CN106497291A - A kind of long-acting stable antibacterial leather coating and preparation method thereof - Google Patents
A kind of long-acting stable antibacterial leather coating and preparation method thereof Download PDFInfo
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- CN106497291A CN106497291A CN201610870955.1A CN201610870955A CN106497291A CN 106497291 A CN106497291 A CN 106497291A CN 201610870955 A CN201610870955 A CN 201610870955A CN 106497291 A CN106497291 A CN 106497291A
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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
- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Plant Pathology (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of long-acting stable antibacterial leather coating, it is made up of following weight parts raw material：Polyurethanes 0.8 1, shitosan 12, disodium hydrogen phosphate 0.8 1, tetrahydrofurfuryl alcohol 0.1 0.2, sodium potassium silicate 12, polyvinylpyrrolidone 1.7 2, polyacrylamide 0.8 1, stannous chloride 1.6 2, triethanolamine 0.1 0.13, methyl methacrylate 190 200, sodium lauryl sulphate 34, hexamethylenamine 0.1 0.2, Ammonium persulfate. 0.2 0.3, 20 25% formalin 67, zinc acetate 16 20, hexafluoroacetylacetone calcium 0.1 0.3, trithiocyanuric acid 0.1 0.3, silver nitrate 47, paranitrophenol 0.1 0.2.The coating of the present invention has good antibiotic property, excellent water vapor permeability and resistance to water, and the leather antibacterial after the covering with paint of gained emulsion is good, sanitation performance is excellent.
Description
Technical field
The present invention relates to leather coating technical field, more particularly to a kind of long-acting stable antibacterial leather coating and its preparation side
Method.
Background technology
Leather finishing agent/spinning coating agent is a kind of macromolecule compound for 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 decides the performance of product to a great extent.Polyacrylate dispersion has the flexible richness of film forming
Flexible, the features such as coating is fast light, ageing-resistant, wet-rub resistance can be excellent, it is the leather-like spinning coating of for 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, human health is endangered.At the same time, coating material defines one in leather/fabric face
Layer fine and close thin film, the perspiration that Severe blockage human body is distributed diffuse to the passage in the external world, cause the health of leather goods/textile
Performance suffers that extreme influence, snugness of fit decline.In recent years, with the continuous improvement of human living standard, research and development are anti-
Leather/weaving that bacterium property is prominent, sanitation performance is excellent is extremely urgent with coating material.
It is that target exploitation nano-ZnO and nanometer ZO/Ag are compound to improve the antibiotic property of polyacrylate coatings, sanitation performance
The antibiotic property of particle, prevents coating breed bacteria, goes mouldy；Huge using nanometer ZO and nano-ZnO/Ag compound particles
Specific surface area, improves the sanitation performance of coating.
Nano material itself has the features such as size is little, and surface energy is high, is thus susceptible to reunion, bad dispersibility.In addition, receiving
In the preparation process of nano composite material, nano material is poor with the affinity of the relatively low polymeric matrix of surface energy, and the two mutually mixes
It is difficult to compatible during conjunction, interface easily space occurs, 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, there is provided a kind of long-acting stable antibacterial leather coating and its
Preparation method.
The present invention is achieved by the following technical solutions：
A kind of long-acting stable antibacterial leather coating, it is made up of the raw material of following weight parts：
Polyurethanes 0.8-1, shitosan 1-2, disodium hydrogen phosphate 0.8-1, tetrahydrofurfuryl alcohol 0.1-0.2, sodium potassium silicate 1-2,
Polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, stannous chloride 1.6-2, triethanolamine 0.1-0.13, methacrylic acid
Methyl ester 190-200, sodium lauryl sulphate 3-4, hexamethylenamine 0.1-0.2, Ammonium persulfate. 0.2-0.3,20-25% formaldehyde molten
Liquid 6-7, zinc acetate 16-20, hexafluoroacetylacetone calcium 0.1-0.3, trithiocyanuric acid 0.1-0.3, silver nitrate 4-7, p-nitrophenyl
Phenol 0.1-0.2
A kind of preparation method of described long-acting stable antibacterial leather coating, comprises the following steps：
（1）Above-mentioned zinc acetate, hexamethylenamine, shitosan mixing is added in the deionized water of compound weight 60-100 times,
Stir, be liquid a；
（2）Above-mentioned disodium hydrogen phosphate is added in the deionized water of its weight 10-14 times, is stirred；
（3）Above-mentioned polyvinylpyrrolidone is added in its weight 20-30 times, 70-75% ethanol solution, is stirred,
Mix with above-mentioned liquid a, ultrasonic 20-30 minutes, add the aqueous solution of above-mentioned disodium hydrogen phosphate, stir, be sent to polytetrafluoro
In ethylene reaction kettle, microwave hydrothermal 20-30 minutes at 160-170 DEG C, be cooled to room temperature, filter, by precipitate with deionized water,
Ethanol is washed 3-4 time successively, is placed in baking oven, is dried, is obtained modified zinc oxide；
（4）Above-mentioned modified zinc oxide, stannous chloride are mixed, is added in the dehydrated alcohol of compound weight 100-120 times, surpassed
Sound 3-5 minutes, above-mentioned silver nitrate, triethanolamine is added, is stirred, the formalin of the above-mentioned 20-25% of Deca, completion of dropping
After be centrifuged off supernatant, precipitate with deionized water, ethanol are washed 3-4 time successively, are placed in baking oven, at 90-100 DEG C do
Dry 10-17 minutes, obtain Ag doping modified zinc oxide；
（5）Above-mentioned sodium potassium silicate is added in the deionized water of its weight 70-100 times, is stirred, add above-mentioned hexafluoro second
Acyl acetone calcium, insulated and stirred 3-10 minute at 50-60 DEG C, adds above-mentioned polyacrylamide, stirs to room temperature, add acetic acid or
Ammonia, regulation pH are 6-7, add above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, obtain modified dispersion liquid；
（6）Above-mentioned Ammonium persulfate. is added in the deionized water of its weight 17-20 times, is stirred；
（7）The 60-70% of above-mentioned methyl methacrylate weight is taken, is mixed with sodium lauryl sulphate, be added to above-mentioned modified point
In dispersion liquid, it is 76-80 DEG C to rise high-temperature, adds above-mentioned paranitrophenol, and insulated and stirred 10-14 minute, Deca is remaining respectively
Methyl methacrylate and ammonium persulfate aqueous solution, insulation reaction 120-130 minute after completion of dropping, discharging are added remaining each
Raw material, stirs to room temperature, obtains the coating.
Described a kind of long-acting stable antibacterial leather coating, the using method of the coating is：Using the front painting by the present invention
Material supersound process 20-30 minute, be sprayed at leather surface under the pressure of 0.2MPa with spray gun, 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 present invention ethanol solution of stannous chloride first
In, Sn2+ will promptly be adsorbed onto zinc oxide surface；Then, the ethanol solution of Ag (TEA) 2+ is added in above-mentioned reactant liquor,
Sn2+ can occur ion-exchange reactionss with Ag (TEA) 2+ for adding so that Ag+ absorption forms silver-colored kind in zinc oxide surface；Reaction
In the later stage, gradually Deca formalin persistently stir in solution, make Ag be reduced into Ag granules；
Preferably, being introduced in polyacrylate can effectively prevent water to ZnO/Ag compound particles resistance to water of the present invention itself
Molecule infiltration is in thin film, and then the water absorption rate of reduction laminated film, improves its resistance to water；
ZnO/Ag compound particles of the present invention have good anti-microbial property, and under illumination condition, ZnO surfaces produce substantial amounts of
Electronics and hole, the electronics that nanometer Ag capture is generated, obtain Ag-, and then, Ag- is reacted with the oxygen molecule of ZnO surface adsorption, raw
Into superoxide ion;Superoxide ion is further reacted with water, generates perhydroxyl radical and hydrogen peroxide;The H2O of hole and ZnO surface adsorption or
HO- ionic reactions, form the activity hydroxy with strong oxidizing property, and activity hydroxy mutually merges generation hydrogen peroxide.Activity hydroxy
Oxidability is most strong in water body oxidant, many Organic substances of can degrading；Additionally, oxidant superoxide ion, hydrogen peroxide, mistake
Hydroxyl etc. can pass through oxidation reaction and the effect of the biomacromolecules such as protein, enzyme, lipid and nucleic acid, destroy biological cell
Structure, so that kill antibacterial.In course of reaction, silver ion plays catalytic active center, and itself does not consume.Nanometer Ag
As 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, the living environment disorder imbalance of antibacterial is made, suppresses which to breathe, ultimately resulted in antibacterial and " contact death " occurs.
After there is the coating of the present invention good antibiotic property, excellent water vapor permeability and resistance to water, gained emulsion to cover with paint, lacquer, colour wash, etc.
Leather antibacterial is good, sanitation performance is excellent.The coating of the present invention has good stability, and non-oxidizability is strong, combination property
Superior.
Specific embodiment
A kind of long-acting stable antibacterial leather coating, it is made up of the raw material of following weight parts：
Polyurethanes 0.8, shitosan 1, disodium hydrogen phosphate 0.8, tetrahydrofurfuryl alcohol 0.1, sodium potassium silicate 1, polyvinylpyrrolidine
Ketone 1.7, polyacrylamide 0.8, stannous chloride 1.6, triethanolamine 0.1, methyl methacrylate 190, sodium lauryl sulphate
3rd, hexamethylenamine 0.1, the formalin 6 of Ammonium persulfate. 0.2,20%, zinc acetate 16, hexafluoroacetylacetone calcium 0.1, three polysulfide cyanogen
Acid 0.1, silver nitrate 4, paranitrophenol 0.1
A kind of preparation method of described long-acting stable antibacterial leather coating, comprises the following steps：
（1）By above-mentioned zinc acetate, hexamethylenamine, shitosan mixing, it is added in the deionized water of 60 times of compound weight, stirs
Uniformly, it is liquid a；
（2）Above-mentioned disodium hydrogen phosphate is added in the deionized water of 10 times of its weight, is stirred；
（3）Above-mentioned polyvinylpyrrolidone is added in 20 times of its weight, 70% ethanol solution, is stirred, and above-mentioned
Liquid a mixes, ultrasound 20 minutes, adds the aqueous solution of above-mentioned disodium hydrogen phosphate, stirs, be sent to ptfe autoclave
In, microwave hydrothermal 20 minutes at 160 DEG C are cooled to room temperature, filter, precipitate with deionized water, ethanol are washed 3 times successively,
It is placed in baking oven, dries, obtain modified zinc oxide；
（4）Above-mentioned modified zinc oxide, stannous chloride are mixed, is added in the dehydrated alcohol of 100 times of compound weight, ultrasound 3
Minute, above-mentioned silver nitrate, triethanolamine being added, is stirred, the formalin of Deca above-mentioned 20%, centrifugation after completion of dropping are removed
Supernatant is removed, precipitate with deionized water, ethanol is washed 3 times successively, is placed in baking oven, dried 10 minutes at 90 DEG C, obtain silver-colored
Doping vario-property zinc oxide；
（5）Above-mentioned sodium potassium silicate is added in the deionized water of 70 times of its weight, is stirred, add above-mentioned hexafluoroacetylacetonate
Ketone calcium, insulated and stirred 3 minutes at 50 DEG C add above-mentioned polyacrylamide, stir to room temperature, add acetic acid or ammonia, adjust
PH is 6, adds above-mentioned Ag doping modified zinc oxide, ultrasound 20 minutes to obtain modified dispersion liquid；
（6）Above-mentioned Ammonium persulfate. is added in the deionized water of 17 times of its weight, is stirred；
（7）The 60% of above-mentioned methyl methacrylate weight is taken, is mixed with sodium lauryl sulphate, be added to above-mentioned modified dispersion
In liquid, it is 76 DEG C to rise high-temperature, adds above-mentioned paranitrophenol, insulated and stirred 10 minutes, the remaining metering system of difference Deca
Sour methyl ester and ammonium persulfate aqueous solution, insulation reaction 120 minutes after completion of dropping, discharging add remaining each raw material, stir to normal
Temperature, obtains the coating.
Described a kind of long-acting stable antibacterial leather coating, the using method of the coating is：Using the front painting by the present invention
Material supersound process 20 minutes, is sprayed at leather surface under the pressure of 0.2MPa with spray gun, normal temperature drying, in 76 DEG C, 80bar
Under the conditions of press, spray again afterwards the present invention coating, normal temperature drying, 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, is 80.0% to the bacteriostasis rate of mycete.
Claims (3)
1. one kind is long-acting stablizes antibacterial leather coating, it is characterised in that it is made up of the raw material of following weight parts：
Polyurethanes 0.8-1, shitosan 1-2, disodium hydrogen phosphate 0.8-1, tetrahydrofurfuryl alcohol 0.1-0.2, sodium potassium silicate 1-2,
Polyvinylpyrrolidone 1.7-2, polyacrylamide 0.8-1, stannous chloride 1.6-2, triethanolamine 0.1-0.13, methacrylic acid
Methyl ester 190-200, sodium lauryl sulphate 3-4, hexamethylenamine 0.1-0.2, Ammonium persulfate. 0.2-0.3,20-25% formaldehyde molten
Liquid 6-7, zinc acetate 16-20, hexafluoroacetylacetone calcium 0.1-0.3, trithiocyanuric acid 0.1-0.3, silver nitrate 4-7, p-nitrophenyl
Phenol 0.1-0.2.
2. a kind of preparation method of long-acting as claimed in claim 1 stable antibacterial leather coating, it is characterised in that including following
Step：
（1）Above-mentioned zinc acetate, hexamethylenamine, shitosan mixing is added in the deionized water of compound weight 60-100 times,
Stir, be liquid a；
（2）Above-mentioned disodium hydrogen phosphate is added in the deionized water of its weight 10-14 times, is stirred；
（3）Above-mentioned polyvinylpyrrolidone is added in its weight 20-30 times, 70-75% ethanol solution, is stirred,
Mix with above-mentioned liquid a, ultrasonic 20-30 minutes, add the aqueous solution of above-mentioned disodium hydrogen phosphate, stir, be sent to polytetrafluoro
In ethylene reaction kettle, microwave hydrothermal 20-30 minutes at 160-170 DEG C, be cooled to room temperature, filter, by precipitate with deionized water,
Ethanol is washed 3-4 time successively, is placed in baking oven, is dried, is obtained modified zinc oxide；
（4）Above-mentioned modified zinc oxide, stannous chloride are mixed, is added in the dehydrated alcohol of compound weight 100-120 times, surpassed
Sound 3-5 minutes, above-mentioned silver nitrate, triethanolamine is added, is stirred, the formalin of the above-mentioned 20-25% of Deca, completion of dropping
After be centrifuged off supernatant, precipitate with deionized water, ethanol are washed 3-4 time successively, are placed in baking oven, at 90-100 DEG C do
Dry 10-17 minutes, obtain Ag doping modified zinc oxide；
（5）Above-mentioned sodium potassium silicate is added in the deionized water of its weight 70-100 times, is stirred, add above-mentioned hexafluoro second
Acyl acetone calcium, insulated and stirred 3-10 minute at 50-60 DEG C, adds above-mentioned polyacrylamide, stirs to room temperature, add acetic acid or
Ammonia, regulation pH are 6-7, add above-mentioned Ag doping modified zinc oxide, ultrasonic 20-30 minutes, obtain modified dispersion liquid；
（6）Above-mentioned Ammonium persulfate. is added in the deionized water of its weight 17-20 times, is stirred；
（7）The 60-70% of above-mentioned methyl methacrylate weight is taken, is mixed with sodium lauryl sulphate, be added to above-mentioned modified point
In dispersion liquid, it is 76-80 DEG C to rise high-temperature, adds above-mentioned paranitrophenol, and insulated and stirred 10-14 minute, Deca is remaining respectively
Methyl methacrylate and ammonium persulfate aqueous solution, insulation reaction 120-130 minute after completion of dropping, discharging are added remaining each
Raw material, stirs to room temperature, obtains the coating.
3. a kind of long-acting stable antibacterial leather 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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| CN201610870955.1A CN106497291A (en) | 2016-09-30 | 2016-09-30 | A kind of long-acting stable antibacterial leather coating and preparation method thereof |
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| CN201610870955.1A CN106497291A (en) | 2016-09-30 | 2016-09-30 | A kind of long-acting stable antibacterial leather coating and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342111A (en) * | 2018-03-01 | 2018-07-31 | 陕西科技大学 | A kind of anti-electrostatic antibiotic shell glycan-casein composite leather coating agent and preparation method thereof |
| US11560487B2 (en) | 2020-09-22 | 2023-01-24 | Swimc Llc | Coating compositions containing low molecular weight chitosan composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-09-30 CN CN201610870955.1A patent/CN106497291A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342111A (en) * | 2018-03-01 | 2018-07-31 | 陕西科技大学 | A kind of anti-electrostatic antibiotic shell glycan-casein composite leather coating agent and preparation method thereof |
| CN108342111B (en) * | 2018-03-01 | 2020-03-31 | 陕西科技大学 | Anti-static antibacterial chitosan-casein composite leather finishing agent and preparation method thereof |
| US11560487B2 (en) | 2020-09-22 | 2023-01-24 | Swimc Llc | Coating compositions containing low molecular weight chitosan composition |
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