CN105256578B - A kind of aqueous three proofings leather finishing agent and its application method - Google Patents
A kind of aqueous three proofings leather finishing agent and its application method Download PDFInfo
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- CN105256578B CN105256578B CN201510759677.8A CN201510759677A CN105256578B CN 105256578 B CN105256578 B CN 105256578B CN 201510759677 A CN201510759677 A CN 201510759677A CN 105256578 B CN105256578 B CN 105256578B
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Abstract
It include following raw material the invention proposes a kind of aqueous three proofings leather finishing agent: the aqueous fluorine-containing or silyl acrylate esters scopiform polymer of low-surface-energy, the fluorine-containing or siliceous linear polymer of hydroxyl reactive group, water soluble acrylic acid esters polymer or aqueous polyurethane quasi polymer, water cross-linking agent and coalescing agent.Aqueous three proofings leather finishing agent aqueous dispersion Environmental Safety, raw material sources are extensive, preparation method is simple for three proofings leather, the three proofings leather of preparation is with excellent Water-proof and oil-proof and anti-pollution and has smooth feel, in addition the gloss style of three proofings leather can be made up of system, and three proofings leather finishing agent and related matching technology and three proofings leather products have significant application prospect and considerable economic benefit.
Description
Technical field
The present invention relates to leather finish field, refer in particular to a kind of water dispersible with waterproof, antifouling, anti-graffiti function
Aqueous three proofings leather finishing agent further relates to the application method of aqueous three proofings leather finishing agent.
Background technique
Super-hydrophobic superoleophobic material is research hotspot in recent years, there is the Tuteja of the Massachusetts Institute of Technology in the world
(Science, 2007,318,1618), the Aizenberg (NAT COMMUN, 2013,4,2167) of Harvard University, moral
The Vollmer(Science of macromolecule research institute of state horse general association, 2012,335,67; NAT COMMUN, 2013, 4,
2512), the Parkin(Science of London university, 2015,347,1132), the Liu Guojun of Canadian Queen's University,
The woods of Australian Deakin University is virgin, the Law in Robert Webster Xerox of U.S. research center, the advanced industrial science technology of Japanese national
The Hozumi of research institute, domestic Chinese Academy of Sciences chemistry a few group such as river thunder realized in laboratory it is super-hydrophobic superoleophobic
The synthetic work of material.Currently, super-hydrophobic superoleophobic material has certain Research foundation, but do not derive yet Related product or
Industrialization technology.Hindering this kind of novel materials to convert mainly in numerous areas application study and the relevant technologies, there are three ask
Topic, first is that coating surface is prone to wear out often with there is fine micro nano structure and loses super-hydrophobic superoleophobic performance;Second is that due to
The characteristics of system hydrophobic oleophobic, generally uses expensive and has the fluoride solvent of certain toxicity as decentralized medium;Third is that super
Hydrophobic oleophobic feature makes have weaker adhesion between this kind of coating materials and substrate.
Summary of the invention
The present invention proposes a kind of aqueous three proofings leather finishing agent and its application method, solves finishing agent in the prior art and deposits
Be prone to wear out, defect toxic, adhesion is weaker.
The technical scheme of the present invention is realized as follows: a kind of aqueous three proofings leather finishing agent includes following raw material: low table
The aqueous fluorine-containing of face energy or the fluorine-containing or siliceous linear polymerization of silyl acrylate esters scopiform polymer, hydroxyl reactive group
Object, water soluble acrylic acid esters polymer or aqueous polyurethane quasi polymer, water cross-linking agent and coalescing agent.
Preferably, the aqueous fluorine-containing of the low-surface-energy or silyl acrylate esters scopiform polymer are by vinyl monomer
The polymer obtained by solution free radical polymerization or emulsion polymerization;The vinyl monomer includes low-surface-energy monomer A and is total to
Polycondensation monomer B, the low-surface-energy monomer A are vinyl fluorochemical monomer or vinyl silicon-containing monomer, the vinyl fluorochemical monomer
Including perfluoroalkyl (butyl, hexyl, octyl or decyl) acrylate, methyl perfluoro alkyl (butyl, hexyl, octyl or decyl)
Acrylate,Trifluoroethyl methacrylate、Hexafluorobutyl acrylate、Hexafluorobutyl mathacrylate、Ten difluoro heptan of acrylic acid Ester、Dodecafluoroheptyl methacrylate、Ten trifluoro monooctyl ester of methacrylic acidOne of or a variety of, the vinyl silicon-containing monomer
Including the different methoxy silane of vinyl three, the different Ethoxysilane of vinyl three, vinyl silane triisopropoxide, etc. vinyl contain
One of silicon monomer is a variety of;The comonomer B includes acrylic acid, methacrylic acid, dimethylaminoethyl acrylate, first
Base dimethylaminoethyl acrylate, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, propylene
Sour octadecyl ester, octadecyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, metering system
One of sour hydroxypropyl acrylate, isobornyl acrylate, styrene are a variety of.
Preferably, the fluorine-containing or siliceous linear polymer of the hydroxyl reactive group includes fluorinated hydroxy polyethers, hydroxyl
One of fluorochemical polyether or polysiloxanes of based polysiloxane and water-solubility modifying are a variety of.
Preferably, the water cross-linking agent is by hydroxy polyethers (molecular weight 100-2000), methyl diethanolamine, two
The final water dispersible isocyanate ester compound or use of the hydrophilic compounds such as hydroxymethyl propionic acid, dimethylolpropionic acid modification
The closed isocyanate ester compound of methyl ethyl ketoxime end-capping reagent;The isocyanate ester compound includes toluene di-isocyanate(TDI)
(TDI), ditolylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), diformazan
Base biphenyl diisocyanate (TODI), polymethylene multi-phenenyl isocyanate (PAPI), 1,6- hexamethylene diisocyanate
(HDI), trimethyl -1,6- hexamethylene diisocyanate, isoflurane chalcone diisocyanate (IPDI), two isocyanide of 1,4- hexamethylene
Acid esters (CHDI), dicyclohexyl diisocyanate (H12MDI), Methylcyclohexyl diisocyanate (HTDI), two methylene of hexamethylene
One or more of group diisocyanate (HXDI), norbornene alkyl diisocyanate (NB-DI), HDI trimer.
Preferably, the water soluble acrylic acid esters polymer includes that the comonomer B is passed through polymerisation in solution or lotion
Polymerize obtained polymer, the aqueous polyurethane quasi polymer be soft segment compound reacted with hydrophilic compounds can water
The aqueous polyurethane quasi polymer of dispersion, the soft segment compound include the isocyanate ester compound, polyether Glycols or
One of polyalcohol, polyester polyol are a variety of, and hydrophilic compounds include methyl diethanolamine, dihydromethyl propionic acid, dihydroxy
One of methylbutanoic acid is a variety of.
Preferably, the coalescing agent includes dibutyltin dilaurate, triethylenediamine, bis- (dimethylamino second
Base) one of ether or a variety of and cosolvent and the compound for having reacted hydroxyl and isocyano catalytic action;It is described to help
Solvent includes methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, glycol ethers, tetrahydrofuran, dioxy
One or more of six rings and halogenated hydrocarbons.
Preferably, the aqueous fluorine-containing of the low-surface-energy or silyl acrylate esters scopiform polymer account for the aqueous three proofings
The fluorine-containing or siliceous linear polymer of the 1-50wt% of leather finishing agent, the hydroxyl reactive group account for the aqueous three proofings
The 0-20wt% of leather finishing agent, the water cross-linking agent account for the 0-80% of the aqueous three proofings leather finishing agent, and described aqueous third
Olefin(e) acid esters polymer or aqueous polyurethane quasi polymer account for the 0-60wt% of the aqueous three proofings leather finishing agent, the film forming
Auxiliary agent accounts for the 0-50wt% of the aqueous three proofings leather finishing agent.
A kind of application method of aqueous three proofings leather finishing agent, it is characterised in that: by the aqueous three proofings leather finishing agent
Surface layer coating is carried out to semifinished leather products by spraying or dip-coating or blade coating after being diluted with water, then leather coating is carried out
130oC~170oThe drying of 1min ~ 10min is crosslinked film forming when C is.
The invention has the benefit that aqueous three proofings leather finishing agent aqueous dispersion Environmental Safety, raw material sources are extensive,
Preparation method is simple for three proofings leather, and the three proofings leather of preparation has excellent Water-proof and oil-proof and anti-pollution and has
Smooth feel, in addition the gloss style of three proofings leather can be made up of system, and three proofings leather finishing agent and correlation are mating
Technology and three proofings leather products have significant application prospect and considerable economic benefit.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other drawings based on these drawings.
Fig. 1 is coating conditions of the aqueous anti-doodling leather finishing agent on glass, it can be seen that coating is fully transparent, oiliness note
Number pen will not leave pen touch on coating.
Fig. 2 is the coated leather of aqueous anti-doodling leather finishing agent, it can be seen that ball pen or permanent pen are coating
It is write on leather afterwards, trace can be used common paper handkerchief to wipe completely.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention uses Industrial raw material, has carried out deep design, transformation and complete to super-hydrophobic oleophobic polymeric system
It is kind, the water dispersible polymer coating materials with Water-proof and oil-proof, anti-graffiti function are successfully prepared, and apply according to leather
Industry technique and performance requirement are adornd, aqueous three proofings leather finishing agent is had developed.Aqueous three proofings leather finishing agent water of the invention
Dispersion Environmental Safety, raw material sources are extensive, and preparation method is simple for three proofings leather, and the three proofings leather of preparation has excellent
Good Water-proof and oil-proof and anti-pollution simultaneously have smooth feel, and in addition the gloss style of three proofings leather can be made up of system
Regulation, three proofings leather finishing agent and related matching technology and three proofings leather products have significant application prospect and considerable warp
Ji benefit.
Embodiment 1: aqueous three proofings leather finishing agent A
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 50g fluorinated hydroxy polyethers, 50g water soluble acrylic acid esters
Polymer, 50g aqueous polyurethane quasi polymer, the aqueous HDI trimer of 100g, 10g dibutyltin dilaurate, 50g acetone
It is uniformly mixed, adding moisture to be dissipated to solid content is 35%, obtains aqueous three proofings leather finishing agent A.
Embodiment 2: aqueous three proofings leather finishing agent B
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 40g fluorinated hydroxy polyethers, 60g water soluble acrylic acid esters
Polymer, 40g aqueous polyurethane quasi polymer, the aqueous HDI trimer of 100g, 5g dibutyltin dilaurate, 50g acetic acid fourth
Ester is uniformly mixed, and adding moisture to be dissipated to solid content is 35%, obtains aqueous three proofings leather finishing agent B.
Embodiment 3: aqueous three proofings leather finishing agent C
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 40g fluorinated hydroxy polyethers, 20g water soluble acrylic acid esters
The aqueous HDI trimer of polymer, 100g, 5g triethylenediamine, 50g butyl acetate are uniformly mixed, and moisture is added to be dissipated to solid content
It is 35%, obtains aqueous three proofings leather finishing agent C.
Embodiment 4: aqueous three proofings leather finishing agent D
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 40g hydroxyl polysiloxanes, 20g water-and acrylate
Quasi polymer, 20g aqueous polyurethane quasi polymer, the aqueous HDI trimer of 50g, 5g triethylenediamine, 50g butyl acetate are mixed
It closes uniformly, adding moisture to be dissipated to solid content is 35%, obtains aqueous three proofings leather finishing agent D.
Embodiment 5: aqueous three proofings leather finishing agent E
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 60g hydroxyl polysiloxanes, 20g water-and acrylate
Quasi polymer, 20g aqueous polyurethane quasi polymer, the aqueous HDI trimer of 100g, 5g triethylenediamine, 50g butyl acetate are mixed
It closes uniformly, adding moisture to be dissipated to solid content is 35%, obtains aqueous three proofings leather finishing agent D.
Embodiment 6: aqueous three proofings leather finishing agent F
By 100g aqueous silicon-acrylate class scopiform polymer, 60g hydroxyl polysiloxanes, 20g water-and acrylate
Quasi polymer, 20g aqueous polyurethane quasi polymer, the aqueous HDI trimer of 100g, 5g dibutyltin dilaurate, 50g acetic acid
Butyl ester is uniformly mixed, and adding moisture to be dissipated to solid content is 35%, obtains aqueous three proofings leather finishing agent F.
Embodiment 7: aqueous three proofings leather finishing agent G
By 100g aqueous fluorine-containing esters of acrylic acid scopiform polymer, 60g hydroxyl polysiloxanes, 20g water-based polyurethane
Polymer, the aqueous HDI trimer of 100g, 5g dibutyltin dilaurate, 50g butyl acetate are uniformly mixed, and moisture is added to be dissipated to
Solid content is 35%, obtains aqueous three proofings leather finishing agent F.
Embodiment 8: aqueous three proofings leather finishing agent H
100g aqueous silicon-acrylate class scopiform polymer, 60g fluorinated hydroxy polyethers, 20g aqueous polyurethane are birdsed of the same feather flock together
Object is closed, the aqueous HDI trimer of 100g, 5g dibutyltin dilaurate, 50g butyl acetate are uniformly mixed, and add moisture to be dissipated to solid
Content is 35%, obtains aqueous three proofings leather finishing agent H.
Embodiment 9: aqueous three proofings leather finishing agent I
100g aqueous silicon-acrylate class scopiform polymer, 60g fluorinated hydroxy polyethers, 20g aqueous polyurethane are birdsed of the same feather flock together
Object is closed, the aqueous HDI trimer of 100g, 5g triethylenediamine, 50g butyl acetate are uniformly mixed, and are added moisture to be dissipated to solid content and are
35%, obtain aqueous three proofings leather finishing agent I.
Test one: coating transparent test
Aqueous three proofings leather finishing agent is coated on glass slide using blade coating mode, using the saturating of ultraviolet method testing coating
Rate is crossed, transmitance is up to 98.9% as the result is shown.It is fully transparent to visually observe coating.
Test two: the anti-ball pen scribble performance of leather after covering with paint
Using blade coating mode, the surface layer for carrying out aqueous three proofings leather finishing agent to leather is coated, 140 after surface dryingoC drying is handed over
It is unified into film 3min, experimental result shows and write on the leather of ball pen after application that trace can be wiped completely with common paper handkerchief.
Test three: leather grease proofness marking pen scribble performance after covering with paint
Using blade coating mode, the surface layer for carrying out aqueous three proofings leather finishing agent to leather is coated, 140 after surface dryingoC drying is handed over
It is unified into film 3min, experimental result shows and write on the leather of permanent pen after application that trace can be complete with common paper handkerchief
Erasing.
Test result is as shown in Figure 1, 2.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of aqueous three proofings leather finishing agent, it is characterised in that including following raw material: the aqueous fluorine-containing of low-surface-energy is siliceous
Esters of acrylic acid scopiform polymer, hydroxyl reactive group fluorine-containing or siliceous linear polymer, water-and acrylate birds of the same feather flock together
Close object or aqueous polyurethane quasi polymer, water cross-linking agent and coalescing agent;
The aqueous fluorine-containing or silyl acrylate esters scopiform polymer of the low-surface-energy are to pass through solution by vinyl monomer certainly
The polymer obtained by base polymerization or emulsion polymerization;
The water soluble acrylic acid esters polymer includes the polymerization for obtaining comonomer B by polymerisation in solution or emulsion polymerization
Object, the aqueous polyurethane quasi polymer are one of polyether Glycols or polyalcohol, polyester polyol or a variety of and isocyanide
The water dispersible aqueous polyurethane quasi polymer that acid esters compound and hydrophilic compounds react, hydrophilic compounds include
One of methyl diethanolamine, dihydromethyl propionic acid, dimethylolpropionic acid are a variety of;
The vinyl monomer includes low-surface-energy monomer A and comonomer B, the low-surface-energy monomer A are that vinyl is fluorine-containing
Monomer or vinyl silicon-containing monomer, the vinyl fluorochemical monomer include perfluoro butyl acrylate, perfluoro hexyl acrylate,
Perfluoro capryl acrylate, perfluoro decyl acrylate, methyl perfluoro butyl propyleneglycol acid esters, methyl perfluoro ethylhexyl acrylate,
Methyl perfluoro octyl acrylate, methyl perfluoro decyl acrylate,FirstBase acrylic acid trifluoro ethyl ester, hexafluorobutyl acrylate,
Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, ten trifluoro monooctyl ester of methacrylic acid
One of or it is a variety of, the vinyl silicon-containing monomer includes the different methoxy silane of vinyl three, the different ethyoxyl silicon of vinyl three
One of alkane, vinyl silane triisopropoxide are a variety of;The comonomer B includes acrylic acid, methacrylic acid, propylene
Sour dimethylaminoethyl, dimethylaminoethyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, first
Base butyl acrylate, octadecyl acrylate, octadecyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, propylene
One of sour hydroxypropyl acrylate, hydroxy propyl methacrylate, isobornyl acrylate, styrene are a variety of.
2. aqueous three proofings leather finishing agent as described in claim 1, it is characterised in that: the hydroxyl reactive group contains
Fluorine or siliceous linear polymer include the fluorochemical polyether or poly- of fluorinated hydroxy polyethers, hydroxyl polysiloxane and water-solubility modifying
One of siloxanes is a variety of.
3. aqueous three proofings leather finishing agent as described in claim 1, it is characterised in that: the water cross-linking agent is by hydroxyl
Base polyethers, methyl diethanolamine, dihydromethyl propionic acid, the modification of dimethylolpropionic acid hydrophilic compounds it is final water dispersible different
Cyanate compound uses the closed isocyanate ester compound of methyl ethyl ketoxime end-capping reagent, and wherein hydroxy polyethers molecular weight is
100-2000;The isocyanate ester compound includes toluene di-isocyanate(TDI) (TDI), ditolylmethane diisocyanate
(MDI), naphthalene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), dimethyl diphenyl diisocyanate (TODI), mostly Asia
The more phenyl isocyanates of methyl (PAPI), 1,6- hexamethylene diisocyanate (HDI), trimethyl -1,6- hexa-methylene two are different
Cyanate, isoflurane chalcone diisocyanate (IPDI), 1,4- cyclohexane diisocyanate (CHDI), dicyclohexyl diisocyanate
(H12MDI), Methylcyclohexyl diisocyanate (HTDI), cyclohexanedimethyleterephthalate diisocyanate (HXDI), norbornane two
One or more of isocyanates (NB-DI), HDI trimer.
4. aqueous three proofings leather finishing agent as described in claim 1, it is characterised in that: the coalescing agent include cosolvent,
The compound of catalytic action has been reacted hydroxyl and isocyano;The cosolvent includes methyl ethyl ketone, acetone, ethyl acetate, second
One or more of acid butyl ester, toluene, dimethylformamide, glycol ethers, tetrahydrofuran, dioxane and halogenated hydrocarbons;It is right
The compound that hydroxyl and isocyano have reacted catalytic action includes dibutyltin dilaurate, triethylenediamine, bis- (two
Methylaminoethyl) one of ether or a variety of.
5. aqueous three proofings leather finishing agent as described in claim 1, it is characterised in that: the aqueous fluorine-containing of the low-surface-energy or
Silyl acrylate esters scopiform polymer accounts for the 1-50wt% of the aqueous three proofings leather finishing agent, the hydroxyl reactivity base
The fluorine-containing or siliceous linear polymer of group accounts for the 20wt% of the aqueous three proofings leather finishing agent hereinafter, not equal to 0, described aqueous
Crosslinking agent accounts for the 80% of the aqueous three proofings leather finishing agent hereinafter, not equal to 0, the water soluble acrylic acid esters polymer or water
Property polyurethane polymer account for the 60wt% of the aqueous three proofings leather finishing agent hereinafter, not equal to 0, the coalescing agent accounts for institute
The 50wt% of aqueous three proofings leather finishing agent is stated hereinafter, not equal to 0.
6. a kind of application method of aqueous three proofings leather finishing agent a method as claimed in any one of claims 1 to 5, it is characterised in that: by institute
It states and surface layer coating is carried out to semifinished leather products by spraying or dip-coating or blade coating after aqueous three proofings leather finishing agent is diluted with water, so
130 are carried out to leather coating afterwardsoC~170oThe drying of 1min ~ 10min is crosslinked film forming when C is.
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