Background technology
Shoe polish ornamenting agent be it is a kind of modify and beautification leather fine chemicals, function mainly have increase remove from office beauty,
The performance of leather is improved, the resistance to usability of leather goods is promoted and prolongs the service life.China is the leather and its system of maximum in the world
Product producing country, the output of leather shoes account for the 60% of global yield, and total industrial output value is more than trillion.Traditional shoe polish ornamenting agent master
It to be made of native paraffin, synthetic wax, turpentine oil, solvent etc., be pungent in formula composition containing a large amount of solvents, smell, glossy effect
Difference does not meet the requirement of environmental protection.The harmless nontoxic requirement for meeting environmental protection of water-borne wax breast shoe polish ornamenting agent, sanitation performance, gas permeability
Can be excellent, can more meet the needs of people's increasing life comfort level.
Wax emulsion is to determine the key component of its performance in wax breast shoe polish ornamenting agent, and wax emulsion is usually with native paraffin, oil
Wax or synthetic wax are primary raw material, with co-emulsifier, thickener etc. by the operation preparations such as stirring, being homogenized.CN 102918085
The wax dispersion stablized disclosed in A, mainly with miniaturization wax, thickener, water-soluble alkali, dispersant, polymer-type binding agent etc.
It prepares, especially suitable for the processing of simulated leather, semi-synthetic leather and leather;Shellac wax nanoemulsions disclosed in 102093723 B of CN
And preparation method thereof, it is mainly prepared with shellac wax, Tween-80, Span-80, triethanolamine and water, has emulsion particle diameter small, divide
The advantages that dissipating property, storage-stable, good centrifugal stability.However, such wax emulsion is directly emulsified using outer emulsifier, it is hydrophilic
Property is relatively strong so that the water proofing property and durability of the wax breast shoe polish ornamenting agent of preparation are poor.
Branched polyethylene wax emulsion disclosed in 102010511 B of CN passes through branched polyethylene wax, cosolvent emulsifier liter
It is prepared after temperature mixing using phase transfer method, coating hardness is high, and scratch-proofness is good;Oxidized polyethylene wax disclosed in 101503519 B of CN
Modified wax emulsion, by will change after mixing heating in oxidized polyethylene wax, organic base, acidic catalyst again toluene solvant in advance
Property, then prepared after coordinating small amount emulsifier, emulsion-stabilizing, feel is smooth, natural.Above two method passes through phase
Reversal process emulsification reduces outer emulsifier or oxidized polyethylene wax hydrophilic modifying is emulsified using self-emulsification, can be certain
Degree improves the performance of wax breast shoe polish ornamenting agent, but its water proofing property and durability are still not ideal enough.
In conclusion being pungent in traditional shoe polish ornamenting agent prescription composition containing a large amount of solvents, smell, glossy effect is poor, no
Meet the requirement of environmental protection, wax breast shoe polish ornamenting agent is more cleaned and environmental protection, more meets the demand of industry development;Outer emulsifier method obtains
The wax emulsion arrived is since it emulsifies the limitation of mechanism, and emulsifier is relatively large, and wax emulsion hydrophily is relatively strong, leads to wax
The poor performances such as the water proofing property of newborn shoe polish ornamenting agent and resistance to wiping;Wax emulsion prepared by published phase inversion and self-emulsifying can carry
Rise water resistance, it is but not good enough with the natural affinity of leather substrate, water resistance, resistance to wiping, durability etc. there are still compared with
Big defect.Therefore, it is disclosed that wax is modified in the technology for preparing wax emulsion, have no the wax breast being modified based on polyurethane chemistry
Liquid, the present invention is based on polyurethane-modified oxidized wax to prepare wax breast shoe polish ornamenting agent, above-mentioned series of defect can be solved the problems, such as, to footwear
The product up-gradation of oily ornamenting agent is particularly important.
Invention content
For series of defect existing for the wax breast shoe polish ornamenting agent of prior art preparation, the present invention is directed to be changed using polyurethane
Property oxidized wax technology be made to obtain self-emulsifying type wax emulsion, using it is more optimal formula and technique prepare water-based system wax breast
Shoe polish ornamenting agent, the advantages that using the excellent mechanical performances of polyurethane and the natural affinity with leather, to solve traditional shoe polish
Ornamenting agent irritation taste is big, and long-time service is easy to cause leather and fades and existing outer emulsion process or common phase reversal legal system
Existing for standby wax breast shoe polish ornamenting agent the defects of resistance to wet friction, durability, poor water proofing property.
Water-borne wax breast shoe polish ornamenting agent provided by the invention based on the modified oxidized wax of anion polyurethane, shoe polish ornamenting agent
Key component composition, be calculated as with mass fraction:
Wherein, the polyurethane-modified oxidation wax emulsion is prepared using following methods, and preparation method mainly includes:
(a) it is 500~3,000 2 by 100 parts of oxidized wax, 5~10 parts of solvents, 1~5 part of stabilizer, 5~10 parts of molecular weight
After first alcohol is warming up to oxidized wax melting completely, 5~10min is stirred with the speed of 200~400r/min;
(b) diisocyanate and 5~10 parts of hydrophilic chain extenders, 100 DEG C~120 DEG C of temperature control for adding in 10~15 parts react
The polyurethane-modified oxidized wax containing hydrophilic group is made in 90min~120min, is cooled to 60~80 DEG C of additions, 10~20 parts of silicone oil;
(c) raising rotating speed be added dropwise 40 dissolved with 6~12 parts of salt forming agents to 800~1000r/min, in 20min~30min~
60 parts of deionized waters keep 1200~1500r/min to continue stirring 15~30min of shearing, then add in 60~70 parts in three times and go
Ionized water is to get to polyurethane-modified oxidation wax emulsion.
In the preparation of above-mentioned polyurethane-modified oxidation wax emulsion, the oxidized wax is selected from oxidation vegetable wax, oxidizing animal
One or more of wax, oxide mineral wax, petroleum oxidate wax and oxidative synthesis wax can specifically be selected from oxidation haze tallow, oxidation
Castor wax, oxidation lanocerin, oxidation lignite wax, oxidized paraffin wax, oxidation ceresine, oxidized polyethylene wax, chlorinated polypropylene wax, oxidation
One or more of Fischer-Tropsch wax and ethylene oxide-vinyl acetate copolymerization wax (EVA waxes), preferably oxidized paraffin wax, oxidic polyethylene
Wax, chlorinated polypropylene wax and one or more of with ethylene oxide-vinyl acetate copolymerization wax;The solvent be selected from propylene glycol ethers,
Diethylene glycol ethers, dipropylene glycol ethers and dimethylformamide class, preferably propandiol butyl ether, butyl, dipropyl two
One kind in alcohol ether, N,N-dimethylformamide.
In the preparation of above-mentioned polyurethane-modified oxidation wax emulsion, the stabilizer can be selected from antioxidant and light is stablized
The one kind of one kind in agent, wherein antioxidant in Hinered phenols, aromatic amine class, thioesters class, phosphorous acid esters, specifically
Irganox 245 (Giba), Vulkanox BHT (Bayer), Irganox 1010 (Giba), Irganox 1098 can be selected from
(Giba), one kind in Irganox 5057 (Giba), Irgafos168 (Giba) and DSTDP (Giba);Light stabilizer is selected from
Benzotriazole, hindered amines and diphenyl ketone can specifically be selected from Tinuvin 213 (Giba), Tinuvin 327
(Giba), Lowlite 28 (U.S. Great Lakes), Tinuvin 622 (Giba), (U.S. Great of Lowlite 77
Lakes), one kind in Sanol LS-770 (Japanese Lifetech) and UV-531.
In the preparation of above-mentioned polyurethane-modified oxidation wax emulsion, the molecular weight is selected from for 500~3000 dihydric alcohols
One kind in polyether Glycols, polyester diol and polycarbonate glycol, preferably polycarbonate glycol (PCDL), polycaprolactone two
Alcohol (PCL), polytetrahydrofuran diol (PTMG), one kind in polyoxypropyleneglycol (PPG);The diisocyanate is selected from fat
One kind in fat (cyclo) aliphatic diisocyanates and alicyclic diisocyanate can specifically be selected from isophorone diisocyanate
(IPDI), dicyclohexyl methyl hydride diisocyanate (H12MDI), 1,4- cyclohexane diisocyanates (CHDI), two methylene of hexamethylene
One in group diisocyanate (HXDI), methylcyclohexane diisocyanate (HTDI) and hexamethylene diisocyanate (HDI)
Kind, the one kind preferably being selected from isophorone diisocyanate (IPDI) and dicyclohexyl methyl hydride diisocyanate (H12MDI).
In the preparation of above-mentioned polyurethane-modified oxidation wax emulsion, the hydrophilic chain extender is selected from dihydroxy carboxylic acids, two
One kind of hydroxyl sulfoacid can specifically be selected from dimethylolpropionic acid (DMBA), dihydromethyl propionic acid (DMPA), dihydroxymethyl penta
One kind of acid, 1,4-butanediol 2- sulfonic acid, preferably one kind in dimethylolpropionic acid (DMBA), dihydromethyl propionic acid (DMPA);
The one kind of the salt forming agent in organic amine, inorganic base, can be in triethylamine, dimethylethanolamine, sodium bicarbonate
One kind, preferably triethylamine.
In the preparation of above-mentioned polyurethane-modified oxidation wax emulsion, the silicone oil is selected from methyl-silicone oil, ethyl silicon oil, benzene
Base silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicon
Oil, methyl vinyl silicon oil, methylhydroxy silicone oil and ethyl containing hydrogen silicone oil, preferably one kind in methyl-silicone oil and ethyl silicon oil.
In the composition of the above-mentioned water-borne wax breast shoe polish ornamenting agent based on the modified oxidized wax of anion polyurethane, colorant choosing
From one kind in pigment paste and dyestuff, black pigment cream, white pigment cream, brown cream, black dyes, brown can be selected from
One kind in dyestuff, white dye;The wetting agent is selected from organic silicon wetting agent, polyacrylic acid wetting agent, acetylenic diols profit
One kind in humectant can be selected fromWet KL 245 (Evonik Degussa companies),Wet 270(Evonik
Degussa companies), BYK 346 (Bi Ke chemistry),FA 115 (this chemistry of hamming), Surfynol 104 are (empty
Chemistry) in one kind.
In the composition of the above-mentioned water-borne wax breast shoe polish ornamenting agent based on the modified oxidized wax of anion polyurethane, described disappears
Steep foam inhibitor selected from mineral oil antifoam agent, containing one kind in silicon defoaming agent, emulsion type defoaming agent, Deform WT- can be selected from
082 (hamming this chemistry), BYK-094 (Bi Ke chemistry), BYK-028 (Bi Ke chemistry),Foamex 822(Evonik
Degussa companies),Foamex 825 (Evonik Degussa companies),Foamex 1488(Evonik
Degussa companies) in one kind;The auxiliary rheological agents are selected from natural polymer subclass, synthesis high score subclass and inorganic rheology
One kind in auxiliary agent, can be selected from hydroxyethyl cellulose, ASE-60 (ROHM AND HAAS, agent for polyacrylic acid thickening),
ViscoPlus 3060 (Evonik Degussa companies),ViscoPlus 3060 (Evonik Degussa companies),
One kind in organobentonite, nano fumed silica.
In the composition of the above-mentioned water-borne wax breast shoe polish ornamenting agent based on the modified oxidized wax of anion polyurethane, described is anti-
Mould fungicide is selected from aqueous mould inhibitor and fungicide, can be selected from ROCIMATM343 (DOW Chemicals), ROCIMATM 371
(DOW Chemical), KATHON LX150 (DOW Chemical), preservative BM (Huffman chemistry), Nipacide CI 15MV (section's Lays
Grace chemical industry), one kind in Nipacide HF-I (Clariant chemical industry).
The present invention discloses the preparations of the water-borne wax breast shoe polish ornamenting agent based on the modified oxidized wax of anion polyurethane
Method, mainly including procedure below:By the mass fraction that shoe polish ornamenting agent component forms, colorant, wetting agent, polyurethane are changed
Property oxidation wax emulsion after being fully ground, control rotating speed be dispersed with stirring 10~40min in 2000r/min~4000r/min, reduce
Rotating speed sequentially adds defoaming foam inhibitor, antimildew disinfectant and auxiliary rheological agents to 400r/min~500r/min, continue stirring 10~
20min is to get to the water-borne wax breast shoe polish ornamenting agent based on the modified oxidized wax of anion polyurethane.
The contribution of the present invention, in addition to disclosing the water-borne wax breast shoe polish based on the modified oxidized wax of anion polyurethane to society
Ornamenting agent and preparation method thereof, highly important contribution are the poly- ammonia also disclosed as wax breast shoe polish ornamenting agent important composition
The preparation method of ester modified oxidation wax emulsion.Polyurethane-modified oxidation wax emulsion is prepared first, and main process is as follows:First will
Oxidized wax and solvent, stabilizer, macromolecule dihydric alcohol mixed melting are uniform, are obtained after adding in diisocyanate, hydrophilic monomer reaction
To hydrophilic segment, silicone oil is added in, salt forming agent obtains the modified oxidized wax emulsion of anion polyurethane after being emulsified by phase inversion;So
It is obtained based on the poly- ammonia of anion by compound colorant, wetting agent, defoaming foam inhibitor, antimildew disinfectant and auxiliary rheological agents etc. afterwards
The water-borne wax breast shoe polish ornamenting agent of ester modified oxidized wax.
The present invention is prominent and beneficial compared with prior art to be had the technical effect that:
(1) it prepares and using process safety environmental protection.It is provided by the invention to be based on the modified oxidized wax emulsion of anion polyurethane,
Using oxidized wax, diisocyanate, macromolecule dihydric alcohol, hydrophilic chain extender as main reaction monomers, after it is dilute by using silicone oil
It is made after releasing with phase inversion, the solvent that reaction process is used is few, and is the environmentally friendly solvent of nonhazardous, finally obtains ornamenting
Agent product is also water-based system, relative to the safer environmental protection of traditional oil type wax breast shoe polish ornamenting agent, when use is nontoxic, pollution-free,
It is nonflammable, there is no irritation taste.
(2) product formula, synthesis and emulsifying technology are more innovative.It is disclosed that prepared by wax emulsion to wax chemical modification
Technology in, have no the wax emulsion being modified based on polyurethane chemistry, the present invention using the activity hydroxy on oxidized wax segment with it is different
Anionic hydrophilic base is linked into oxidized wax segment, and then the breast certainly obtained using phase inversion by the response characteristic of cyanic acid ester group
Change wax emulsion, formula, synthesis and emulsifying technology are more innovative, can perform to the effectiveness of hydrophilic radical ultimate attainment so that breast
Liquid has the features such as grain size is small, excellent storage stability, while the coating overwhelming majority of natural or synthetic leather is polyurethane
Material, the shoe polish ornamenting agent which obtains is stronger to the interface interaction of leather, has relative to common ornamenting agent preferably attached
Put forth effort.
(3) performances such as durability, resistance to wiping, water resistance are more excellent.The shoe polish ornamenting agent of the present invention is gathered based on anion
Urethane material, the infiltration and adhesive capacity with leather substrate are more prominent, and the access of polyurethane increases the elasticity and toughness of dry film,
Material mechanical performance is more excellent, while containing light heat stabilizer in component, the leather of ornamenting agent processing is with superior resistance to
Wait durability;Hydrophilic radical is performed to maximum utility, shown by the wax emulsion in the invention using being prepared after chemical modification oxidized wax
Writing reduces the hydrophily of ornamenting agent dry film, contains the very strong silicone oil of water repellency be formulated in addition in so that the skin of finishing agent processing
Leather be difficult to it is wetted, thus with superior resistance to wiping and water resistance.
Water-borne wax breast shoe polish ornamenting agent based on the modified oxidized wax of anion polyurethane prepared by the present invention, bin stability
Good, construction is simple is easy, can solve that solvent taste existing for traditional oiliness shoe polish ornamenting agent is big, and long-time service leads to leather
Hydrophily existing for the defects of fading and existing common outer emulsion process wax breast shoe polish ornamenting agent is relatively strong, resistance to wiping, waterproof
Property and durability it is poor wait series of problems, it is much to the product up-gradation benefit of shoe polish ornamenting agent, can be widely applied to leather shoes, skin
The ornamenting and maintenance of packet, fur clothing etc., great environmental benefit, social benefit, economic benefit.
Embodiment 3
1. the preparation of polyurethane-modified oxidation wax emulsion:
By 40g parts of oxidized paraffin waxs and 60g polyethylene glycol oxides wax, 9g N,N-dimethylformamides (solvent), 3g Tinuvin
After 327 (stabilizers), 7g polycarbonate glycol (Mn=1000) are warming up to oxidized wax melting completely, stirred with the speed of 350r/min
Mix 6min;Add in the HDI (hexamethylene diisocyanate) of 11g and 6g DMPA (dihydromethyl propionic acid), 105 DEG C of reactions of temperature control
The polyurethane-modified oxidized wax containing hydrophilic group is made in 95min, is cooled to 75 DEG C of addition 16g methyl-silicone oils;Increase rotating speed extremely
The 55g deionized waters dissolved with 6.5g triethylamines are added dropwise in 900r/min, 25min, 1250r/min is kept to continue stirring shearing
25min, then 68g deionized waters are added in three times to get to polyurethane-modified oxidation wax emulsion.
2. the formula composition of water-borne wax breast shoe polish ornamenting agent
3. the preparation process of water-borne wax breast shoe polish ornamenting agent:
By water-borne wax breast shoe polish ornamenting agent component form mass fraction, by black pigment cream,Wet 270, poly- ammonia
For ester modified oxidation wax emulsion after being fully ground, control rotating speed is dispersed with stirring 35min in 2500r/min, reduces rotating speed to 450r/
Min sequentially adds Deform WT-082, Nipacide HF-I and ViscoPlus 3030, continue stir 15min after to get
To the water-borne wax breast shoe polish ornamenting agent based on the modified oxidized wax of anion polyurethane.
Comparative example
Comparative example uses commercially available outer emulsifying wax emulsion, and the main formula of water-borne wax breast shoe polish ornamenting agent is as follows:
Preparation process is as follows:By water-borne wax breast shoe polish ornamenting agent component form mass fraction, by brown cream,
After being fully ground, control rotating speed is dispersed with stirring in 3000r/min for Surfynol 104, polyurethane-modified oxidation wax emulsion
25min reduces rotating speed to 450r/min, sequentially adds BYK-028, ROCIMATM371 and ViscoPlus 3060 continues to stir
15min is to get to the water-borne wax breast shoe polish ornamenting agent of comparison.
Embodiment 1, embodiment 2, embodiment 3 and comparative example are applied on the cow leather upper leather of same base material, test it
Water resistance (contact angle, 200 contact angle instruments of OCAH), resistance to wiping properties (with reference to the resistance to wet frictions of QB/T 2537-2001,
50 are reciprocal), durability (with reference to QB/T 2727-2005), obtain that test result is as follows shown in table:
The performance of 1 embodiment of table and comparative example
Test event |
Comparative example 1 |
Comparative example 2 |
Comparative example 3 |
Embodiment |
Water resistance (contact angle) |
119° |
117° |
116° |
108° |
Resistance to wiping properties (resistance to wet friction) |
4-5 |
4-5 |
4-5 |
3-4 |
Durability (color fastness to light) |
4 |
4-5 |
4-5 |
3 |
Above-described embodiment is only presently preferred embodiments of the present invention, is not limited the scope of the invention according to this, therefore:It is all according to
The equivalence changes that structure, shape, the principle of the present invention is done, should all be covered by within protection scope of the present invention.