CN106554690A - A kind of silane-modified leather special coating and preparation method thereof - Google Patents
A kind of silane-modified leather special coating and preparation method thereof Download PDFInfo
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- CN106554690A CN106554690A CN201611092985.0A CN201611092985A CN106554690A CN 106554690 A CN106554690 A CN 106554690A CN 201611092985 A CN201611092985 A CN 201611092985A CN 106554690 A CN106554690 A CN 106554690A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of silane-modified leather special coating, it is made up of the raw material of following weight parts：Anilinomethyl triethoxysilane 0.6 1, casein 10 14, the caprolactam aqueous solution 10 16 of triethanolamine 24,27 30%, cresyl diphenyl phosphate 0.1 0.3, butyl titanate 23, methyl methacrylate 80 90, butyl acrylate 50 60, the acid 0.6 1, calcium mahogany sulfonate 0.1 0.2 of Ammonium persulfate. 0.1 0.13, hydrocarbyl succinimide, thiol-butyl tin 0.3 1, sodium bicarbonate 0.7 2, linalool 0.01 0.02, β hydroxyalkyl amides 0.5 1, APP 12.The coating of the present invention has good water-resistance, pliability, is particularly suitable for leather use, and the feature of environmental protection is good.
Description
Technical field
The present invention relates to leather coating technical field, more particularly to a kind of silane-modified leather special coating and its preparation side
Method.
Background technology
Leather be by animal husbandry side-product natural animal skin made by after tanning, dyeing, stuffing and covering with paint not
Rotten material.Leather has that special viscoelasticity, softness, plentiful, outward appearance are good, intensity is high, consolidation, flexible, resist bending, can
Retractility, against weather, good hand touch.Conventional leather finishing agent component has pigment, dyeing liquor, resin binder, polyacrylic acid
Ester, polyurethane, wax, filler and nitrocellulose.We improve the performance of leather coating using TiO2 nano-particle.Nanometer material
Expect because showing special property with great surface-to-volume ratio, because of chemical bond ability strong between polymer
Show new characteristic.TiO2 nanoparticles have an extensive use in many fields, for example antibacterial, Superhydrophilic material, thoroughly
Steam material, solaode, ultraviolet absorber, catalysis material, plastics, fiber, controlled release, pigment, heat-barrier material, coating are glued
Mixture, automatic cleaning coating, scratch resistance abrasion-resistant material etc..The nano material used in leather finish has very strong durability,
Contribute to leather and withstand time test.
The content of the invention
The object of the invention is exactly for the defect for making up prior art, there is provided a kind of silane-modified leather special coating and its
Preparation method.
The present invention is achieved by the following technical solutions：
A kind of silane-modified leather special coating, it is made up of the raw material of following weight parts：
Anilinomethyl triethoxysilane 0.6-1, casein 10-14, the caprolactam aqueous solution of triethanolamine 2-4,27-30%
10-16, cresyl diphenyl phosphate 0.1-0.3, butyl titanate 2-3, methyl methacrylate 80-90, butyl acrylate
50-60, Ammonium persulfate. 0.1-0.13, hydrocarbyl succinimide acid 0.6-1, calcium mahogany sulfonate 0.1-0.2, thiol-butyl tin 0.3-1, carbonic acid
Hydrogen sodium 0.7-2, linalool 0.01-0.02, beta-hydroxy alkylamide 0.5-1, APP 1-2.
A kind of preparation method of described silane-modified leather special coating, comprises the following steps：
（1）Above-mentioned calcium mahogany sulfonate is added in the dehydrated alcohol of its weight 40-50 times, is stirred, add above-mentioned aniline
The 20-30% of MTES weight, at 60-70 DEG C is incubated 3-4 minutes, obtains silanol solution；
（2）Above-mentioned sodium bicarbonate is added in the deionized water of its weight 10-14 times, is stirred, add above-mentioned metatitanic acid four
Butyl ester, stirring reaction 20-30 minute, adds above-mentioned silanol solution, and it is 80-86 DEG C to rise high-temperature, insulated and stirred 20-30 point
Clock, is silane-modified precursor solution；
（3）By the acid of above-mentioned hydrocarbyl succinimide, linalool mixing, stir, add the 5-7% of above-mentioned methyl methacrylate weight,
The slow high-temperature that rises is 70-80 DEG C, and sulphuric acid of the Deca concentration for 96-98%, regulation pH are 1-2, add thiol-butyl tin, insulation
Reaction 30-40 minutes, obtain modified monomer；
（4）Above-mentioned casein is added in the deionized water of its weight 7-10 times, it is 60-65 DEG C to rise high-temperature, adds three second
Hydramine, insulated and stirred 30-40 minute, it is 70-75 DEG C to rise high-temperature, the caprolactam aqueous solution of the above-mentioned 27-30% of Deca, Deca
Rear insulated and stirred 1.7-2 hour is finished, 10-15 DEG C is naturally cooled to, regulation pH is 5-6, adds above-mentioned silane-modified presoma
Solution, it is 80-85 DEG C to rise high-temperature, insulated and stirred 90-100 minute, obtains casein titanium colloidal sol；
（5）Remaining anilinomethyl triethoxysilane is added in casein titanium colloidal sol, β-hydroxyl alkane under stirring condition, is added
Base amide, 200-300 rev/min of stirring 17-20 minute, obtains silane-modified casein titanium colloidal sol；
（6）Ammonium persulfate. is added in the deionized water of its weight 60-70 times, is stirred；
（7）Above-mentioned casein titanium colloidal sol is sent in 76-80 DEG C of water bath with thermostatic control, the above-mentioned remaining methyl methacrylate of Deca
The mixed liquor of ester, butyl acrylate, adds above-mentioned modified monomer, stirs after completion of dropping, add above-mentioned Ammonium persulfate. water
Solution, insulation reaction 80-90 minute, adds remaining each raw material, stirs, discharge, stir to room temperature, obtain described leather special
Use coating.
A kind of silane-modified leather special coating, the using method of the coating is：Using the front coating ultrasound by the present invention
20-30 minutes are processed, leather surface is sprayed under the pressure of 0.2MPa with spray gun, normal temperature drying, in 76-80 DEG C, 80bar
Under the conditions of press, spray again afterwards the present invention coating, normal temperature drying, you can.
It is an advantage of the invention that：Present invention synthesis of caprolactam modified Casein first, itself has certain self emulsifying
Agent is acted on；When nanometer presoma is introduced therein to, with the hydrolysis of presoma, the nanoparticle of generation can gradually spread and wrap
Caprolactam modified Casein outer layer is rolled in, so as to form hud typed caprolactam modified Casein/titanium dioxide component system；When to
When adding acrylic ester monomer in system, the system provides solubilized place for monomer, in the presence of initiator, by nanometer
Titanium dioxide and polyacrylate segment are successfully introduced into casein base material, ultimately form hud typed casein based nano-titanium dioxide hydridization
Emulsion；When emulsion drying and forming-film, nano titanium oxide is distributed in coating material surface, forms one layer of protection in substrate surface
Layer；
The coating of the present invention has good self-cleaning performance：
When coating surface be infected with organic dirt when, due to tetrabutyl titanate hydrolysis formed nano titanium oxide surface adsorption it is a large amount of
Hydroxyl, under ultraviolet light, be conducive to produce ultra-hydrophilic surface, be catalyzed photodissociation organic dirt segment, formed carbon dioxide
And water, so as to decompose organic dirt, show self-cleaning performance；
The coating of the present invention is strong with the caking property of leather substrate, and peel strength is high；
On the one hand be because titania nanoparticles have bigger specific surface area promote binding agent, other finish auxiliaries with
The reactivity of leather matrix；On the other hand titania nanoparticles very little is because, hole between leather fiber can be penetrated,
Produce and the higher interaction between materials with hide glue fibril, therefore presence of the titanium dioxide nano-particle in film is also apparent from
The caking property of coatings and epidermis face is increased, peel strength is improve.
The coating of the present invention has good water-resistance, pliability, is particularly suitable for leather use, and the feature of environmental protection is good.
Specific embodiment
A kind of silane-modified leather special coating, it is made up of the raw material of following weight parts：
Anilinomethyl triethoxysilane 0.6, casein 10, the caprolactam aqueous solution 10 of triethanolamine 2,27%, tolyl two
Phenyl phosphate ester 0.1, butyl titanate 2, methyl methacrylate 80, butyl acrylate 50, Ammonium persulfate. 0.1, hydrocarbyl succinimide
Acid 0.6, calcium mahogany sulfonate 0.1, thiol-butyl tin 0.3, sodium bicarbonate 0.7, linalool 0.01, β hydroxyalkyl amides 0.5, poly- phosphorus
Sour ammonium 1.
A kind of preparation method of described silane-modified leather special coating, comprises the following steps：
（1）Above-mentioned calcium mahogany sulfonate is added in the dehydrated alcohol of 40 times of its weight, is stirred, add above-mentioned anilinomethyl
The 20% of triethoxysilane weight, at 60 DEG C is incubated 3 minutes, obtains silanol solution；
（2）Above-mentioned sodium bicarbonate is added in the deionized water of 10 times of its weight, is stirred, add above-mentioned four fourth of metatitanic acid
Ester, stirring reaction 20 minutes add above-mentioned silanol solution, and it is 80 DEG C to rise high-temperature, and insulated and stirred 20 minutes, is silane-modified
Precursor solution；
（3）By the acid of above-mentioned hydrocarbyl succinimide, linalool mixing, stir, add the 5% of above-mentioned methyl methacrylate weight, delay
Slowly it is 70 DEG C to rise high-temperature, and Deca concentration is 96% sulphuric acid, and it is 1 to adjust pH, addition thiol-butyl tin, insulation reaction 30 minutes,
Obtain modified monomer；
（4）Above-mentioned casein is added in the deionized water of 7 times of its weight, it is 60 DEG C to rise high-temperature, adds triethanolamine, protects
Temperature stirring 30 minutes, it is 70 DEG C to rise high-temperature, the caprolactam aqueous solution of Deca above-mentioned 27%, insulated and stirred 1.7 after completion of dropping
Hour, 10 DEG C are naturally cooled to, it is 5 to adjust pH, adds above-mentioned silane-modified precursor solution, and it is 80 DEG C to rise high-temperature, insulation
Stirring 90 minutes, obtains casein titanium colloidal sol；
（5）Remaining anilinomethyl triethoxysilane is added in casein titanium colloidal sol, β hydroxyalkyls under stirring condition, are added
Amide, 200 revs/min are stirred 17 minutes, obtain silane-modified casein titanium colloidal sol；
（6）Ammonium persulfate. is added in the deionized water of 60 times of its weight, is stirred；
（7）Above-mentioned casein titanium colloidal sol is sent in 76 DEG C of water bath with thermostatic control, the above-mentioned remaining methyl methacrylate of Deca, third
The mixed liquor of olefin(e) acid butyl ester, adds above-mentioned modified monomer, stirs after completion of dropping, add above-mentioned ammonium persulfate aqueous solution,
Insulation reaction 80 minutes, adds remaining each raw material, stirs, and discharges, stirs to room temperature, obtains described leather special coating.
A kind of silane-modified leather special coating, the using method of the coating is：Using the front coating ultrasound by the present invention
Process 20 minutes, leather surface, normal temperature drying, under conditions of 76 DEG C, 80bar are sprayed under the pressure of 0.2MPa with spray gun
Flatiron, sprays the coating of the present invention, normal temperature drying afterwards again, you can.
Performance test：
Profile pattern is good, entirely without flake；
Resistance to dry medium is flexible（100000 times）：Flawless；
Coating dry state cementability（N/10mm）：4.63；
Coating hygrometric state cementability（N/10mm）：2.30.
Claims (3)
1. a kind of silane-modified leather special coating, it is characterised in that it is made up of the raw material of following weight parts：
Anilinomethyl triethoxysilane 0.6-1, casein 10-14, the caprolactam aqueous solution of triethanolamine 2-4,27-30%
10-16, cresyl diphenyl phosphate 0.1-0.3, butyl titanate 2-3, methyl methacrylate 80-90, butyl acrylate
50-60, Ammonium persulfate. 0.1-0.13, hydrocarbyl succinimide acid 0.6-1, calcium mahogany sulfonate 0.1-0.2, thiol-butyl tin 0.3-1, carbonic acid
Hydrogen sodium 0.7-2, linalool 0.01-0.02, beta-hydroxy alkylamide 0.5-1, APP 1-2.
2. a kind of preparation method of silane-modified leather special coating as claimed in claim 1, it is characterised in that including following
Step：
（1）Above-mentioned calcium mahogany sulfonate is added in the dehydrated alcohol of its weight 40-50 times, is stirred, add above-mentioned aniline
The 20-30% of MTES weight, at 60-70 DEG C is incubated 3-4 minutes, obtains silanol solution；
（2）Above-mentioned sodium bicarbonate is added in the deionized water of its weight 10-14 times, is stirred, add above-mentioned metatitanic acid four
Butyl ester, stirring reaction 20-30 minute, adds above-mentioned silanol solution, and it is 80-86 DEG C to rise high-temperature, insulated and stirred 20-30 point
Clock, is silane-modified precursor solution；
（3）By the acid of above-mentioned hydrocarbyl succinimide, linalool mixing, stir, add the 5-7% of above-mentioned methyl methacrylate weight,
The slow high-temperature that rises is 70-80 DEG C, and sulphuric acid of the Deca concentration for 96-98%, regulation pH are 1-2, add thiol-butyl tin, insulation
Reaction 30-40 minutes, obtain modified monomer；
（4）Above-mentioned casein is added in the deionized water of its weight 7-10 times, it is 60-65 DEG C to rise high-temperature, adds three second
Hydramine, insulated and stirred 30-40 minute, it is 70-75 DEG C to rise high-temperature, the caprolactam aqueous solution of the above-mentioned 27-30% of Deca, Deca
Rear insulated and stirred 1.7-2 hour is finished, 10-15 DEG C is naturally cooled to, regulation pH is 5-6, adds above-mentioned silane-modified presoma
Solution, it is 80-85 DEG C to rise high-temperature, insulated and stirred 90-100 minute, obtains casein titanium colloidal sol；
（5）Remaining anilinomethyl triethoxysilane is added in casein titanium colloidal sol, β-hydroxyl alkane under stirring condition, is added
Base amide, 200-300 rev/min of stirring 17-20 minute, obtains silane-modified casein titanium colloidal sol；
（6）Ammonium persulfate. is added in the deionized water of its weight 60-70 times, is stirred；
（7）Above-mentioned casein titanium colloidal sol is sent in 76-80 DEG C of water bath with thermostatic control, the above-mentioned remaining methyl methacrylate of Deca
The mixed liquor of ester, butyl acrylate, adds above-mentioned modified monomer, stirs after completion of dropping, add above-mentioned Ammonium persulfate. water
Solution, insulation reaction 80-90 minute, adds remaining each raw material, stirs, discharge, stir to room temperature, obtain described leather special
Use coating.
3. a kind of silane-modified leather special coating according to claim 1,2, it is characterised in that the user of the coating
Method is：Using the front coating supersound process 20-30 minute by the present invention, leather table is sprayed under the pressure of 0.2MPa with spray gun
Face, normal temperature drying, under conditions of 76-80 DEG C, 80bar press, spray again afterwards the present invention coating, normal temperature drying, i.e.,
Can.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611092985.0A CN106554690A (en) | 2016-12-02 | 2016-12-02 | A kind of silane-modified leather special coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611092985.0A CN106554690A (en) | 2016-12-02 | 2016-12-02 | A kind of silane-modified leather special coating and preparation method thereof |
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| CN106554690A true CN106554690A (en) | 2017-04-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107855118A (en) * | 2017-12-12 | 2018-03-30 | 成都育芽科技有限公司 | A kind of environment-friendly dye sewage-treating agent and preparation method thereof |
-
2016
- 2016-12-02 CN CN201611092985.0A patent/CN106554690A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107855118A (en) * | 2017-12-12 | 2018-03-30 | 成都育芽科技有限公司 | A kind of environment-friendly dye sewage-treating agent and preparation method thereof |
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