CN106380987A - Oxidation-resistant antibacterial leather paint and preparation method thereof - Google Patents
Oxidation-resistant antibacterial leather paint and preparation method thereof Download PDFInfo
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- CN106380987A CN106380987A CN201610979983.7A CN201610979983A CN106380987A CN 106380987 A CN106380987 A CN 106380987A CN 201610979983 A CN201610979983 A CN 201610979983A CN 106380987 A CN106380987 A CN 106380987A
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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
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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
- C09D5/14—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Plant Pathology (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses an oxidation-resistant antibacterial leather paint which is prepared from the following raw materials in parts by weight: 1-2 parts of aluminum dihydrogen phosphate, 0.7-1 part of zinc dialkyl dithiophosphate, 0.1-0.3 part of 2-bromo-4-methylphenol, 0.1-0.2 part of trimethyl hydroxyethyl ethylenediamine, 1.7-2 parts of polyvinylpyrrolidone, 0.8-1 part of polyacrylamide, 1.6-2 parts of stannous chloride, 0.1-0.13 part of triethanolamine, 190-200 parts of methyl methacrylate, 3-4 parts of lauryl sodium sulfate, 0.1-0.2 part of urotropine, 0.2-0.3 part of ammonium persulfate, 16-20 parts of zinc acetate, 4-7 parts of silver nitrate, 0.8-1 part of sodium fluorborate, 0.7-1 part of polyoxyethylene oleate, 0.1-0.2 part of n-salicylanilide and 6-7 parts of 20-25% formaldehyde solution. The paint has the advantages of favorable antibacterial property, excellent water vapor permeability and excellent water resistance. The leather coated by the obtained emulsion has favorable antibacterial property and excellent hygienic property.
Description
Technical field
The present invention relates to leather coating technical field, more particularly, to a kind of antioxidation 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 thin 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 thin film, the perspiration 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 affinity 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 antioxidation antibacterial leather coating and its system
Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of antioxidation antibacterial leather coating, it is made up of the raw material of following weight parts：
Aluminium dihydrogen phosphate 1-2, zinc dialkyl dithiophosphate 0.7-1,2- bromo-4-methylphenol 0.1-0.3, trimethyl hydroxyethylammonium
Ethylenediamine 0.1-0.2, Polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, stannous chloride 1.6-2, triethanolamine 0.1-
0.13rd, methyl methacrylate 190-200, sodium lauryl sulphate 3-4, hexamethylenamine 0.1-0.2, Ammonium persulfate. 0.2-0.3,
Zinc acetate 16-20, silver nitrate 4-7, Sodium fluoroborate 0.8-1, polyoxyethylene oleic acid ester 0.7-1, n- N-phenylsalicylamide 0.1-0.2,
Formalin 6-7 of 20-25%.
A kind of preparation method of described antioxidation antibacterial leather coating, comprises the following steps：
（1）It is added to above-mentioned zinc acetate, hexamethylenamine 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, be sent in ptfe autoclave, microwave hydrothermal 20- at 160-170 DEG C
30 minutes, it is cooled to room temperature, filters, precipitate with deionized water, ethanol are washed 3-4 time successively, is placed in baking oven, be dried, obtain
Modified zinc oxide；
（3）By above-mentioned modified zinc oxide, stannous chloride mixing, it is added in the dehydrated alcohol of compound weight 100-120 times, surpasses
Sound 3-5 minute, adds above-mentioned silver nitrate, triethanolamine, stirs, the formalin of the above-mentioned 20-25% of Deca, completion of dropping
After add above-mentioned zinc dialkyl dithiophosphate, stir, be centrifuged off supernatant, by precipitate with deionized water, ethanol according to
Secondary washing 3-4 time, be placed in baking oven, 10-17 minute be dried at 90-100 DEG C, obtain Ag doping modified zinc oxide；
（4）Above-mentioned aluminium dihydrogen phosphate is added in the deionized water of its weight 17-20 times, stirs, add Sodium fluoroborate,
Rise high-temperature and be 60-65 DEG C, insulated and stirred 10-15 minute, add above-mentioned Ag doping modified zinc oxide, liter high-temperature is 90-95
DEG C, insulated and stirred to water is done, and obtains pretreatment Ag doping modified zinc oxide；
（5）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 pretreatment Ag doping modified zinc oxide, ultrasonic 20-30 minute, obtains modified dispersion liquid；
（6）Above-mentioned Ammonium persulfate. is added in the deionized water of its weight 17-20 times, stirs；
（7）Take above-mentioned 2- bromo-4-methylphenol, be added in the isopropanol of its weight 5-7 times, stir, add n- bigcatkin willow
Anilide, stirs, and obtains antioxidation alcohol liquid；
（8）Take the 60-70% of above-mentioned methyl methacrylate weight, mix with sodium lauryl sulphate, be added to above-mentioned modified point
In dispersion liquid, rise high-temperature and be 76-80 DEG C, insulated and stirred 10-14 minute, the remaining methyl methacrylate of Deca and over cure respectively
Sour aqueous ammonium, adds above-mentioned antioxidation alcohol liquid, insulation reaction 120-130 minute, discharging after completion of dropping, add remaining each former
Material, stirs to room temperature, obtains described coating.
A kind of described antioxidation antibacterial leather coating, the using method of this coating is：Using the front coating by the present invention
Supersound process 20-30 minute, is sprayed at leather surface with spray gun under the pressure of 0.2MPa, normal temperature drying, 76-80 DEG C,
Press under conditions of 80bar, spray the coating of the present invention, normal temperature 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 reactionss can occur so that Ag+ absorption forms silver kind in zinc oxide surface；Reaction
Later stage, the gradually Deca formalin continuously stirred in solution, make Ag be reduced into Ag granule；
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 thin 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 surface 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 surface 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 substances 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 biomacromolecules such as protein, enzyme, lipid and nucleic acid
Structure, thus kill antibacterial.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 antibacterials, so just constrains the work of antibacterial
Dynamic, make the disorderly imbalance of living environment of antibacterial, suppress its breathing, ultimately result in antibacterial 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 antioxidant of the present invention is strong, excellent storage stability.
Specific embodiment
A kind of antioxidation antibacterial leather coating, it is made up of the raw material of following weight parts：
Aluminium dihydrogen phosphate 1, zinc dialkyl dithiophosphate 0.7,2 bromomethyl phenol 0.1, trimethyl hydroxyethylammonium ethylenediamine 0.1, poly-
Vinylpyrrolidone 1.7, polyacrylamide 0.8, stannous chloride 1.6, triethanolamine 0.1, methyl methacrylate 190,12
Alkyl sodium sulfate 3, hexamethylenamine 0.1, Ammonium persulfate. 0.2, zinc acetate 16, silver nitrate 4, Sodium fluoroborate 0.8, Oleic acid polyoxyethylene
Ester 0.7, the formalin 6 of n N-phenylsalicylamide 0.1,20%.
A kind of preparation method of described antioxidation antibacterial leather coating, comprises the following steps：
（1）By above-mentioned zinc acetate, hexamethylenamine 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, is sent in ptfe autoclave, microwave hydrothermal 20 minutes at 160 DEG C, is often cooled to
Temperature, filters, precipitate with deionized water, ethanol is washed 3 times successively, is placed in baking oven, is dried, obtains modified zinc oxide；
（3）By above-mentioned modified zinc oxide, stannous chloride mixing, it is added in the dehydrated alcohol of 100 times of compound weight, ultrasonic 3
Minute, add above-mentioned silver nitrate, triethanolamine, stir, the formalin of Deca above-mentioned 20%, add after completion of dropping
State zinc dialkyl dithiophosphate, stir, be centrifuged off supernatant, precipitate with deionized water, ethanol are washed 3 successively
Secondary, it is placed in baking oven, be dried 10 minutes at 90 DEG C, obtain Ag doping modified zinc oxide；
（4）Above-mentioned aluminium dihydrogen phosphate is added in the deionized water of 17 times of its weight, stirs, add Sodium fluoroborate, rise
High-temperature is 60 DEG C, insulated and stirred 10 minutes, adds above-mentioned Ag doping modified zinc oxide, rises high-temperature and is 90 DEG C, insulated and stirred
Do to water, obtain pretreatment Ag doping modified zinc oxide；
（5）Above-mentioned polyacrylamide is added in the deionized water of 80 times of its weight, stirs, add acetic acid or ammonia,
Adjusting pH is 6, adds above-mentioned pretreatment Ag doping modified zinc oxide, ultrasonic 20 minutes, obtains modified dispersion liquid；
（6）Above-mentioned Ammonium persulfate. is added in the deionized water of 17 times of its weight, stirs；
（7）Take above-mentioned 2 bromomethyl phenol, be added in the isopropanol of 5 times of its weight, stir, add n N-phenylsalicylamide,
Stir, obtain antioxidation alcohol liquid；
（8）Take the 60% of above-mentioned methyl methacrylate weight, mix with sodium lauryl sulphate, be added to above-mentioned modified dispersion
In liquid, rise high-temperature and be 76 DEG C, insulated and stirred 10 minutes, the remaining methyl methacrylate of Deca and Ammonium persulfate. are water-soluble respectively
Liquid, adds above-mentioned antioxidation alcohol liquid after completion of dropping, insulation reaction 120 minutes, discharging, adds remaining each raw material, stirs to normal
Temperature, obtains described coating.
A kind of described antioxidation antibacterial leather coating, the using method of this coating is：Using the front coating by the present invention
Supersound process 20 minutes, is sprayed at leather surface with spray gun, normal temperature drying, in the bar of 76 DEG C, 80bar under the pressure of 0.2MPa
Press under part, spray the coating of the present invention, normal temperature 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 mycete is 80.0%.
Claims (3)
1. a kind of antioxidation antibacterial leather coating is it is characterised in that what it was made up of the raw material of following weight parts：
Aluminium dihydrogen phosphate 1-2, zinc dialkyl dithiophosphate 0.7-1,2- bromo-4-methylphenol 0.1-0.3, trimethyl hydroxyethylammonium
Ethylenediamine 0.1-0.2, Polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, stannous chloride 1.6-2, triethanolamine 0.1-
0.13rd, methyl methacrylate 190-200, sodium lauryl sulphate 3-4, hexamethylenamine 0.1-0.2, Ammonium persulfate. 0.2-0.3,
Zinc acetate 16-20, silver nitrate 4-7, Sodium fluoroborate 0.8-1, polyoxyethylene oleic acid ester 0.7-1, n- N-phenylsalicylamide 0.1-0.2,
Formalin 6-7 of 20-25%.
2. a kind of preparation method of antioxidation 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, hexamethylenamine 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, be sent in ptfe autoclave, microwave hydrothermal 20- at 160-170 DEG C
30 minutes, it is cooled to room temperature, filters, precipitate with deionized water, ethanol are washed 3-4 time successively, is placed in baking oven, be dried, obtain
Modified zinc oxide；
（3）By above-mentioned modified zinc oxide, stannous chloride mixing, it is added in the dehydrated alcohol of compound weight 100-120 times, surpasses
Sound 3-5 minute, adds above-mentioned silver nitrate, triethanolamine, stirs, the formalin of the above-mentioned 20-25% of Deca, completion of dropping
After add above-mentioned zinc dialkyl dithiophosphate, stir, be centrifuged off supernatant, by precipitate with deionized water, ethanol according to
Secondary washing 3-4 time, be placed in baking oven, 10-17 minute be dried at 90-100 DEG C, obtain Ag doping modified zinc oxide；
（4）Above-mentioned aluminium dihydrogen phosphate is added in the deionized water of its weight 17-20 times, stirs, add Sodium fluoroborate,
Rise high-temperature and be 60-65 DEG C, insulated and stirred 10-15 minute, add above-mentioned Ag doping modified zinc oxide, liter high-temperature is 90-95
DEG C, insulated and stirred to water is done, and obtains pretreatment Ag doping modified zinc oxide；
（5）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 pretreatment Ag doping modified zinc oxide, ultrasonic 20-30 minute, obtains modified dispersion liquid；
（6）Above-mentioned Ammonium persulfate. is added in the deionized water of its weight 17-20 times, stirs；
（7）Take above-mentioned 2- bromo-4-methylphenol, be added in the isopropanol of its weight 5-7 times, stir, add n- bigcatkin willow
Anilide, stirs, and obtains antioxidation alcohol liquid；
（8）Take the 60-70% of above-mentioned methyl methacrylate weight, mix with sodium lauryl sulphate, be added to above-mentioned modified point
In dispersion liquid, rise high-temperature and be 76-80 DEG C, insulated and stirred 10-14 minute, the remaining methyl methacrylate of Deca and over cure respectively
Sour aqueous ammonium, adds above-mentioned antioxidation alcohol liquid, insulation reaction 120-130 minute, discharging after completion of dropping, add remaining each former
Material, stirs to room temperature, obtains described coating.
3. a kind of antioxidation antibacterial leather coating according to claim 1,2 is it is characterised in that the using method of this coating
For：Using the front coating supersound process 20-30 minute by the present invention, it is sprayed at leather table under the pressure of 0.2MPa with spray gun
Face, normal temperature drying, under conditions of 76-80 DEG C, 80bar press, afterwards again spray the present invention coating, normal temperature drying, that is,
Can.
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| CN201610979983.7A CN106380987A (en) | 2016-11-08 | 2016-11-08 | Oxidation-resistant antibacterial leather paint and preparation method thereof |
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| CN201610979983.7A CN106380987A (en) | 2016-11-08 | 2016-11-08 | Oxidation-resistant antibacterial leather paint and preparation method thereof |
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| CN107033716A (en) * | 2017-05-16 | 2017-08-11 | 上海正邻机电自动化设备有限公司 | A kind of anti-oxidant leather |
| CN108659388A (en) * | 2018-05-08 | 2018-10-16 | 温州市赢创新材料技术有限公司 | A kind of hydrophobic CABLE MATERIALS and preparation method thereof |
| CN116446173A (en) * | 2023-04-20 | 2023-07-18 | 泰兴市思辰物流科技有限公司 | Antibacterial flannelette fabric for protecting automobile parts and preparation process thereof |
| CN116731565A (en) * | 2023-06-12 | 2023-09-12 | 米格（浙江）创新科技有限公司 | Mildew-proof antibacterial interior wall coating for decoration |
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| CN116731565A (en) * | 2023-06-12 | 2023-09-12 | 米格（浙江）创新科技有限公司 | Mildew-proof antibacterial interior wall coating for decoration |
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