CN109169706A - Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained - Google Patents
Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained Download PDFInfo
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- CN109169706A CN109169706A CN201810794405.5A CN201810794405A CN109169706A CN 109169706 A CN109169706 A CN 109169706A CN 201810794405 A CN201810794405 A CN 201810794405A CN 109169706 A CN109169706 A CN 109169706A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The present invention provides a kind of complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coatings obtained, and wherein the complex antimicrobials include Ag/Cu nano particle and chitosan.The antibacterial agent and comprising its coating have good antibacterial bacteriostatic effect.
Description
Technical field
The invention belongs to antibacterial agent technical fields, are related to a kind of complex antimicrobials, especially bioactivity composite antibacterial
Agent, further to the antibacterial bacteriostatic type multifunctional inorganic ecologic coating comprising it.
Background technique
Inorganic antiseptic received significant attention in recent years, such as silver or the compound colloid of silver etc. are studied, and
Corresponding product has been sold, such as carry silver/cu zn zeolite, carry silver/cu zn titanium dioxide etc..Bioactivity Ag/Cu from
Son is strong fungicide, and silver or copper nano particles have been used for the antimicrobial coating based on polymer.Due to the appearance and prevalence of new strains
There is the design for enhancing active antibacterial agent and exploitation to become in human lives and several technical operations for the increase of disease
It is more and more important.Novel antibacterial and sterilization formulation based on noble metal nano particles are of concern.
The antibacterial activity mechanism of noble metal nano particles includes: that metal antibacterial is added in product such as coating or plastics etc.
After agent, with other materials contact or with the contact of environment, material surface can be sustained micro metallic element, Neng Gouqi
To the effect of catalytic active center, which can be by absorbing environmental energy, the air of activation absorption on the surface of the material
Oxygen in moisture generates hydroxyl radical free radical and oxygen activity ion, also by oxidation possessed by these free radicals or active ion
Proper energy power destroys the proliferative capacity of bacterial cell, inhibits or kills bacterium, generate bacteriostatic activity.
In addition, chitosan is generally acknowledged broad-spectrum antiseptic antibacterial material, the chitosan of different physical states can be with life
Object (including bacterium, saccharomycete, fungi and algae etc.) interaction plays its antimicrobial acivity.The organic chemistry of chitosan
Structure determines its antibacterial bacteriostatic performance.
For coating application, for environment and healthy reason, people also increasingly pay close attention to the lower coating of VOC content
Exploitation.Nontoxic, tasteless, low VOC (Volatile Organic Compound, VOC), even " Diamond Search "
Environment-friendly water-based paint be becoming increasingly popular.VOC is mainly derived from residual monomer in lotion, coalescing agent in water paint
With other auxiliary agents.How so that the residual monomer content in lotion is gone to zero by improving polymerization technique, and coalescing agent is not added
It can form a film, all be the emphasis studied at present.
CN101095414A discloses coating for internal and external wall, paint method of synthesizing inorganic antibacterial agent: silver is formed argentiferous
Anion complex solution is mixed with the weak tendency salting liquid of zinc, is mixed with silicon solution, dry, sintering.
CN101125934 A discloses a kind of preparation method of the chitosan/nylon composite antibacterial film of silver ion, gained
Composite membrane anti-microbial property is good, and antibacterial action is lasting, and intensity is high, good biocompatibility, and physical and chemical performance is stablized, and the composite membrane is to leather
Gram-negative bacteria and gram-positive bacterium have good antibacterial effect.
CN101245211 A discloses a kind of coating composition with antibacterial and air-cleaning function, and component is by weight
Part meter is measured, including adulterates 1~10 part of four acicular type zinc oxide crystal whisker, 1~10 part of mesoporous filler, 40~55 parts of acrylic acid ester emulsion,
10~30 parts of titanium dioxide, 10~25 parts of filler talcum powder, 0.5~10 part of auxiliary agent.Wherein Doped ions are Fe3+, Cu2+, Ag+
Or one of V5+ or a variety of.
CN102405932A discloses a kind of bearing copper silicon nano mesoporous inorganic antimicrobial agent and preparation method thereof for carrying silver.It is
Polyethylene glycol propylene glycol-polyethyleneglycol block copolymer, deionized water and acid is stirred evenly, be added silicon source, copper nitrate and
Silver nitrate obtains sol-gel liquid, dries sol-gel, then passes through roasting direct, obtains the copper silicon nanometer of argentiferous simple substance
Mesoporous inorganic antibacterial.
CN103911053 A discloses a kind of antibiotic paint, which consists of the following parts by weight: titanium dioxide 18
~29%, acrylate copolymer emulsion 15~30%, polythene wax emulsion 5~10%, butyl carbitol 3~5%, thickener 1~
3%, dispersing agent 2~5%, defoaming agent 0.5~3%, deionized water 16~28%, propylene glycol 3.5~8%, agglomerated solvent 2~
3%, chitosan-inorganic metal ion complex 10~20%.
CN104592856A discloses a kind of water corrosion-resistant epoxy paint that joined chitosan, including following weight group
Point: 35-40 parts of epoxy emulsion, 16-20 parts of iron oxide red, 4-8 parts of rust resisting pigment, 2-3 parts of talcum powder, 2-3 parts of dispersing agent, defoaming agent
0.1-0.5 parts, 0.1-0.5 parts of levelling agent, 0.3-1.5 parts of wetting agent, 2-10 parts of emulsifier, 10-50 parts of chitosan, deionized water
20-35 parts.
CN105482517A discloses a kind of ecological multifunction inorganic coating without formaldehyde and V0C, and constituent presses matter
Amount percentage is divided into: ultra-fine sierozem power 15-35%, TF-05 powder thickener 0.2-0.5%, P871 powder coalescing agent 0.2-
0.5%, ripple stone 45-55%, pigments and fillers 4% and functional additive 6%.
CN107964262A discloses a kind of water paint, and the coating is made of following raw material: edible glue, carbonic acid
Calcium, calcium bicarbonate, diatomite, talcum powder, pulverized limestone, cellulose, organosilicon fluorescein polymer, mountain flour, rubber powder, corn flour,
Silica flour, mica titanium, kaolin, methyl methacrylate, butyl methacrylate, natural synthetic resin, methyl acrylate, third
Olefin(e) acid ethyl ester.
CN107779078A discloses a kind of low smell water-borne wood coating of low VOC, the low smell Waterborne wood of the low VOC
Device coating is made of feedstock composition, and the feedstock composition includes: polyether polyol 50-80 parts by weight, diisocyanate 50-
80 parts by weight, acrylic resin 60-100 parts by weight, catalyst 3-8 parts by weight, graphene oxide 2-10 parts by weight, starch 3-12
Parts by weight, castor oil 5-15 parts by weight, emulsifier 2-9 parts by weight, defoaming agent 1-5 parts by weight, thickener 2-8 parts by weight, film forming
Auxiliary agent 1-5 parts by weight, preservative 1-3 parts by weight.
CN105885668A discloses a kind of water borne soft-feel coating of Diamond Search comprising the raw material of following mass parts: aqueous
30-90 parts of polyether-modified type polyurethane dispersion, 1-10 parts of feel auxiliary agent, 1-8 parts of leveling auxiliary agent, 1-10 parts of crosslinking agent, pH tune
Agent 1-8 parts, 1-30 parts of deionized water of section.
CN107083167A discloses a kind of waterborne radiation curable coating of zero VOC discharge, and the coating is by following
The raw material of weight percentage forms: synthesis of polyurethane 72-85%, inorganic additive 3-10%, auxiliary agent 0.5-3%, deionized water
10-15%；Wherein the synthesis of polyurethane is water soluble hydroxy NCO grade separation structure tree shaped polymer.
CN102732077B discloses the low VOC/ Diamond Search glycol ether-ester of the coalescent as aqueous polymer dispersions,
And the water-based paint compositions comprising the compound, it includes aqueous polymer dispersions and 0.1-40 weight %(with described
Counted on the basis of the weight of aqueous polymer dispersions solid) glycol ether-ester coalescent, and by the water-based paint compositions shape
At the method for coating.
CN104987758A discloses a kind of aqueous inorganic shop primer, and the aqueous inorganic shop primer is by component A and B group
It is grouped as, the weight ratio of component A and B component is 3:5, and by weight, the composition and content of component A and B component are as follows: A group
Point composition and content: Baume degrees is 90-120 parts of waterglass of 38-42,25-30 parts of silicone acrylic emulsion, 0.8-1.2 parts of levelling agent,
1-1.5 parts of dispersing agent, 0.5-0.8 parts of corrosion inhibiter, 25-40 parts of water；The composition and content of B component: 80-100 parts of zinc powder, apatite
60-72 parts of powder, 15-18 parts of mica powder, 5-15 parts of calcium silicates powder, 0-7 parts of SiO 2 powder.
US4891394A discloses a kind of coating composition, wherein using epoxy resin binder for film formation, and wherein extremely
The pyrolysis amorphous silica of few four kinds of different size grades exists with special ratios and average particle size, while having oil factor
The crystalline silica being less than.
US5167701A discloses a kind of one pack system zinc-rich paint composition, with inorganic bond, protects metal
Substrate is from environmental attack, and include percent by volume: the alkyl solid content of about 55% to about 60% is about 35% to about 45%
The silicate solutions of (weight)；The zinc powder of about 10% to about 14% of at least one different grain size grade；About 0.5% to about
2.5% zinc metal sheet；The graininess ferric phosphate of about 3% to about 6%；By ASTM Test D 281-84 measurement about 10% to about
Crystalline particulate silica of 17% oil factor less than 20；The different size grades of at least two of about 1% to about 2.5%
It is pyrolyzed amorphous silica, average particle size is about 0.007 to about 0.04 micron；The wetting agent of about 0.3% to about 0.5%；
About 7% to about 8% anhydrous alcoholic solvent.
" development of novel building inorganic coating " thanks literary peak etc., New Building Materials, 2013,40 (11): 35-39, disclosure
A kind of inorganic coating adds a small amount of low VOC macromolecule emulsion and correlation helps with potassium silicate, silica solution for main film forming matter
Agent, and the filler systems with certain high temperature resistance are equipped with, aqueous inorganic building coating is made.The coating decorative performance is good
Good, environmentally protective, low VOC emission meets JG/T 26-2002 " exterior wall inorganic architectural coatings " and GB 24408-2009 " building
With limits of harmful substances in exterior coating " standard requirements, meet GB 8624-2006 " construction material and product burns performance point
Grade " as defined in A2 grade require, can be applied to skyscraper, public building etc..
In existing coating antibiosis agent, the organic antibacterial agent durability difference and performance used is relatively single, antibacterial wide spectrum
Property it is insufficient, and other COMPONENTS COMPATIBILITYs in the inorganic antiseptic and coating used are poor, and this severely limits the uses of antibacterial agent.
In addition, currently, a variety of methods can be used in order to reduce the volatile organic compounds in emulsion paint (VOC)
To provide low VOC or Diamond Search emulsion paint.For example, replacing conventional solvent using reactive diluent.But high response diluent
Shelf-life is short, is not suitable for building coating, and low activity diluent is not efficient enough, and adhesion resistance is poor.For another example, using inorganic mineral
Main component of the powder as coating, however, it is easy to happen particle coalescence when using inorganic particle as paint ingredient, and
It is poor with other COMPONENTS COMPATIBILITYs.
In addition, general film forming agent has a possibility that VOC volatilization, this gives the coating composition for preparing low VOC or Diamond Search
Bring certain difficulty.How to prevent inorganic constituents particle from sedimentation or aggregation, and a current problem occurs.For example, inorganic
Mineral slurries are usually incompatible with latex adhesive used in water-based paint compositions.The form of inorganic mineral particles aggregation,
Which reduce the light scattering efficiencies of pigment, or due to depositing in the form of compared with low gloss in slurry there are incompatible dispersing agent
?.
Therefore, this field needs a kind of effective coating antibacterial agent and the coating comprising the antibacterial agent, and the coating is also
It also needs that there is alap VOC or Diamond Search, in addition, to need to be improved inorganic pigment compatible in aqueous coating for this field
Property.
Summary of the invention
In order to solve the above-mentioned technical problem, the present inventor is on the basis of previous research, by further furtheing investigate and
Many experiments provide following technical scheme by developing jointly with scientific research institution.
In one aspect of the invention, a kind of complex antimicrobials (i.e. bioactivity complex antimicrobials) are provided, wherein this is multiple
Closing antibacterial agent includes AgCu nano particle and chitosan.
Preferably, the AgCu nano particle is alloy state, which has S phase microscopic structure.Certainly, two kinds of nanometers
Grain can also be in isolated state, i.e., non-alloyed state.
Preferably, the AgCu nano particle is supported on chitosan.It is highly preferred that the Ag/Cu nano particle (Ag/
Cu duplex metal nano granule) growth in situ is on the surface of chitosan
The size of the Ag nano particle and Cu nano particle can be 2-80nm, preferably 10-50nm independently of one another.
Preferably, the chitosan is chitosan.It is highly preferred that the deacetylation of institute's chitosan is 30-80%,
Most preferably 40-70%.
In a particularly preferred embodiment of the invention, the complex antimicrobials are that chitosan loaded Ag/Cu is bis-
Metal nanoparticle.The complex antimicrobials are preferably prepared by following method: (1) by ultrasonic treatment by chitosan (such as
It 0.03g) is dispersed in (such as 11ml) water, is ultrasonically treated 5-15 minutes, then, the AgNO of 0.001-0.1M concentration is added3Water
Solution, and mixture is ultrasonically treated 30-60 minutes, obtain suspension；(2) N, N- dimethyl methyl are added into gained suspension
Amide, and under stiring in 80-100 DEG C reaction 4-8 hours, the obtained Ag nano particle-of recycling is then washed with deionized
Chitosan hybrid object；(3) the Ag nano particle-chitosan hybrid object for preparing step (2) under ultrasonic treatment, with 0.001-
The CuCl of 0.2M concentration2Solution mixing, stirs 1-2 hours, is then slowly added to the potassium borohydride aqueous solution of 0.01-0.5M, and
It reacts the mixture 12-24 hours at 100 DEG C, is then washed with water and dries, obtain the bis- gold of chitosan loaded Ag/Cu
Metal nano-particle.
In the preparation method, DMF(N, dinethylformamide are used in step (1)) it is used as reducing agent, help to make
Ag nano particle loads stronger on chitosan.In step (2), using potassium borohydride as reducing agent, so that Ag receives
The Cu nano particle that rice grain and reduction are formed can have better degrees of fusion.Two kinds of different being applied in combination for reduction mode make
Obtaining Ag nano particle and Cu nano particle has higher conjugation.
Preferably, the potassium borohydride and CuCl2Molar ratio be 1.1 times of stoichiometric ratio.This molar ratio can be with
Copper ion is reduced sufficiently.
In step (1), DMF also acts as solvent action, and dosage is enough to be reduced silver ion.
In fact, different from conventional reduction mode, the present invention selects this reduction synthesis sequence, makes Ag+Ion exists first
It is grown on chitosan, is more advantageous to the Ag/Cu composite nanometer particle to form alloying or class alloying, and in this case more
Be conducive to the formation of S phase.
The chitosan is preferably the chitosan activated, is preferably activated by following method: will include 0.10-
0.20M HNO3With 0.10-0.30M H2SO4Acidic aqueous solution be added in chitosan, then be ultrasonically treated while in 60-
It heats 6-10 hours, is then separated resulting chitosan with acid within 10-30 minutes with 4500-6000rpm centrifugation, then at 80 DEG C
It is washed with water to neutral pH, then dries the chitosan to get activation at 60-90 DEG C.
Preferably, the solid-to-liquid ratio of the chitosan and acidic aqueous solution is 1:5-1:20(w/w).
The study found that chitosan surface functionalization can be made by carrying out above-mentioned ultrasonic sonochemical oxidation to chitosan, to increase
Affinity of the Qiang Qiyu for the precursor of subsequent metal nano particle (Ag nano particle and Cu nano particle) growth, and increase institute
Stability of the metal nanoparticle of generation on chitosan surface.
Preferably, in the chitosan loaded Ag/Cu duplex metal nano granule of preparation, the content of Ag is 0.1-2.0
wt.%；The content of Cu is 0.1-5.0 wt.%.
Conventionally, by the way that in the case where adding complex antimicrobials of the invention, detection Escherichia coli liquid is trained
Growing state (by Colony Forming Unit in terms of, CFU) of the bacterium in the period up to 6 hour incubation period in base is supported, to study
The antibacterial action of complex antimicrobials.When using chitosan loaded Ag/Cu duplex metal nano granule of the invention, with identical use
The Ag/Cu duplex metal nano granule of amount is compared, and CFU reduces at least 1 times, and compared with the chitosan of same amount, CFU is reduced at least
2 times.While obtaining better antibacterial effect, reduce the dosage of noble metal, to greatly save catalyst cost.
In another aspect of this invention, a kind of multifunctional inorganic ecologic coating composition without formaldehyde and VOC is provided,
By weight, which includes: 50-90 parts of inorganic mineral powder, 5-60 parts of emulsion polymer, and 0.1-10.0 parts of thickener, surface
0.1-5.0 parts of activating agent, 0.01-5.0 parts of pigment, above-mentioned complex antimicrobials 0.01-2.0 parts.
Preferably, inorganic mineral powder be 60-80 parts, 20-50 parts of emulsion polymer, 1.0-5.0 parts of thickener, surface-active
0.1-3.0 parts of agent, 0.1-2.0 parts of pigment, above-mentioned complex antimicrobials 0.1-1.0 parts.
The emulsion polymer may be used as film forming agent in coating composition of the invention.General film forming agent, which has, to be waved
A possibility that sending out VOC, this is to preparing low VOC or the coating composition of Diamond Search brings certain difficulty.For this purpose, the present invention provides
A kind of extremely low, even Diamond Search emulsion polymer.The emulsion polymer is the polymer of functionalization, i.e. functionalization emulsion polymerization
Object, more preferably poly- (the methyl acrylate -co- methyl methacrylate -co- glycidyl methacrylate) of silanization.
The emulsion polymer can be prepared by semi-continuous emulsion polymerizing method.
In a particularly preferred embodiment, which is made by the following method:
(1) reaction vessel is led to nitrogen to protect, initial charge is then added into reaction vessel；
(2) reaction vessel is then heated to 80-90 DEG C using water-bath, is continuously added to monomer feed and aqueous feed, it is continuous to add
Material completion in 3-5 hour, after adding, by reaction system 80-90 DEG C holding 1-2 hours to complete to polymerize, then filter, obtain
To emulsion polymer.
Preferably, in step (1), the initial charge includes the water and 0.0001-0.002 weight of 240-260 parts by weight
Measure the HEDTA-3NA of part.HEDTA-3NA plays chelating agent during the reaction.
Preferably, in step (2), the monomer feed includes 100-120 parts by weight of acrylic acid methyl esters, 50-70 weight
The methyl methacrylate of part, the glycidyl methacrylate of 10-20 parts by weight, γ-metering system of 5-10 parts by weight
Acryloxypropylethoxysilane trimethoxy silane.
Preferably, in step (2), aqueous feed include 50-60 parts by weight of deionized water, the ten of 2.0-3.0 parts by weight
Dialkyl diphenyl ether sodium disulfonate surfactant, the sodium peroxydisulfate of 0.2-1.0 parts by weight, the bicarbonate of 0.1-1.0 parts by weight
Sodium.
It is indicated herein to be, each ingredient in weight of material part and coating composition in the emulsion polymer preparation method
Parts by weight it is mutually indepedent, that is, be not based on same benchmark or same datum.In emulsion polymer preparation method, all wt part
It is based on same benchmark.And the parts by weight of each ingredient are based on same benchmark in coating composition
The study found that the water paint of the invention based on the latex dispersions, VOC content is far below solvent based coating.
It is known in the art to replace solvent-borne formulation that obtain suitable or improved property with suitable or lower cost with latex base coating
Energy.Compared with solvent based coating, the coating of these types has the advantages that several, such as low smell, quick-drying and manufacturing cost be cheap.
The study found that the latex paint formulations of most commercial still contain a large amount of organic solvent (VOC of 15-30 weight %), to add
The purpose for entering organic solvent is glass transition temperature as coalescing aid to reduce latex polymer (also referred to as emulsion polymer)
It spends (Tg).In the case where these no solvents, latex particle has 25 DEG C of Tg >, cannot form film at room temperature, because
This is used as fugitive plasticizer using solvent to reduce polymer Tg and reduce its modulus, these, which are all given, prepares low VOC coatings and bring
It is difficult.
Test shows that emulsion polymer of the invention by self-crosslinking mode, has particularly good film forming and polymer
Diffusion rate.The polymer Tg of the drying regime of emulsion polymerization composition granule of the invention is 4-6 DEG C, it is not necessary that solvent is added as poly-
Tie auxiliary agent.In addition, epoxy group and carboxylic acid in glycidyl methacrylate are anti-in emulsion polymer of the invention
It answers, they are reacted on the surface that can be used for that surfactant is grafted to carboxylate latex particle with acid, and epoxy group rises
It is acted on to crosslink sites, by being crosslinked, the mechanical performance of polymer, such as filming performance can be improved, and being capable of polymer
Stability significantly improves, and can effectively inhibit the generation and evolution of possible VOC.
The present inventor it is also found that: when silane functional is integrated in emulsion polymer, and wherein mixes hydroxyl through research
The routine functionalizing method of functional group is on the contrary, make polymer material have excellent crosslinking ability compared with standard monomer, together
When with significant reduced solution viscosity.This reduced polymer viscosity provides the reduction of coating composition viscosity in turn, from
And provide higher spraying solid and lower volatile organic content (VOC).
The weight average molecular weight of the emulsion polymer can be 60000-80000, preferably 70000-80000.
Preferably, the inorganic mineral powder is selected from ripple mountain flour, ultra-fine sierozem power, diatomite in powder, talcum powder, mica titanium
One of powder, kaolin powder, dolomite, wollastonite, magnesite, feldspar, quartz sand powder and potassium silicate powder are a variety of.
Preferably, the inorganic mineral powder is the surface modified inorganic mineral powder of powder granule.It is highly preferred that surface changes
Property include carrying out hydrophobically modified or hydrophilic modifying or surface coated polymer.
Preferably, the pigment is inorganic pigment.It is highly preferred that the inorganic pigment is selected from MnO2、MgSiO3、
CaCO3, one of ZnO or a variety of inorganic pigments.
The average grain diameter of the inorganic mineral powder can be 10-300nm, preferably 50-200nm.
The mean particle size of the inorganic pigment can be 10-200nm, preferably 20-150nm.
The thickener is the common thickener for water paint.
In coating composition of the invention, since the inorganic mineral powder and inorganic pigment that have used larger proportion (can also
It is referred to as inorganic mineral), the particle and emulsion polymer of inorganic mineral powder and inorganic pigment can be produced due to the difference of various properties
Raw consistency problem.In the prior art, in order to solve described problem, a kind of method be inorganic particle height is ground, however
This method can not fundamentally solve consistency problem, and grinding is high energy consumption, high cost process process, will lead to coating
Cost dramatically increases；It is using dispersion that another method, which reduces the method that inorganic particle occurs to settle and assemble in the polymer,
Agent, the conventional dispersant used include the sodium salt etc. of 2-amino-2-methyl-1-propanol, triethanolamine and polymerization of carboxylic acid, however
The use of this substance is only more effective for the situation of the inorganic mineral in coating containing minor proportion, and can seriously affect painting
The film forming of material reduces and applies the performances such as film strength.For this purpose, the present invention is for inorganic mineral and latex used in coating
Polymer improves the compatibility between aforementioned substances as compatilizer using lower surface activating agent, aforementioned to avoid generating
Sedimentation, isolation and rendezvous problem.
Preferably, surfactant of the invention is lower formula (I) compound represented:
Formula (I)
Wherein R1For group shown in lower formula (II):
The present invention by adding above-mentioned surfactant in the coating composition, seldom generation or several in the water-based paint compositions
The aggregation that inorganic mineral particles or granules of pigments do not occur has good dispersing uniformity and compatible in emulsion polymer
Property.As illustrated in fig. 1 and 2, compared with the coating composition for using conventional commercial surfactant, coating composition of the invention is protected
Hold the more preferable dispersion of inorganic particle or granules of pigments and compatible.Due to described good uniformly dispersed, painting prepared by the present invention
Feed composition also has excellent shear viscosity, low-shear viscosity and excellent gloss and covering power, and film obtained has
Higher intensity, such as the hardness of film made from coating composition of the invention can be usually reached at least 2B, and if using one
As commercial surfactant, hardness is usually 4B.
It is particularly preferred that surfactant shown in the formula (I) is prepared via a method which:
It will (such as 130g, i.e. 1.0mol) 2-Hydroxyethyl methacrylate and (such as 0.2g, that is, 1.61mmol) mono-methylether hydroquinone
Be placed in the reactor equipped with mechanical agitator, thermometer and condenser, make about 50 DEG C of temperature of reactor, then will (such as
59.22g, that is, 0.35mol) phosphorus pentoxide is slowly added into reactor, and reaction temperature is maintained at 50 DEG C hereinafter, in nitrogen ring
Reaction 2-6 hours is carried out under border, is cooled to room temperature, is filtered, and is purified to get surfactant shown in formula (I).
It is characterized by IR, in 990cm-1Neighbouring strong peak shows the formation of C-O-P key in synthetic product.
The purifying can be carried out by way of conventional adjusting pH value of reaction system.
The preparation method is simple and reliable compared with phosphoric acid method, high income and product purity height, and exists with including phosphoric acid method
Interior other preparation methods are compared, and remaining a small amount of impurity is to by the coating preparation in surfactant made from this method
Film performance is for example mechanical and luster performance is almost without influence.In addition, research also found, the insatiable hunger in the surfactant molecule
Polymerizing curable effect can occur with key and emulsion polymer, and the hydroxyl on phosphorus atoms simultaneously can be with inorganic particle surfaces
Hydroxyl occur hydrogen bond action, to realize the fine dispersion of emulsion polymer and inorganic particle.
As known to paint field, it can also be added into ecologic coating composition of the invention suitable chosen from the followings
At least one additive: plasticizer, retarder, dispersing agent, wetting agent, rheology modifier, defoaming agent, coalescent, mould inhibitor,
Toner, fragrance etc..Those skilled in the art can according to need selected from these conventional additives addition specific type and
Dosage is to meet specific coating property requirement.
In another aspect of this invention, the method for preparing above-mentioned multifunctional inorganic ecologic coating, this method packet are provided
It includes and is uniformly mixed each coating composition.
Preferably, in the method, mixing step is included in surfactant and latex polymer, thickener and inorganic
Pigment mixes surfactant with inorganic mineral powder with before mixing.When the surfactant is mixed with inorganic mineral powder,
It is preferred that using as an aqueous solution.When as an aqueous solution in use, the concentration of surfactant is preferably 10-30 wt.%.It is excellent
The surfactant and inorganic mineral powder are thoroughly mixed uniformly by selection of land.It is highly preferred that by the aqueous solution form
Surfactant and inorganic mineral powder are thoroughly mixed uniformly.
In still another aspect of the invention, the method using above-mentioned multifunctional inorganic ecologic coating, this method packet are provided
It includes and mixes the coating with water, wherein the dosage of the water can be 10-500 parts.The dosage of the water does not include when surface is living
Property agent water used when using as an aqueous solution.In fact, it will be appreciated by those of skill in the art that when surfactant with
Aqueous solution form is in use, the dosage of water and few.
In fact, the water can also be considered as a part of multifunctional inorganic ecologic coating composition, dosage can be
It is 10-500 parts, preferably 20-200 parts, 50-100 parts more preferable.
For the present invention, " low VOC " refers to that the VOC content of coating composition is not greater than about 150g/L, preferably no greater than
About 50g/L, more preferably less than 20g/L, such as no more than about 10g/L or it is not greater than about 8g/L.
For the present invention, referring to the definition of U.S. EPA Method Method 24, " Diamond Search " refers to coating composition
VOC content is not greater than about 5g/L, such as no more than about 2g/L or is not greater than about 1g/L, or the detection limit of such as less than this method；
Alternatively, referring to that detection of the VOC lower than GB 18582-2008 limits.
Preferably, desciccator diaphragm made of coating composition of the invention has at least 60 glossiness at 60 DEG C.It is preferred that
Ground, desciccator diaphragm made of coating composition of the invention have at least Pencil Hardness values of 9H.Above-mentioned measurement refers to GB/T
1743-1979, GB/T 6739-1996 are carried out.
Compared with prior art, multifunctional ecological coating of the invention is free of formaldehyde and VOC, is suitable as indoor coating.
In addition, the coating can effectively prevent inorganic constituents particle (i.e. inorganic mineral particles and inorganic pigment granules) to occur in use
Sedimentation or aggregation, inorganic constituents particle can be well dispersed into emulsion polymer, so that good film-forming property, intensity is high, gloss
It is good.Due to the use of self-crosslinking emulsion polymer, the coating is without formaldehyde and low without VOC or VOC content.Coating of the invention
In without can produce the ingredient of formaldehyde, and based on inorganic constituents, therefore the coating composition is referred to as without first
The multifunctional inorganic ecologic coating of aldehyde and VOC.
In addition, inorganic mineral powder can have not with the function of the excellent antimildew and antibacterial of imparting coating under lower cost
Whiten, without degradation, there is best thickening fixed effect in coating, has good scrub resistance, adhesive force, increase machinery strong
Degree has good weatherability, wearability, water resistance, stain resistance and excellent painting effect, and production process is simple, environmental protection
Health can meet the market demand in this field.
Detailed description of the invention
Fig. 1 is the XRD diagram of chitosan loaded Ag/Cu duplex metal nano granule according to the present invention；
Fig. 2 show according to comparative example 2(be added commercial surfactant) inorganic particle and latex particle diluted mixture
Form；
Fig. 3, which is shown, is added surfactant according to the present invention according to embodiment 4() inorganic particle and latex particle it is dilute
Release the form of mixture；
Fig. 4 is the SEM-EDX spectrogram of surfactant according to the present invention.
Specific embodiment
It is to illustrate specific embodiments of the present invention, but the present invention is not limited thereto below.
Embodiment 1
The preparation of chitosan loaded Ag/Cu duplex metal nano granule: chitosan 3g is dispersed in 100ml water by being ultrasonically treated
In, it is ultrasonically treated 10 minutes, the AgNO of 0.01M concentration is then added3Aqueous solution 20ml, and mixture is ultrasonically treated 60 points
Clock obtains suspension；(2) 100ml n,N-Dimethylformamide is added into gained suspension, and anti-in 90 DEG C under stiring
It answers 6 hours, Ag nano particle-chitosan hybrid object that recycling obtains then is washed with deionized；It (3) will under ultrasonic treatment
Ag nano particle-chitosan hybrid object and 0.01M concentration CuCl of step (2) preparation2Solution 20ml mixing, is stirred 2 hours,
It is then slowly added to the potassium borohydride aqueous solution 4.4ml of 0.1M, and reacts the mixture 24 hours at 100 DEG C, is then used
Water washing and drying obtain chitosan loaded Ag/Cu duplex metal nano granule.
Embodiment 2
Reaction vessel is led to nitrogen to protect, initial charge is then added into reaction vessel, wherein the initial charge packet
The HEDTA-3NA of water and 0.0001 parts by weight containing 250 parts by weight；Then flask is heated to 90 DEG C using water-bath, it is continuous to add
Enter monomer feed and aqueous feed, continuous charging is completed in 4 hours, wherein the monomer feed includes 110 parts by weight propylene
Sour methyl esters, the methyl methacrylate of 60 parts by weight, the glycidyl methacrylate of 10 parts by weight, γ-first of 6 parts by weight
Base acryloyloxypropyltrimethoxysilane, the aqueous feed include 60 parts by weight of deionized water, the 12 of 2.0 parts by weight
Alkyl diphenyl ether disulphonic acid natrium surfactant, the sodium peroxydisulfate of 0.3 parts by weight, the sodium bicarbonate of 0.2 parts by weight, after adding,
Latex is kept for 1 hour at 90 DEG C to complete polymerization, then filters, obtains emulsion polymer.
The granularity of emulsion polymer can use fluid dynamics chromatography determination, and average grain diameter is about 92nm.Pass through differential
The T of scanning calorimetry measurement dry polymer sampleg(glass transition temperature): being cooled to about -40 DEG C for sample, with 10 DEG C/
Min is cooled to -40 DEG C from -40 DEG C of scannings to 200 DEG C, then is scanned for the first time with 10 DEG C/min from -40 DEG C of scannings to 200 DEG C
For adjusting sample, using the point of inflexion on a curve of second of scanning as Tg.After tested, the T of the emulsion polymergIt is about 4.5 DEG C.
The lower TgIt ensures the film forming under low temperature, without coalescing aid is added, avoids the production of VOC
It is raw.
Embodiment 3
In the 500mL flask of the neck flask equipped with mechanical agitator, thermometer and condenser, by 130g methacrylic acid 2- hydroxyl
Ethyl ester and 0.2g mono-methylether hydroquinone, which are placed in, makes about 50 DEG C of reactor, and then by 59.16g, phosphorus pentoxide is slowly added into instead
It answers in device, temperature is maintained at 50 DEG C and reacts 3 hours hereinafter, going in a nitrogen environment, is cooled to room temperature, filters, use sodium hydroxide
Solution regulation system pH value is about 8.0, filtering, then filtrate pH value is adjusted to 3-6, places, filters out precipitating, is washed, dry, i.e.,
Obtain surfactant shown in formula (I).
Embodiment 4
Multifunctional inorganic ecologic coating composition is prepared, by weight, by 60 parts of ripple mountain flour bodies and 1.0 parts according to embodiment 2
Surfactant obtained is sufficiently mixed, and 30 parts of emulsion polymer, thickener according to made from embodiment 1 is then added
0.2 part of (Rheovis HS 1152 derives from BASF), 0.2 part of pigment (zinc oxide newly reaches Xin Ye Co., Ltd derived from Yangzhou), then
100 parts of water are added, stir, obtain the aqueous form i.e. water paint of coating.The water-borne dispersions of coating are cast
Onto quartz plate, covering is placed 48 hours at room temperature, is made it dry, film thickness 0.2-0.6mm, flawless.
Comparative example 1
Embodiment 3 is repeated, difference is only that emulsion polymer flexible acrylic acid emulsion (RS-300 is purchased from Ahmedabad richness company) replaces
Generation.
The VOC of the coating of (GB 18582-2008) testing example 3 and comparative example 1 according to national standards.Test equipment and
Condition is as follows:
Instrument: Agilent 7890A gas chromatograph (test VOC content use)；Detector: flame ionization ditector；Color
Compose column: HP-1301；Reagent: DMF, with 5 molecular sieve dehydrations；Isopropanol, with 5 molecular sieve dehydrations；Acetonitrile, isobutanol.It is above equal
It is pure to analyze.
65 DEG C of column temperature initial temperature, keep 18 min；210 DEG C of 5 min of holding are risen to 30 DEG C/min；Again with 30 DEG C/min liter
To 250 DEG C of 5 min of holding；Injector temperature is 250 DEG C, and detector temperature is 300 DEG C, and carrier gas is high pure nitrogen, and internal standard compound is
Isobutanol, flow rate of carrier gas are 0.8 mL/min, and combustion gas is 40mL/min H2, combustion-supporting gas is 400 mL/min air, and sample volume is
1 μL.Calculation formula is VOC=(V-VH2O)×ρ Sample×103。
The VOC content of embodiment 3 is lower than detection limit, and the VOC of the coating of comparative example 1 is 120.2 g/L.
Comparative example 2
Embodiment 3 is repeated, difference is only that (DEMOL EP derives from Japan to surfactant using polycarboxylate surfactant
Flower king).
By Fig. 2 and 3 clearly it can be seen from the use of coating of the invention due to the surfactant, emulsion polymerization
Composition granule and inorganic particle have good compatibility, and latex particle is perfectly adhered to the surface of inorganic particle.And use city
It sells in the comparative example 2 of polycarboxylic acids surfactant, emulsion polymerization composition granule and the inorganic particle of significant proportion isolate, and do not have
It is attached to the surface of inorganic particle, the two compatibility is poor, is easy to happen aggregation, this can lead to the multinomial performance such as gloss of film
Property and mechanical performance are deteriorated.
Embodiment 5
Multifunctional inorganic ecologic coating composition is prepared, by weight, by 60 parts of ripple mountain flour bodies and 1.0 parts according to embodiment 3
Surfactant obtained is sufficiently mixed, and 30 parts of emulsion polymer, thickener according to made from embodiment 2 is then added
0.2 part of (Rheovis HS 1152 derives from BASF), 0.2 part of pigment (zinc oxide newly reaches Xin Ye Co., Ltd derived from Yangzhou), root
According to 0.2 part of chitosan loaded Ag/Cu duplex metal nano granule prepared by embodiment 1,100 parts of water are added, are sufficiently stirred
It is even, obtain the aqueous form i.e. water paint of coating.The water-borne dispersions of coating are cast on quartz plate, are covered, in room temperature
It is lower to place 48 hours, it makes it dry, film thickness 0.2-0.6mm, flawless.The illumination 240h(luminous intensity in UV irradiation experiment room
For 720w/cm2), and referring to aforementioned VOC test method, VOC content is lower than detection limit.Conventionally, by adding this
In the case where the complex antimicrobials of invention, bacterium is in the growth for being up to 6 hour incubation period in detection Escherichia coli fluid nutrient medium
Situation (in terms of Colony Forming Unit, CFU), concentration 1.1E+8(CFU/ml).
Comparative example 3
Embodiment 5 is repeated, difference is only that commercial antimicrobial agent (chitosan antimicrobial agent, Shanghai He Tai chemical industry using same amount
Company) substitution, bacterial growth concentration is 8.4E+8(CFU/ml).
Comparative example 4
Embodiment 5 is repeated, difference is only that the AgCu nano particle substitution using same amount, bacterial growth concentration are 4.6E+8
(CFU/ml).
From above-described embodiment and comparative example it can be clearly seen that antibacterial agent of the invention has obvious preferable antibacterial effect
Fruit.Ag/Cu duplex metal nano granule plays synergy by being supported on chitosan.This may be attributed to metal nano
Grain dispersion more evenly, so as to avoid agglomeration, and it is more stable, the ion of enhancing is generated when being exposed to bacteria culture media
Release.In addition, the synergistic effect of the two kinds of different metals coexisted on surface and the humidification of graphene carrier, it can be into one
Step improves antibacterial activity.
This written description discloses the present invention, including optimal mode using example, and also enables those skilled in the art
The manufacture and use present invention.It is of the invention can patentable scope be defined by the claims, and may include this field skill
Other examples that art personnel expect.If this other examples have not different from the structural elements of the literal language of claims
Element, or if this other examples include the equivalent structure element with the literal language of claims without substantial differences,
Then this other examples are intended within the scope of claims.In the case where not will cause inconsistent degree, by reference to
It will be incorporated herein in place of all references referred to herein.
Claims (10)
1. a kind of complex antimicrobials, wherein the complex antimicrobials include Ag/Cu nano particle and chitosan.
2. complex antimicrobials according to claim 1, wherein the Ag/Cu is alloy state, which has micro- group of S phase
It knits.
3. complex antimicrobials according to claim 1, wherein the AgCu nano particle is supported on chitosan.
4. complex antimicrobials according to any one of the preceding claims, wherein the chitosan is chitosan.
5. indoor air purification type multifunctional inorganic ecologic coating, by weight, which includes: 50-90 parts of inorganic mineral powder,
5-60 parts of emulsion polymer, 0.1-10.0 parts of thickener, 0.1-5.0 parts of surfactant, 0.01-5.0 parts of pigment, according to right
It is required that described in any item complex antimicrobials 0.01-2.0 parts of 1-4.
6. multifunctional inorganic ecologic coating according to any one of the preceding claims, wherein the pigment is inorganic face
Material.
7. the method for preparing multifunctional inorganic ecologic coating according to claim 5 or 6, this method includes by each coating group
Divide and is uniformly mixed.
8. according to the method described in claim 7, wherein mixing step is included in surfactant and latex polymer, thickening
Agent and inorganic pigment mix surfactant with inorganic mineral powder with before mixing.
9. according to the method described in claim 8, wherein the surfactant and inorganic mineral powder are thoroughly mixed
It is even.
10. this method includes by the coating using the method for multifunctional inorganic ecologic coating according to claim 5 or 6
It is mixed with water, wherein the dosage of the water is 10-500 parts.
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| CN111847975A (en) * | 2020-06-11 | 2020-10-30 | 中建西部建设建材科学研究院有限公司 | Preparation and application method of gypsum composite mildew inhibitor with waterproof function |
| CN112225456A (en) * | 2020-10-22 | 2021-01-15 | 林玉婷 | Antibacterial and mildewproof ceramic glaze as well as preparation method and application thereof |
| WO2023024661A1 (en) * | 2022-04-20 | 2023-03-02 | 山东海科创新研究院有限公司 | Antibacterial agent, and antibacterial polysulfone composite material and preparation method therefor |
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