agent that the present invention is provided 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 technology
In leather manufacture, especially handbag product manufacturing industry, the elastic recovery of ox-hide is particularly significant, the property
The outward appearance of product, which can not only be influenceed, more influences the function of product.
In existing leather processing, using organic silicone finishing agent or wax, grease-filled leather, it is set to soften, and
Improve its elastic recovery.But the elastic recovery of the leather of these processing methods acquisition can not 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
During, ox-hide is extruded by external force F causes filler 12 between collagen fabric 11 by different degrees of extrusion, simultaneously
New chemical bond 13 is formed between collagen fabric 11, causes ox-hide thinning and elastic recovery is reduced.Therefore, how
Improving the elasticity and elastic stability of ox-hide turns into study hotspot.
Polyurethane correlation finishing agent early has record, for example, a kind of Publication No. CN102070759A " aqueous polyurethane skins
The preparation method of leather retanning agent ", Publication No. CN103030769A " a kind of polyurethane retanning agent ", notification number
CN104073575B " fur tanning agent based on isocyanates and preparation method thereof ", which discloses polyurethane finishing agent, to be had well
Filling effect, however, fillibility polyurethane does not crosslink reaction with ox-hide, after long-time use, ox-hide impaired performance.In addition
In preparation process, it is related to the use of toxic organic solvent, such as tetrahydrofuran, benzene, toluene are unfavorable for industrialized production.
In United States Patent (USP) US2923594, US2523326 and Publication No. 20060080784A1 U.S. Patent application
Disclose 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 effectively can be crosslinked with collagen molecules, so as to improve the shrinkage temperature of leather, but leather can not be improved
Elasticity.
The content of the invention
In order to overcome the defect of prior art, the present invention proposes one kind when can improve leather elasticity and prepare without using poison
The polyurethane finishing agent of property organic solvent.
For up to this purpose, a kind of polyurethane finishing agent that the present invention is provided, including：Alcohols solvent and polyurethane solute,
The polyurethane prepolymer and sodium hydrogensulfite that wherein described polyurethane is formed by oligomer polyol and diisocyanate are blocked
Agent is prepared from for raw material, and the mol ratio of the oligomer polyol, diisocyanate and sodium hydrogensulfite is 1：2~3：2
~3.
It is preferred that, described alcohols solvent is ethanol or isopropanol.
It is preferred that, the solid content of the polyurethane finishing agent is 45~49%.
It is preferred that, the molecular weight of the oligomer polyol is 1000~8000, and degree of functionality is 2~3.
It is preferred that, the oligomer polyol is selected from the one or more of PPG or hydroxyalkyl silicone oil.
It is preferred that, described diisocyanate is selected from IPDI, the isocyanide of 4,4- dicyclohexyl methyl hydrides two
Acid esters, cyclohexanedimethyl diisocyanate and toluene di-isocyanate(TDI).
It is preferred that, use dibutyl tin laurate when the oligomer polyol is with diisocyanate formation prepolymerization reaction
It is used as catalyst.
It is preferred that, consumption of the dibutyl tin laurate in the prepolymerization reaction is 20~100ppm.
It is preferred that, the pH value of the polyurethane finishing agent is 3~5.
It is preferred that, sulfuric acid, hydrochloric acid, acetic acid or the formic acid regulation that the pH value of the polyurethane finishing agent is used are formed.
Beneficial effects of the present invention are：Polyurethane finishing agent in the present invention is with multi-functional flexible molecule
Chain, can occur many sites with the collagenous fibres in leather and be crosslinked.The polyurethane finishing agent of the present invention has two to three active officials
It can roll into a ball, can be bonded simultaneously from different collagenous fibres, similar to " bridge " is costed between tropocollagen molecule, play effective friendship
Connection is acted on；Meanwhile, will not be excessive because of crosslinking points, so as to cause to make collagenous fibres too bond, it is unfavorable for leather elasticity on the contrary
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.It is applied to using polyurethane finishing agent of the present invention after leather arrangement, when leather is by bending external force, between collagen
Polyurethane molecular chain play a part of support, after external force is removed, polyurethane molecular chain can play the effect of " spring ", side
Its resilience is helped, the elasticity of leather is improved.
Brief description of the drawings
The schematic diagram that Fig. 1 is deformed in use for the collagen fabric structure of prior art heifer；
The chemical reaction schematic diagram that Fig. 2 is step S12 in embodiment 1；
The chemical reaction schematic diagram that Fig. 3 is step S14 in embodiment 1；
The cross-linking reaction schematic diagram that Fig. 4 is step A11 in embodiment 1；
Fig. 5 is the schematic diagram of ox-hide wet blue that step A11 is used in embodiment 1；
Fig. 6 illustrates to use the collagen fabric structure change before and after the disposal methods ox-hide that provides of the present invention
Figure；
The schematic diagram that Fig. 7 is deformed in use for the collagen fabric structure of the ox-hide after being handled in Fig. 6.
Embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment one
A kind of polyurethane finishing agent S1 and preparation method thereof and use the polyurethane finishing agent that the present embodiment is provided
Ox-hide processing method.
The preparation method of the polyurethane finishing agent S1 comprises the following steps：
S11：By 0.1mol degrees of functionality Fn=3, number-average molecular weight Mn=1000g/mol PPOX triol (abbreviation
For PPG) and 0.3mol IPDI (english abbreviation is IPDI) composition reactant and 20ppm two bays
Sour dibutyl tin (english abbreviation DBTDL) catalyst is added in 1000ml there-necked flask；
S12：Under conditions of 85 DEG C of oil baths, mechanical agitation is carried out to the reactant in the there-necked flask, reacted 2 hours
Afterwards, the polyurethane prepolymer for reacting formation is down to room temperature, its schematic diagram that chemically reacts is as shown in Fig. 2 the polyurethane prepolymer
PPG and IPDI interconnections in thing, form PPG-IPDI-PPG-IPDI ... chain-like molecular structure；
S13：The polyurethane prepolymer is diluted to the solution that solidification amount is 50% using ethanol；
S14：Use quality percentage is 30% sodium hydrogensulfite (NaHSO3) aqueous solution adds into the solution
0.3mol sodium hydrogensulfites carry out end capping reaction to the polyurethane prepolymer, react 1 hour at room temperature, its chemical reaction shows
It is intended to as shown in Figure 3；
S15：Use quality percentage is 20% dilute sulfuric acid (H2SO4) adjust the pH value of the solution to 5, that is, formed
The polyurethane finishing agent S1 that solid content is about 45%.
Comprised the following steps using polyurethane finishing agent S1 ox-hide processing method：
A11：Referring to Fig. 5, when tanning is arranged, it is put into using ox-hide wet blue 50 as raw material in rotary drum, it is blue with ox-hide
Quality on the basis of the quality of wet skin 50, first adds the water of 100% Reference mass, then adds 6%, 5% and 5% benchmark matter 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 end-blocking depart from, expose the NCO group 21 of end and the NH of the collagen fabric in the ox-hide2Group 31
It is bonded, the elastic connection of strand 30 by the polyurethane between crosslinking points 35, each crosslinking points 35 is formed, 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：The pigment of 1% Reference mass is added, is handled 1 hour；
A13：Draining, adds the Synthetic Oil of 8% Reference mass, is handled 1 hour at 50 DEG C；
A14：Ox-hide after taking-up processing, using vacuum ironing machine, presses the ox-hide 3~4 minutes at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
A15：Moisture is sprayed at the ox-hide inner surface after drying again, the moisture for making the ox-hide reaches 10%~
15%；
A16：The soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface, by ox-hide surface rubbing, is applied to ox-hide
Color/color spray processing, the ox-hide is pressed by rotary ironing machine, and ironing temperature is 100~150 DEG C, and this implementation is obtained after flatiron
The ox-hide A1 of example ox-hide disposal methods.
In step A11, the polyurethane finishing agent S1 is spaced addition in three times, is conducive to slow infiltration, it is to avoid once
Property add excessive concentration and react too fast on the ox-hide surface, hinder the further infiltration of the polyurethane finishing agent S1 and anti-
Should.In step A14, pressed using vacuum ironing machine, add the adhesion of pigment, grease and ox-hide, dye ox-hide
Firmly, the hydrophobicity and elasticity of ox-hide are improved.The pliability of soft adjustable ox-hide is drawn in mechanical oscillation in step A16, makes ox-hide fine
It is loose that dimension becomes, so that the softness that ox-hide becomes；The flaw on ox-hide surface can be covered by carrying out modification to ox-hide surface；Tint/spray
Color can protect ox-hide surface property and make the uniform of ox-hide surface color change；Ox-hide is pressed by rotary ironing machine, reduces ox-hide
Moisture, makes the smooth of ox-hide change.In various embodiments, can according to the demand of ox-hide product, repeat it is described draw it is soft, apply
Color/color spray, flatiron process.
In order to contrast prior art tannin ox-hide and the ox-hide A1 of the ox-hide disposal methods using the present embodiment, use
Common tanning agent is handled with the ox-hide wet blue at position same batch, is made conventional kraft B1, is comprised the following steps：
B11：When tanning is arranged, it is put into using ox-hide wet blue 50 as raw material in rotary drum, with ox-hide wet blue 50
Quality on the basis of quality, first adds 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
It is secondary to add, 2.5% Reference mass, every minor tick 10~15 minutes are added every time；
B12：By the neutralization tannin (english abbreviation is NTL) and the acrylate resin tanning of 8% Reference mass of 4% Reference mass
Added in three times after agent mixing, 4% Reference mass, every minor tick 10~15 minutes are 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 add after, handle 2 hours；
B14：Draining, adds the Synthetic Oil of 8% Reference mass, is handled 1 hour at 50 DEG C；
B15：Ox-hide after taking-up processing, using vacuum ironing machine, presses the ox-hide 3~4 minutes at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
B16：Moisture is sprayed at the ox-hide inner surface after drying again, the moisture for making the ox-hide reaches 10%~
15%；
B17：The soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface, by ox-hide surface rubbing, is applied to ox-hide
Color/color spray processing, after flatiron, obtains the ox-hide B1 of common tanning agent processing.
It is Y-direction along the direction of the ridge line 51 of ox-hide wet blue 50 referring to Fig. 5, is X perpendicular to the direction of ridge line 51
To.Using AATCC 66-2008Wrinkle Recovery of Woven Fabrics:RecoveryAngle(AATCC 66-
2008 woven fabric wrinkle recoveries：Recovery angle is tested) testing standard carries out recovery angle test to ox-hide A1 and ox-hide B1, folds 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 and preparation method thereof and use the polyurethane finishing agent that the present embodiment is provided
Ox-hide processing method.
The preparation method of the polyurethane finishing agent S2 comprises the following steps：
S21：By 0.1mol degrees of functionality Fn=3, number-average molecular weight Mn=4000g/mol APEO trihydroxylic alcohol and
The 0.3mol reactant of cyclohexanedimethyl diisocyanate composition and 50ppm dibutyltin dilaurate catalyst is added
Into 1000ml there-necked flask；
S22：Under conditions of 90 DEG C of oil baths, mechanical agitation is carried out to the reactant in the there-necked flask, reacted 3 hours
Afterwards, the APEO trihydroxylic alcohol and the ring polyurethane prepolymer for reacting formation being down in room temperature, the polyurethane prepolymer
Hexane diformazan group diisocyanate interconnection；
S23：The polyurethane prepolymer is diluted to the solution that solidification amount is 50% using ethanol；
S24：Use quality percentage adds 0.2mol sulfurous into the solution for 30% aqueous solution of sodium bisulfite
Sour hydrogen sodium carries out end capping reaction to the polyurethane prepolymer, reacts 1.5 hours at room temperature；
S25：Use quality percentage adjusts the pH value of the solution to 3 for 20% dilute sulfuric acid, that is, forms solid content
About 48.5% polyurethane finishing agent S2.
Comprised the following steps using polyurethane finishing agent S2 ox-hide processing method：
A21：When tanning is arranged, it is put into using ox-hide wet blue as raw material in rotary drum, with the quality of ox-hide wet blue
On the basis of quality, first add the water of 150% Reference mass, then press 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
It is secondary to add, 8% Reference mass, every minor tick 15 minutes are added every time；
A23：The pigment of 1% Reference mass is added, is handled 1.5 hours；
A24：Draining, adds the natural oil of 15% Reference mass, is handled 1.5 hours at 50 DEG C；
A25：Ox-hide after taking-up processing, using vacuum ironing machine, presses the ox-hide 3~4 minutes at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
A26：Moisture is sprayed at the ox-hide inner surface after drying again, the moisture for making the ox-hide reaches 10%~
15%；
A27：The soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface, by ox-hide surface rubbing, is applied to ox-hide
Color/color spray processing, the ox-hide is pressed by rotary ironing machine, and ironing temperature is 100~150 DEG C, and this implementation is obtained after flatiron
The ox-hide A2 of example ox-hide disposal methods.
In step A22, interval is added in three times after polyurethane finishing agent S2 and the resin retaning agent mixing, is had
Slowly permeated beneficial to the polyurethane finishing agent S2, it is to avoid the disposable excessive concentration that adds reacts too fast on the ox-hide surface,
Hinder the further infiltration and reaction of the polyurethane finishing agent S2.In alternative embodiments, in step A22 resin is answered
Tanning agent consumption can also be the 6% of Reference mass.
For the ox-hide A2 of the ox-hide disposal methods that contrast prior art tannin ox-hide and the present embodiment, by embodiment
Step B11 to B17 in one, the ox-hide wet blue used step A21 is handled with batch with the ox-hide wet blue at position,
It is consistent wherein in step B11 amount of water and step A21, step B14 with and step A24 it is consistent, ox-hide B2 is obtained after processing.
Ox-hide A2 and ox-hide B2 is carried out to test with the identical recovery angle of embodiment one, test data is as shown in table 2.
Table 2
Embodiment three
A kind of polyurethane finishing agent S3 and preparation method thereof and use the polyurethane finishing agent that the present embodiment is provided
Ox-hide processing method.
The preparation method of the polyurethane finishing agent S3 comprises the following steps：
S31：By 0.1mol degrees of functionality Fn=2, number-average molecular weight Mn=8000g/mol polyoxypropyleneglycol (English
Be abbreviated as PEG), 0.2mol toluene di-isocyanate(TDI) (english abbreviation is TDI) and 100ppm dibutyl tin laurate urge
The reactant of agent composition is added in 1000ml there-necked flask；
S32：Under conditions of 90 DEG C of oil baths, mechanical agitation is carried out to the reactant in the there-necked flask, reacted 4 hours
Afterwards, PEG the and TDI interconnections polyurethane prepolymer for reacting formation being down in room temperature, the polyurethane prepolymer；
S33：The polyurethane prepolymer is diluted to the solution that solidification amount is 50% using isopropanol；
S34：Use quality percentage adds 0.3mol sulfurous into the solution for 30% aqueous solution of sodium bisulfite
Sour hydrogen sodium carries out end capping reaction to the polyurethane prepolymer, reacts 4 hours at room temperature；
S35：Use quality percentage adjusts the pH value of the solution to 3 for 10% dilute sulfuric acid, that is, forms solid content
About 49% polyurethane finishing agent S3.
Comprised the following steps using polyurethane finishing agent S3 ox-hide processing method：
A31：When tanning is arranged, it is put into using ox-hide wet blue as raw material in rotary drum, with the quality of ox-hide wet blue
On the basis of quality, first add the water of 200% Reference mass, then by the resin tannin of 2% Reference mass, 5.5% Reference mass
Added in three times after synthesizing composite filled tannin mixing, 2.5% Reference mass, every minor tick 10~15 minutes are 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
It is secondary to add, 4% Reference mass, every minor tick 10~15 minutes are added 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 mixing of the polymer tannin of 2% Reference mass, 6% Reference mass polyurethane finishing agent S3 and 1% Reference mass
Add, handle 2 hours；
A34：Draining, adds the Synthetic Oil of 6% Reference mass and the natural oil of 4% Reference mass, locates at 50 DEG C
Reason 1.2 hours；
A35：Ox-hide after taking-up processing, using vacuum ironing machine, presses the ox-hide 3~4 minutes at 40 DEG C, with
After take out ox-hide, by ox-hide hang airing 2~3 days；
A36：Moisture is sprayed at the ox-hide inner surface after drying again, the moisture for making the ox-hide reaches 10%~
15%；
A37：The soft ox-hide is drawn using mechanical oscillation, modification ox-hide surface, by ox-hide surface rubbing, is applied to ox-hide
Color/color spray processing, the ox-hide is pressed by rotary ironing machine, and ironing temperature is 100~150 DEG C, and this implementation is obtained after flatiron
The ox-hide A3 of example ox-hide disposal methods.
For the ox-hide A3 of the ox-hide disposal methods that contrast prior art tannin ox-hide and the present embodiment, by embodiment
Step B11 to B17 in one, the ox-hide wet blue used step A31 is handled with batch with the ox-hide wet blue at position,
It is consistent wherein in step B11 amount of water and step A31, step B14 with and step A34 it is consistent, ox-hide B3 is obtained after processing.
Ox-hide A3 and ox-hide B3 is carried out to test with the identical recovery angle of embodiment one, test data is as shown in table 3.
Table 3
Certainly, in the polyurethane finishing agent that other alternate embodiments of the invention are provided, the polyurethane is formed pre-
In the reactant of polymers, the oligomer polyol can also be one kind or many of other PPGs or hydroxyalkyl silicone oil
Kind, the diisocyanate can also select 4,4- dicyclohexyl methyl hydride diisocyanates.In alternative embodiments, step
Hydrochloric acid, acetic acid or formic acid can also be used to carry out pH value regulation to the solution in S15, S25 or S25.To sum up, the present invention is provided
Polyurethane finishing agent preparation method without using toxic organic solvent, it is harmless to environment and operating personnel, be conducive to industry
Metaplasia is produced.
Referring to Fig. 6, what the ox-hide handled using the polyurethane finishing agent of the present invention was constituted in original collagen fabric 41
In structure, it is crosslinked by polyurethane with collagen fabric 41, collagen fabric 41 is passed through into flexible polyurethane molecular
Chain 42 connect it is more firm while, filler 43 is more fully filled in the collagen fabric 41 and polyurethane
In the space of the formation of strand 42.After polyurethane finishing agent processing through the present invention, shape between the collagen fabric of the ox-hide
Into elastic construction, the elasticity of the ox-hide can be effectively improved.Referring to Fig. 7, when the ox-hide is being acted on by external force, the glue
Although former azelon 41 deforms, but not forms new molecular link.Therefore, after external force effect is lost, polyurethane point
Subchain 42 and the elastic construction of the formation of the collagen fabric 41 can make the ox-hide be returned to original shape as far as possible
State.
In summary, the present invention in polyurethane be with multi-functional flexible strand, can be with the glue in leather
Many site crosslinkings occur for fibrillation.The polyurethane finishing agent of the present invention has 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, will not
Because crosslinking points are excessive, so as to cause to make collagenous fibres too bond, it is unfavorable for the enhancing of leather elasticity on the contrary.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, polyurethane finishing agent is had compared with high-flexibility.Using this hair
Bright polyurethane finishing agent is applied to after leather arrangement, when leather is by bending external force, and the polyurethane molecular chain between collagen rises
To the effect of support, after external force is removed, polyurethane molecular chain can play the effect of " spring ", help its resilience, improve skin
The elasticity of leather.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of 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, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as to the claim involved by limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It may be appreciated other embodiment.
Claims (10)
1. a kind of polyurethane finishing agent, including：Alcohols solvent and polyurethane solute, wherein the polyurethane is polynary by oligomer
The polyurethane prepolymer and sodium hydrogensulfite end-capping reagent that alcohol is formed with diisocyanate are prepared from for raw material, the oligomer
The mol ratio of polyalcohol, diisocyanate and sodium hydrogensulfite is 1：2~3：2~3.
2. polyurethane finishing agent according to claim 1, it is characterised in that：Described alcohols solvent is ethanol or isopropyl
Alcohol.
3. polyurethane finishing agent according to claim 1, it is characterised in that：The solid content of the polyurethane finishing agent is 45
~49%.
4. polyurethane finishing agent according to claim 1, it is characterised in that：The molecular weight of the oligomer polyol is
1000~8000, degree of functionality is 2~3.
5. polyurethane finishing agent according to claim 1, it is characterised in that：The oligomer polyol is selected from polyether polyols
The one or more of alcohol or hydroxyalkyl silicone oil.
6. polyurethane finishing agent according to claim 1, it is characterised in that：Described diisocyanate is selected from isophorone
Diisocyanate, 4,4- dicyclohexyl methyl hydride diisocyanates, cyclohexanedimethyl diisocyanate and toluene di-isocyanate(TDI).
7. polyurethane finishing agent according to claim 1, it is characterised in that：The oligomer polyol and diisocyanate
Dibutyl tin laurate is used as catalyst when forming prepolymerization reaction.
8. polyurethane finishing agent according to claim 7, it is characterised in that：The dibutyl tin laurate is described pre-
Consumption during poly- reaction is 20~100ppm.
9. polyurethane finishing agent as claimed in any of claims 1 to 8, it is characterised in that：The polyurethane is arranged
The pH value of agent is 3~5.
10. polyurethane finishing agent according to claim 9, it is characterised in that：The pH value of the polyurethane finishing agent is used
Sulfuric acid, hydrochloric acid, acetic acid or formic acid regulation form.
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