CN106380984A - Decorative antibacterial leather coating and preparation method thereof - Google Patents
Decorative antibacterial leather coating and preparation method thereof Download PDFInfo
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- CN106380984A CN106380984A CN201610870874.1A CN201610870874A CN106380984A CN 106380984 A CN106380984 A CN 106380984A CN 201610870874 A CN201610870874 A CN 201610870874A CN 106380984 A CN106380984 A CN 106380984A
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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
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a decorative antibacterial leather coating. The decorative antibacterial leather coating is prepared from the following raw materials in parts by weight: 0.7 to 1 part of ammonium metaborate, 1.7 to 2 parts of polyvinylpyrrolidone, 0.8 to 1 part of polyacrylamide, 0.1 to 0.13 part of triethanolamine, 190 to 200 parts of methyl methacrylate, 3 to 4 parts of sodium dodecyl sulfate, 0.1 to 0.2 part of urotropin, 0.2 to 0.3 part of ammonium persulfate, 6 to 7 parts of 20 to 25 percent formaldehyde solution, 16 to 20 parts of zinc acetate, 4 to 7 parts of silver nitrate, 1.6 to 2 parts of microcrystalline wax, 0.8 to 1 part of dodecyl trimethyl ammonium chloride, 0.1 to 0.2 part of trimethylolpropane, 0.1 to 0.2 part of guaiacol, 1 to 2 parts of butyl oleate, 2 to 3 parts of ash calcium powder and 1.6 to 2 parts of stannous chloride. The coating disclosed by the invention has good bacteria resistance and excellent water vapor permeability and water resistance; a leather coated by obtained emulsion is good in bacteria resistance and excellent in sanitary property.
Description
Technical field
The present invention relates to leather coating technical field, more particularly, to a kind of decoration type antibacterial leather coating and its preparation side
Method.
Background technology
Leather finishing agent/spinning coating agent is a kind of macromolecule compound being spread evenly across leather/textile surface.It
One or more layers film is formed in leather/fabric face by adhesive effect.Therefore, coating material quality, not only directly affects
Product appearance, quality, and decide the performance of product to a great extent.Polyacrylate dispersion has the pliable and tough richness of film forming
Flexible, the features such as coating is fast light, ageing-resistant, wet-rub resistance can be excellent, it is the class leather spinning coating being widely used at present
Material.But, the presence of some polar groups in conventional polypropylene acid esters emulsion, and product storing, transports, using process
In affected by environmental condition, often occur go mouldy, the phenomenon such as bacteria breed, not only waste raw material when serious, and
The important propagating source of disease can be become, endanger human health.Meanwhile, coating material defines one in leather/fabric face
Layer fine and close film, the sweat that Severe blockage human body distributes diffuses to the passage in the external world, leads to the health of leather goods/textile
Performance suffers extreme influence, and snugness of fit declines.In recent years, with the continuous improvement of human living standard, research and development are anti-
Leather/weaving that bacterium property projects, sanitation performance is excellent uses coating material extremely urgent.
With the antibiotic property of raising polyacrylate coatings, sanitation performance is target exploitation nano-ZnO and nanometer ZO/Ag is combined
The antibiotic property of particle, prevents coating breed bacteria, goes mouldy；Huge using nanometer ZO and nano-ZnO/Ag compound particle
Specific surface area, improves the sanitation performance of coating.
Nano material has the features such as size is little, and surface energy is high in itself, is thus susceptible to reunion, bad dispersibility.In addition, receiving
In the preparation process of nano composite material, the compatibility of the nano material polymeric matrix relatively low with surface energy is poor, and the two is mutually mixed
It is difficult to compatible during conjunction, interface easily space, there is phenomenon of phase separation.In order that nano material is evenly dispersed in polymer matrix
In body, essential to its modifying surface.
Content of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of decoration type antibacterial leather coating and its system
Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of decoration type antibacterial leather coating, it is made up of the raw material of following weight parts：
Ammonium metaborate 0.7-1, polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, triethanolamine 0.1-0.13, methyl-prop
E pioic acid methyl ester 190-200, lauryl sodium sulfate 3-4, methenamine 0.1-0.2, the first of ammonium persulfate 0.2-0.3,20-25%
Aldehyde solution 6-7, zinc acetate 16-20, silver nitrate 4-7, microcrystalline wax 1.6-2, DTAC 0.8-1, three hydroxyls
Methylpropane 0.1-0.2, guaiacol 0.1-0.2, butyl oleate 1-2, sierozem power 2-3, stannous chloride 1.6-2.
A kind of preparation method of described decoration type antibacterial leather coating, comprises the following steps：
（1）It is added to above-mentioned zinc acetate, methenamine mixing in the deionized water of compound weight 60-100 times, stirring is all
Even, it is liquid a；
（2）Above-mentioned polyvinylpyrrolidone is added in its weight 20-30 times, 70-75% ethanol solution, stirs,
Mix with above-mentioned liquid a, ultrasonic 20-30 minute, mix with above-mentioned sierozem power, stir, be sent to ptfe autoclave
In, microwave hydrothermal 20-30 minute at 160-170 DEG C, it is cooled to normal temperature, filter, precipitate with deionized water, ethanol are washed successively
Wash 3-4 time, be placed in baking oven, be dried, obtain modified zinc oxide；
（3）Take above-mentioned guaiacol, be added in the absolute ethyl alcohol of its weight 10-14 times, stir, add trihydroxy methyl third
Alkane, stirs, and obtains propane alcohol liquid；
（4）By above-mentioned modified zinc oxide, stannous chloride mixing, it is added in the absolute ethyl alcohol of compound weight 100-120 times, surpasses
Sound 3-5 minute, adds above-mentioned silver nitrate, triethanolamine, stirs, and drips the formalin of above-mentioned 20-25%, completion of dropping
After add above-mentioned propane alcohol liquid, rise high-temperature and be 60-65 DEG C, insulated and stirred 20-30 minute, be centrifuged off supernatant, will precipitate
Deionized water, ethanol wash 3-4 time successively, are placed in baking oven, and 10-17 minute is dried at 90-100 DEG C, obtain Ag doping and change
Property zinc oxide；
（5）By above-mentioned ammonium metaborate, DTAC mixing, be added to compound weight 10-15 times go from
In sub- water, stir, obtain ammonium dispersion liquid；
（6）Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, stirs, add acetic acid or ammonia
Water, regulation pH is 6-7, adds above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minute, obtains modified dispersion liquid；
（7）Above-mentioned ammonium persulfate is added in the deionized water of its weight 17-20 times, stirs；
（8）Take the 60-70% of above-mentioned methyl methacrylate weight, mix with butyl oleate, lauryl sodium sulfate, be added to
In above-mentioned modification dispersion liquid, rise high-temperature and be 76-80 DEG C, insulated and stirred 10-14 minute, add above-mentioned ammonium dispersion liquid, stirring is all
Even, drip remaining methyl methacrylate and ammonium persulfate aqueous solution respectively, after completion of dropping, insulation reaction 120-130 is divided
Clock, discharging, add remaining each raw material, stir to normal temperature, obtain described coating.
A kind of described decoration type antibacterial leather coating, the using method of this coating is：Using the front coating by the present invention
Ultrasonically treated 20-30 minute, is sprayed at leather surface with spray gun under the pressure of 0.2MPa, air drying, 76-80 DEG C,
Press under conditions of 80bar, spray the coating of the present invention, air drying afterwards again, you can.
It is an advantage of the invention that：Zinc oxide particles are evenly dispersed into the ethanol solution of stannous chloride by the present invention first
In, Sn2+ will promptly be adsorbed onto zinc oxide surface；Then, add the ethanol solution of Ag (TEA) 2+ in above-mentioned reactant liquor,
Sn2+ with Ag (TEA) 2+ adding, ion-exchange reactions can occur so that Ag+ absorption forms silver kind in zinc oxide surface；Reaction
In the later stage, gradually drip formalin continuously stirred in solution, make Ag be reduced into Ag particle；
ZnO/Ag compound particle of present invention resistance to water itself preferably, is introduced in polyacrylate and can effectively prevent water
Molecule infiltration is in film, and then the water absorption rate of reduction laminated film, improves its resistance to water；
ZnO/Ag compound particle of the present invention has good anti-microbial property, and under illumination condition, ZnO surface produces substantial amounts of
Electronics and hole, the electronics that nanometer Ag capture generates, obtain Ag-, then, the oxygen molecule of Ag- and ZnO adsorption reacts, raw
Become superoxide ion;Superoxide ion is reacted further with water, generates perhydroxyl radical and hydrogen peroxide;The H2O of hole and ZnO adsorption or
HO- ionic reaction, forms the activity hydroxy with strong oxidizing property, and activity hydroxy mutually merges generation hydrogen peroxide.Activity hydroxy
Oxidability is the strongest in water body oxidant, many organic matters of can degrading；Additionally, oxidant superoxide ion, hydrogen peroxide, mistake
Hydroxyl etc. all can destroy biological cell by oxidation reaction and the effect of the large biological molecules such as protein, enzyme, lipid and nucleic acid
Structure, thus kill bacterium.In course of reaction, silver ion plays the effect of catalytic active center, and itself does not consume.Nanometer Ag
Because granularity is minimum, specific surface area big, surface energy is higher, is easily adsorbed by various bacteriums, so just constrains the work of bacterium
Dynamic, make the disorderly imbalance of living environment of bacterium, suppress its breathing, ultimately result in bacterium and " contact is dead " occurs.
The coating of the present invention has good antibiotic property, excellent water vapor permeability and resistance to water, after gained emulsion is covered with paint, lacquer, colour wash, etc.
Leather antibacterial is good, sanitation performance is excellent.The coating of the present invention can form uniform and stable coating, has good decoration
Property.
Specific embodiment
A kind of decoration type antibacterial leather coating, it is made up of the raw material of following weight parts：
Ammonium metaborate 0.7, polyvinylpyrrolidone 1.7, polyacrylamide 0.8, triethanolamine 0.1, methyl methacrylate
190th, lauryl sodium sulfate 3, methenamine 0.1, the formalin 6 of ammonium persulfate 0.2,20%, zinc acetate 16, silver nitrate 4,
Microcrystalline wax 1.6, DTAC 0.8, trimethylolpropane 0.1, guaiacol 0.1, butyl oleate 1, ash
Calcium powder 2, stannous chloride 1.6.
A kind of preparation method of described decoration type antibacterial leather coating, comprises the following steps：
（1）By above-mentioned zinc acetate, methenamine mixing, it is added in the deionized water of 60 times of compound weight, stirs, be
Liquid a；
（2）Above-mentioned polyvinylpyrrolidone is added in 20 times of its weight, 70% ethanol solution, stirs, and above-mentioned
Liquid a mixes, and ultrasonic 20 minutes, mixes with above-mentioned sierozem power, stirs, be sent in ptfe autoclave, at 160 DEG C
Lower microwave hydrothermal 20 minutes, is cooled to normal temperature, filters, precipitate with deionized water, ethanol is washed 3 times successively, is placed in baking oven,
It is dried, obtain modified zinc oxide；
（3）Take above-mentioned guaiacol, be added in the absolute ethyl alcohol of 10 times of its weight, stir, add trimethylolpropane,
Stir, obtain propane alcohol liquid；
（4）By above-mentioned modified zinc oxide, stannous chloride mixing, it is added in the absolute ethyl alcohol of 100 times of compound weight, ultrasonic 3
Minute, add above-mentioned silver nitrate, triethanolamine, stir, the formalin of dropping above-mentioned 20%, add after completion of dropping
State propane alcohol liquid, rise high-temperature and be 60 DEG C, insulated and stirred 20 minutes, it is centrifuged off supernatant, by precipitate with deionized water, ethanol
Wash 3 times successively, be placed in baking oven, be dried 10 minutes at 90 DEG C, obtain Ag doping modified zinc oxide；
（5）By above-mentioned ammonium metaborate, DTAC mixing, it is added to the deionized water of 10 times of compound weight
In, stir, obtain ammonium dispersion liquid；
（6）Above-mentioned polyacrylamide is added in the deionized water of 80 times of its weight, stirs, add acetic acid or ammoniacal liquor,
Adjusting pH is 6, adds above-mentioned Ag doping modified zinc oxide, ultrasonic 20 minutes, obtains modified dispersion liquid；
（7）Above-mentioned ammonium persulfate is added in the deionized water of 17 times of its weight, stirs；
（8）Take the 60% of above-mentioned methyl methacrylate weight, mix with butyl oleate, lauryl sodium sulfate, be added to above-mentioned
In modified dispersion liquid, rise high-temperature and be 76 DEG C, insulated and stirred 10 minutes, add above-mentioned ammonium dispersion liquid, stir, drip respectively
Remaining methyl methacrylate and ammonium persulfate aqueous solution, insulation reaction 120 minutes after completion of dropping, discharging, add remaining
Each raw material, stirs to normal temperature, obtains described coating.
A kind of described decoration type antibacterial leather coating, the using method of this coating is：Using the front coating by the present invention
Ultrasonically treated 20 minutes, it is sprayed at leather surface under the pressure of 0.2MPa with spray gun, air drying, in the bar of 76 DEG C, 80bar
Press under part, spray the coating of the present invention, air drying afterwards again, you can.
Performance test：
Leather after liquid is covered with paint, lacquer, colour wash, etc. is 96.33% to the bacteriostasis rate of Candida albicans, and the bacteriostasis rate to mould is 80.0%.
Claims (3)
1. a kind of decoration type antibacterial leather coating is it is characterised in that what it was made up of the raw material of following weight parts：
Ammonium metaborate 0.7-1, polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, triethanolamine 0.1-0.13, methyl-prop
E pioic acid methyl ester 190-200, lauryl sodium sulfate 3-4, methenamine 0.1-0.2, the first of ammonium persulfate 0.2-0.3,20-25%
Aldehyde solution 6-7, zinc acetate 16-20, silver nitrate 4-7, microcrystalline wax 1.6-2, DTAC 0.8-1, three hydroxyls
Methylpropane 0.1-0.2, guaiacol 0.1-0.2, butyl oleate 1-2, sierozem power 2-3, stannous chloride 1.6-2.
2. a kind of preparation method of decoration type antibacterial leather coating as claimed in claim 1 is it is characterised in that include following walking
Suddenly：
（1）It is added to above-mentioned zinc acetate, methenamine mixing in the deionized water of compound weight 60-100 times, stirring is all
Even, it is liquid a；
（2）Above-mentioned polyvinylpyrrolidone is added in its weight 20-30 times, 70-75% ethanol solution, stirs,
Mix with above-mentioned liquid a, ultrasonic 20-30 minute, mix with above-mentioned sierozem power, stir, be sent to ptfe autoclave
In, microwave hydrothermal 20-30 minute at 160-170 DEG C, it is cooled to normal temperature, filter, precipitate with deionized water, ethanol are washed successively
Wash 3-4 time, be placed in baking oven, be dried, obtain modified zinc oxide；
（3）Take above-mentioned guaiacol, be added in the absolute ethyl alcohol of its weight 10-14 times, stir, add trihydroxy methyl third
Alkane, stirs, and obtains propane alcohol liquid；
（4）By above-mentioned modified zinc oxide, stannous chloride mixing, it is added in the absolute ethyl alcohol of compound weight 100-120 times, surpasses
Sound 3-5 minute, adds above-mentioned silver nitrate, triethanolamine, stirs, and drips the formalin of above-mentioned 20-25%, completion of dropping
After add above-mentioned propane alcohol liquid, rise high-temperature and be 60-65 DEG C, insulated and stirred 20-30 minute, be centrifuged off supernatant, will precipitate
Deionized water, ethanol wash 3-4 time successively, are placed in baking oven, and 10-17 minute is dried at 90-100 DEG C, obtain Ag doping and change
Property zinc oxide；
（5）By above-mentioned ammonium metaborate, DTAC mixing, be added to compound weight 10-15 times go from
In sub- water, stir, obtain ammonium dispersion liquid；
（6）Above-mentioned polyacrylamide is added in the deionized water of its weight 80-100 times, stirs, add acetic acid or ammonia
Water, regulation pH is 6-7, adds above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minute, obtains modified dispersion liquid；
（7）Above-mentioned ammonium persulfate is added in the deionized water of its weight 17-20 times, stirs；
（8）Take the 60-70% of above-mentioned methyl methacrylate weight, mix with butyl oleate, lauryl sodium sulfate, be added to
In above-mentioned modification dispersion liquid, rise high-temperature and be 76-80 DEG C, insulated and stirred 10-14 minute, add above-mentioned ammonium dispersion liquid, stirring is all
Even, drip remaining methyl methacrylate and ammonium persulfate aqueous solution respectively, after completion of dropping, insulation reaction 120-130 is divided
Clock, discharging, add remaining each raw material, stir to normal temperature, obtain described coating.
3. a kind of decoration type antibacterial leather coating according to claim 1,2 is it is characterised in that the using method of this coating
For：Using the ultrasonically treated 20-30 minute of the front coating by the present invention, it is sprayed at leather table under the pressure of 0.2MPa with spray gun
Face, air drying, under conditions of 76-80 DEG C, 80bar press, afterwards again spray the present invention coating, air drying, that is,
Can.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610870874.1A CN106380984A (en) | 2016-09-30 | 2016-09-30 | Decorative antibacterial leather coating and preparation method thereof |
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| CN201610870874.1A CN106380984A (en) | 2016-09-30 | 2016-09-30 | Decorative antibacterial leather coating and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108659597A (en) * | 2018-04-04 | 2018-10-16 | 福建皓尔宝新材料科技有限公司 | It is a kind of to be used to purify mould composite inhibiting of air interior wall coating and preparation method thereof |
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| CN105936788A (en) * | 2016-05-11 | 2016-09-14 | 滁州职业技术学院 | Self-cleaning antibiosis leather coating and preparation method thereof |
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| CN105969164A (en) * | 2016-07-13 | 2016-09-28 | 蚌埠市正园电子科技有限公司 | Antioxidant waterborne polyester coating and preparation method thereof |
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2016
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Patent Citations (5)
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| CN105778440A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Environment-friendly pbt material and preparing method thereof |
| CN105925099A (en) * | 2016-05-11 | 2016-09-07 | 滁州职业技术学院 | Anti-flaming antisepsis leather coating and preparation method thereof |
| CN105936788A (en) * | 2016-05-11 | 2016-09-14 | 滁州职业技术学院 | Self-cleaning antibiosis leather coating and preparation method thereof |
| CN105969168A (en) * | 2016-07-13 | 2016-09-28 | 安徽省和翰光电科技有限公司 | Waterborne high-corrosion-resistance polyester coating and preparation method thereof |
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