CN107955482A - A kind of graphene-based antibacterial, wear-resisting dual-component coating and preparation method thereof, application and application method - Google Patents
A kind of graphene-based antibacterial, wear-resisting dual-component coating and preparation method thereof, application and application method Download PDFInfo
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- CN107955482A CN107955482A CN201711258629.6A CN201711258629A CN107955482A CN 107955482 A CN107955482 A CN 107955482A CN 201711258629 A CN201711258629 A CN 201711258629A CN 107955482 A CN107955482 A CN 107955482A
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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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
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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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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
- E04G21/00—Preparing, conveying, or working-up building materials or building elements in situ; Other devices or measures for constructional work
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The present invention provides a kind of graphene-based antibacterial, wear-resisting dual-component coating, concrete scheme is：Component A is：Using acrylic acid series polymeric compounds aqueous dispersions as matrix, it is antiseptic and 2 propylene oxygen ethyl tributyl phosphorus chloride trimethoxyvinyl silicon oligomer and other auxiliary agents containing fluoroalkyl to add graphene-supported titanium dioxide；B component is ketimide；The graphene-supported titanium dioxide is uniformly dispersed in water in 1 10 microns of graphene oxide, 10 50 nanometers of titanium dioxide granule and silane coupling agent, through reducing, being dried to obtain；Acrylic acid series polymeric compounds are selected by monomer and introduce glass microballoon raising wearability, and the product finally obtained has excellent antibacterial, wear-resisting, resistant and adhesive force, its excellent antibiotic property and wearability are suitable for the very big hospital of flow of the people, school uses.
Description
Technical field
The present invention relates to a kind of antibacterial, wear-resisting dual-component coating field, and in particular to a kind of graphene-based antibacterial, resistance to of having concurrently
Dual-component coating field is ground, the present invention is further directed to antibacterial, the preparation method of wear-resisting dual-component coating, application and user
Method.
Background technology
Coating is as most common construction material in construction and decoration, and to covering wall, most basic effect is beautiful.It is existing
It is usually high molecular polymer to have coating in technology, and acrylic polymer is common species.With in construction and decoration to ring
Guaranteed request is higher and higher, and water paint becomes the hot spot of research and development.
Coating with functionalization is more popular direction, it is possible to achieve, can be with while decoration function is played
Play and assign other functional characteristics etc., such as antibacterial, wear-resisting, uvioresistant function is specific.For the coating of antibacterial characteristics, if plus
Enter part small molecule antiseptic, first, constituent part has the taste for making one not pleasant, second, small molecule antiseptic short run effect can
With, but moving out with small molecule antiseptic, antibacterial effect decline quickly.And for the coating of antiwear characteristic, typically add
Enter a part of wear resistant filler, but the addition of wear resistant filler can cause the flatness of coating surface to have a certain impact；It is if it is desired to simultaneous
Both characteristics of tool are just more difficult to control.Therefore, how to obtain the wear resistnat paint of long acting antibiotic and become the phase to be solved asking
Topic.
In view of the above-mentioned problems, having carried out the research of series in person, technical scheme has been obtained.
The content of the invention
Goal of the invention：The present invention is intended to provide a kind of coating with excellent antibacterial, resistant and adhesive force, it can meet
Daily conventional demand, simultaneously as its outstanding antibacterial action, can be adapted to the use of hospital and school, raising uses ring
The air quality in border, reduces germ.Ultraviolet light disinfection, the irradiation excitation two of ultraviolet light can be generally carried out in school and hospital
The antibacterial effect of titanium oxide, can significantly lift the bactericidal effect of coating.Meanwhile to belong to flow of the people intensive for hospital and school
Public domain, the Rubbing number of wall is more, the present invention also to bactericidal effect, good coating further improves its wear-resisting spy
Property.
The said goods in order to obtain, present invention also offers the preparation method and applications and application method of above-mentioned coating.
In order to reach the effect above, the present invention provides following technical solution.
Summary of the invention
[1] a kind of graphene-based antibacterials of, wear-resisting dual-component coating, it includes component A and B component, component A is：With propylene
Sour based polymer aqueous dispersions are matrix, and it is antiseptic and the 2- propylene oxygen containing fluoroalkyl to add graphene-supported titanium dioxide
Ethyl tributyl phosphorus chloride-trimethoxyvinyl silicon oligomer and other auxiliary agents；B component is ketimide；Component A and B groups
The mass ratio divided is 100:0.5-3..
[2] graphene-based antibacterials of the according to scheme [1], wear-resisting dual-component coating, the acrylic acid series polymeric compounds water
Dispersion liquid by the butyl acrylate of 20-25 parts by weight, the methyl acrylate of 5-10 parts by weight, 5-8 parts by weight epoxy acrylic
Ester, the hydroxy-ethyl acrylate of 3-8 parts by weight, acrylic acid -2- phenethyl esters, the calcium carbonate of 3-10 parts by weight, the 5- of 12-16 parts by weight
The glass microballoon of 20 parts by weight, the silane coupling agent of 0.5-3 parts by weight, the surfactant of 1-5 parts by weight, 0.5-3 parts by weight
Initiator and 100-200 parts by weight water.
[3] graphene-based antibacterials of the according to scheme [1], wear-resisting dual-component coating, the graphene-supported titanium dioxide
Titanium is uniformly dispersed in water in 1-10 microns of graphene oxide, 10-50 nanometers of titanium dioxide granule and silane coupling agent,
Through reduction, drying and other steps, to obtain the final product.
[4] graphene-based antibacterials of the according to scheme [3], wear-resisting dual-component coating, graphene oxide, titanium dioxide
The weight ratio of particle and silane coupling agent is 10：5-15：0.5-1.
[5] graphene-based antibacterials of the according to scheme [1], wear-resisting dual-component coating, graphene-supported titanium dioxide are
Antiseptic addition is the 0.5-1wt% of acrylic acid series polymeric compounds aqueous dispersions, three fourth of 2- propylene oxygen ethyl containing fluoroalkyl
Base phosphorus chloride-trimethoxyvinyl silicon oligomer addition is the 0.2-1.2wt% of acrylic acid series polymeric compounds aqueous dispersions.
[6] graphene-based antibacterials of the according to scheme [5], wear-resisting dual-component coating, graphene-supported titanium dioxide with
The mass ratio of 2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxyvinyl silicon oligomer containing fluoroalkyl is 0.5-1.5：
1, both total additions are not more than the 1wt% of acrylic acid series polymeric compounds aqueous dispersions.
[7] graphene-based antibacterials of the according to scheme [1], wear-resisting dual-component coating, further also receive containing 10-100
The graphene of rice, addition are the 0.01-0.5wt% of acrylic acid series polymeric compounds aqueous dispersions.
[8] graphene-based antibacterials of the according to scheme [1], wear-resisting dual-component coating, auxiliary agent described further can be
Antioxidant, ultraviolet absorber, levelling agent, pigment, said components addition are the 0.01- of acrylic acid series polymeric compounds aqueous dispersions
1.0wt%.
[9] the graphene-based antibacterial in any one of schemes [1]-[7], the preparation method of wear-resisting dual-component coating, it is included such as
Under：
The preparation of component A：
A, acrylic acid series polymeric compounds aqueous dispersions are prepared；
B, it is antiseptic and the 2- propylene oxygen ethyl tributyl chlorinations containing fluoroalkyl to add graphene-supported titanium dioxide
Phosphorus-trimethoxyvinyl silicon oligomer, stirs evenly；
C, other auxiliary agents are added, are uniformly mixed '
The preparation of B component：B component is directly packed for ketimide.
[10] the graphene-based antibacterial in any one of schemes [1]-[7], wear-resisting dual-component coating are in external and internal wall brushing
Using.
[11] the graphene-based antibacterial in any one of schemes [1]-[7], wear-resisting dual-component coating are applied in hospital, school's interior wall
Application in brush.
[12] the graphene-based antibacterial in any one of schemes [1]-[7], wear-resisting dual-component coating, in use, component A and B groups
Divide with 100:The mass ratio of 0.5-3 is uniformly mixed, brushing of the mixed process control in 5min, after mixing progress wall.
Detailed description of the invention
For the technical solution of better understanding invention, it is introduced separately below, particular content is as follows：
The graphene-based antibacterial of the present invention, the basic composition of wear-resisting dual-component coating：Component A is with acrylic acid series polymeric compounds water
Dispersion liquid is matrix, and it is antiseptic and the 2- propylene oxygen ethyl tributyl chlorine containing fluoroalkyl to add graphene-supported titanium dioxide
Change phosphorus-trimethoxyvinyl silicon oligomer and other auxiliary agents, B component use ketimide as epoxy in acrylate copolymer
The curing agent of acrylate, 24 after the brushing interior curings secondary to coating progress when small, improves strength of coating.With acrylic acid
Compound of birdsing of the same feather flock together is main body, and the feature of environmental protection of aqueous dispersions is higher, organic solvent-free, does not produce pollution.Graphene-supported titanium dioxide
2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxyvinyl silicon oligomer for antiseptic and containing fluoroalkyl is as multiple
Antiseptic, organo-mineral complexing are closed, organic antibacterial agent can also improve the dispersion effect of inorganic antiseptic.With being filled out in previous research
Material species is also adjusted, and partial replacement calcium carbonate be glass microballoon, improves the flatness of coating surface, and raising is wear-resisting
Property.
Specifically chosen and mechanism is described below：
Acrylic acid series polymeric compounds
Acrylic acid series polymeric compounds aqueous dispersions are by the butyl acrylates of 20-25 parts by weight, 5-10 parts by weight in the present invention
Methyl acrylate, the epoxy acrylate of 5-8 parts by weight, the hydroxy-ethyl acrylate of 3-8 parts by weight, the propylene of 12-16 parts by weight
Acid -2- phenethyl esters, the calcium carbonate of 3-10 parts by weight, the glass microballoon of 5-20 parts by weight, 0.5-3 parts by weight silane coupling agent,
The water of the surfactant of 1-5 parts by weight, the initiator of 0.5-3 parts by weight and 100-200 parts by weight.
For the composition based on short chain acrylates, the polymer strength that it is obtained is larger, has after curing larger hard
Degree, while acrylic acid -2- phenethyl esters are specifically added, such short chain substantially increases the wearability of coating containing benzene monomer, and addition contains
Benzene monomer can cause yellowing resistance to reduce to a certain extent, therefore such coating is more suitable for indoor use.If applicable in outdoor, build
View adds ultraviolet absorber, antioxidant etc. in coating and improves basic performance.Acrylic acid -2- phenethyl esters dosage is 12-16 weight
Part, it is preferably 14 parts by weight, if dosage is excessive, adhesive force reduces, if dosage is too small, wearability is relatively low.In order to realize
The secondary curing effect in later stage, in the monomer that can improve hardness, intensity, selection adds epoxy acrylate, its middle ring
Oxygen groups carry out secondary curing in the later stage, are further improved on the basis of original strength of coating, improve wear-resisting characteristic.
Hydroxy-ethyl acrylate can improve the adhesive force to wall as hydroxyl monomer, preferable amount 3-8 parts by weight,
More preferably 5-6 parts by weight, if dosage is too low, adhesive force deficiency, easy peeling-off situation, if excessive, system dispersiveness drop
It is low, cause the dispersiveness variation of filler-calcium carbonate and inorganic antiseptic, comprehensive performance has declined.
Calcium carbonate adds as basic filler and improves intensity, in order to improve dispersiveness, it is proposed that adds coupling agent and anticipates
Calcium carbonate.Since calcium carbonate contains certain microcellular structure, and surface smoothness deficiency, if calcium carbonate disperses in coating surface
When measuring larger, the hydro-oleophobicity on surface declines, and also has the tendency for reducing wearability.Present invention employs a part of glass is micro-
Pearl replaces calcium carbonate, improves the flatness of coating surface, improves wearability.It is preferred that calcium carbonate：The weight ratio of glass microballoon is 3-
10：5-20, more preferably ratio are 5:10.
Complex antimicrobials
The complex antimicrobials of the present invention are the compound of inorganic antiseptic and organic antibacterial agent, and inorganic antiseptic is born for graphene
Carrying of titanium dioxide is antiseptic, and organic antibacterial agent is 2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxy containing fluoroalkyl
Vinyl silicon oligomer, inorganic antiseptic belong to long-acting antibiotic agent, and the short run effect of organic antibacterial agent is more excellent.
Graphene-supported titanium dioxide has antibiotic property as antiseptic, wherein titanium dioxide, it is irradiated in ultraviolet light
Under be activated after antibacterial effect it is excellent, and graphene has very much not structure, preferably has large stretch of structure, under ultraviolet light
The activation effect of titanium dioxide can be assisted, improves the antibacterial effect of titanium dioxide.
The graphene-supported titanium dioxide is graphene oxide, 10-50 nanometers of the titanium dioxide at 1-10 microns
Grain be uniformly dispersed in water with silane coupling agent, through reduce, drying and other steps, to obtain the final product.Graphene oxide, titanium dioxide granule and
The weight ratio of silane coupling agent is 10：5-15：0.5-1.Using graphene oxide because its good dispersion, polarity are high, it is possible to achieve
With being sufficiently mixed for titanium dioxide, meanwhile, further add silane coupling agent, both good keys linked up, but the later stage must
Graphene oxide must be reduced to graphene by reduction.
Organic antibacterial agent is oligomeric for 2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxyvinyl silicon containing fluoroalkyl
Thing, it is that the material that fluorine-based and silicon substrate is formed is combined with phosphorus, becomes while has the sterilization of phosphorus, antibacterial, fluorine is hated
Water increases oiliness, the novel and multifunctional material of grade easily compatible with silica glass material.The inorganic antiseptic is by peroxidating fluoroalkyl alcohol
Reacted with 2- propylene oxygen ethyl tributyl phosphorus chloride and trimethoxyvinyl silicon, synthesize the 2- propylene oxygen containing fluoroalkyl
The oligomer of ethyl tributyl phosphorus chloride-trimethoxyvinyl silicon.Simultaneously as containing alkoxy in its structure, it is dissociated
After can be attached on inorganic antiseptic, avoid conventional organic antibacterial agent it is easily free the problem of.The inorganic antiseptic may be used also
To improve antifouling property.
Graphene-supported titanium dioxide is the 0.5-1wt% that antiseptic addition is acrylic acid series polymeric compounds aqueous dispersions,
2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxyvinyl silicon oligomer addition containing fluoroalkyl is gathered for acrylic acid series
The 0.2-1.2wt% of compound aqueous dispersions.Graphene-supported titanium dioxide and the 2- propylene oxygen ethyl tributyls containing fluoroalkyl
The mass ratio of phosphorus chloride-trimethoxyvinyl silicon oligomer is 0.5-1.5：1, preferably 1.5：1, if organic antimicrobial levels
Too low, short-acting antibiotic property reduces, if inorganic antibacterial agent content is too low, long-term antimicrobial efficiency is too low, and preferably both total additions are small
In the 1wt% of acrylic acid series polymeric compounds aqueous dispersions.
For the antiseptic also containing 10-100 nanometers of graphene, addition is acrylic acid series polymeric compounds aqueous dispersions
0.01-0.5wt%.The small size graphene is nanoscale, coordinates with big size graphene, improves energy transmission, can be with
Antibiotic property is further improved, while the addition of graphene can also improve stain resistance.
Other factors
Auxiliary agent can be antioxidant, ultraviolet absorber, levelling agent, pigment in the present invention, and said components addition is third
The 0.01-1.0wt% of olefin(e) acid based polymer aqueous dispersions, auxiliary agent commonly used in the art can add as needed.
The preparation method of coating
The preparation method of graphene-based antibacterial, wear-resisting dual-component coating, it includes as follows：
The preparation of component A：
A, acrylic acid series polymeric compounds aqueous dispersions are prepared；
B, it is antiseptic and the 2- propylene oxygen ethyl tributyl chlorinations containing fluoroalkyl to add graphene-supported titanium dioxide
Phosphorus-trimethoxyvinyl silicon oligomer, stirs evenly；
C, other auxiliary agents are added, are uniformly mixed '
The preparation of B component：B component is directly packed for ketimide.
The purposes of coating
The application in external and internal wall brushing of graphene-based antibacterial, wear-resisting dual-component coating of the present invention, preferably hospital,
Application in school's interior wall brushing.In the use of the present invention, being coated on wall, a ultraviolet irradiation is preferably carried out.It is ultraviolet
It can promote the abundant curing of acrylic monomers after line irradiation, activate the fungistatic effect of silica, while titanium dioxide promotes
Graphene is catalyzed the principal Guo of organic bacteriostatic agent, promotes the raising of antibiotic property on the whole.
The application method of coating
In use, component A and B component are with 100:The mass ratio of 0.5-3 is uniformly mixed, and mixed process is controlled in 5min, is mixed
The brushing of wall is carried out after closing uniformly.Due in B component ketimide under conditions of water it is unstable, epoxide group consolidates after decomposition
Change is immediately begun to, therefore the mixing of A, B component is rapid, and general validity period is interior when 1 is small.
Beneficial technique effect：
The present invention provides a kind of coating with excellent antibacterial, resistant and adhesive force, it can meet daily conventional
Demand, simultaneously as its outstanding antibacterial action, can be adapted to the use of hospital and school, improves the air matter of use environment
Amount, reduces germ.From the point of view of specific, its by being used as hydroxyl monomer in the acrylic acid series polymeric compounds of matrix, containing aromatic structure
Selection, balance adhesive force and wearability, the effect of intensity, and consider follow-up filler it is scattered the problems such as.In filler
Using glass microballoon, the surface smoothness after paint solidification is improved, also realizes the effect for improving wearability.
The present invention is also by organic antibacterial agent and the complex antimicrobials of inorganic antiseptic, and wherein inorganic antiseptic is using large stretch of
Graphene-supported titanium dioxide nanoparticle, can further coordinate small size graphene, and graphene obtains performance and promotes dioxy
Change titanium and obtain bactericidal effect；Organic antibacterial agent uses 2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxy second containing fluoroalkyl
The oligomer of alkenyl silicon, it can improve the actual effect of antiseptic, while its alkoxy can have been improved with inorganic antiseptic
The stability of machine antiseptic, inorganic antiseptic have long acting antibiotic effect.The present invention is suitable for the brushing of Discussion on architecture, more applicable
In the interior wall coating of school and hospital, ultraviolet light disinfection, the irradiation excitation of ultraviolet light can be generally carried out in school and hospital
The antibacterial effect of titanium dioxide, can significantly lift the bactericidal effect of coating.
The present invention is also using A, B component, and ketimide promotes the curing of epoxide group in B component, improve coating intensity and
Wearability.
To sum up, the concrete composition and dosage and application method of structure adjusting each component of the present invention, has obtained comprehensive performance
Very excellent graphene-based antibacterial, wear-resisting dual-component coating.
Embodiment
In order to make technical staff's more intuitive understanding technical scheme, select below several exemplary embodiments into
Row is introduced, these embodiments do not form limiting the scope of the invention, and any scheme without departing substantially from inventive concept is all at this
In invention protection domain.
Preparation example
1. acrylic acid series polymeric compounds
Acrylic acid series polymeric compounds A：Form for acrylic acid series polymeric compounds aqueous dispersions by 22 parts by weight butyl acrylate, 8
The methyl acrylate of parts by weight, the epoxy acrylate of 6 parts by weight, the hydroxy-ethyl acrylate of 5 parts by weight, the propylene of 14 parts by weight
Acid -2- phenethyl esters, the calcium carbonate of 6 parts by weight, the glass microballoon of 14 parts by weight, the silane coupling agents of 1 parts by weight, 2 parts by weight
The water of surfactant, the initiator of 2 parts by weight and 120 parts by weight, said components obtain acrylic acid series by radical polymerization
Polymer A.
Acrylic acid series polymeric compounds B：Form for acrylic acid series polymeric compounds aqueous dispersions by 25 parts by weight butyl acrylate, 11
The methyl acrylate of parts by weight, the hydroxy-ethyl acrylate of 5 parts by weight, the acrylic acid -2- phenethyl esters of 14 parts by weight, 6 parts by weight
Calcium carbonate, the glass microballoon of 14 parts by weight, the silane coupling agent of 1 parts by weight, the surfactant of 2 parts by weight, 2 parts by weight are drawn
The water of agent and 120 parts by weight is sent out, said components obtain acrylic acid series polymeric compounds B by radical polymerization.
Acrylic acid series polymeric compounds C：Form for acrylic acid series polymeric compounds aqueous dispersions by 22 parts by weight butyl acrylate, 8
The methyl acrylate of parts by weight, the epoxy acrylate of 6 parts by weight, the hydroxy-ethyl acrylate of 5 parts by weight, the propylene of 14 parts by weight
Acid -2- phenethyl esters, the calcium carbonate of 20 parts by weight, the silane coupling agent of 1 parts by weight, the surfactant of 2 parts by weight, 2 parts by weight
Initiator and 120 parts by weight water, said components obtain acrylic acid series polymeric compounds C by radical polymerization.
Acrylic acid series polymeric compounds D：Form for acrylic acid series polymeric compounds aqueous dispersions by 22 parts by weight butyl acrylate, 8
The methyl acrylate of parts by weight, the epoxy acrylate of 6 parts by weight, the hydroxy-ethyl acrylate of 5 parts by weight, the propylene of 14 parts by weight
Acid -2- phenethyl esters, the calcium carbonate of 18 parts by weight, the glass microballoon of 2 parts by weight, the silane coupling agents of 1 parts by weight, 2 parts by weight
The water of surfactant, the initiator of 2 parts by weight and 120 parts by weight, said components obtain acrylic acid series by radical polymerization
It polymerize D.
Acrylic acid series polymeric compounds E：Form for acrylic acid series polymeric compounds aqueous dispersions by 27 parts by weight butyl acrylate, 13
The methyl acrylate of parts by weight, the epoxy acrylate of 10 parts by weight, the hydroxy-ethyl acrylate of 5 parts by weight, the carbonic acid of 6 parts by weight
Calcium, the glass microballoon of 14 parts by weight, the silane coupling agent of 1 parts by weight, the surfactant of 2 parts by weight, the initiator of 2 parts by weight
With the water of 120 parts by weight, said components obtain acrylic acid series polymeric compounds D by radical polymerization.
Acrylic acid series polymeric compounds F：Form for acrylic acid series polymeric compounds aqueous dispersions by 23 parts by weight butyl acrylate, 9
The methyl acrylate of parts by weight, the epoxy acrylate of 7 parts by weight, the hydroxy-ethyl acrylate of 2 parts by weight, the propylene of 14 parts by weight
Acid -2- phenethyl esters, the calcium carbonate of 6 parts by weight, the glass microballoon of 14 parts by weight, the silane coupling agents of 1 parts by weight, 2 parts by weight
The water of surfactant, the initiator of 2 parts by weight and 120 parts by weight, said components obtain acrylic acid series by radical polymerization
Polymer F.
2. inorganic antiseptic
Inorganic antiseptic I1：By about 8 microns of graphene oxide of 10 parts by weight, 20 nanometers of titanium dioxide of 12 parts by weight
Titanium particle and the silane coupling agent of 1 parts by weight are uniformly dispersed in water, through reducing, dry, up to graphene-supported nano-silica
Change titanium.
Inorganic antiseptic I2：By about 8 microns of graphene oxide of 22 parts by weight and the silane coupling agent of 1 parts by weight in water
In be uniformly dispersed, through reducing, being drying to obtain.
Inorganic antiseptic I3：The silane coupling agent of 20 nanometers of titanium dioxide granule of 22 parts by weight and 1 parts by weight is existed
It is uniformly dispersed, is drying to obtain in water.
Inorganic antiseptic I4：By about 0.5 micron of graphene oxide of 10 parts by weight, 20 nanometers of dioxy of 12 parts by weight
Change titanium particle and the silane coupling agent of 1 parts by weight is uniformly dispersed in water, through reducing, dry, up to graphene-supported nanometer two
Titanium oxide.
Performance test methods
1. coating pollution resistance is tested
Test method described in above-mentioned test method referenced patent CN104312232A carries out.
2. bacteriostasis rate test method
Bacterium solution is spread evenly across on the glass slide for scribbling antibacterial and mouldproof taste removal coating, when 0,2,4,8,12,24 is small after
Bacterium solution is gently wiped with swab stick and is placed in physiological saline, vibrates, takes 0.3ml to pour into culture medium in culture dish, in culture
When culture 48 is small in case, number clump count is taken out, bacteriostasis rate is calculated according to following formula.
Bacteriostasis rate=(A0-Ae)/A0 × 100%, wherein：The initial clump counts of A0- (a)；Clump count (a) after Ae- sterilizations.
3. wearability test
Wearability test is tested using ISO7784-2-1997, test condition 1000g, rotating speed 500r.
Embodiment and test result
Following preparation method is essentially identical, and general preparation process is following (having remarks explanation if any special modification)：
The preparation of component A：
A, acrylic acid series polymeric compounds aqueous dispersions are prepared；
B, it is antiseptic and the 2- propylene oxygen ethyl tributyl chlorinations containing fluoroalkyl to add graphene-supported titanium dioxide
Phosphorus-trimethoxyvinyl silicon oligomer, stirs evenly；
C, other auxiliary agents are added, are uniformly mixed '
The preparation of B component：B component is directly packed for ketimide.
It is uniformly mixed in 5 minutes using preceding A, B component, is coated on wall；Shone when curing 24 is small by ultraviolet excessively
Every test is carried out after penetrating.
PS：Above-mentioned organic antibacterial agent is 2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxy ethene containing fluoroalkyl
Base silicon oligomer.Embodiment 3 is tested without using ultraviolet irradiation, remaining embodiment and comparative example use ultraviolet light
After test；Ketimide is not added in embodiment 4 as curing agent, but test still 24 it is small when carry out.
Claims (10)
1. a kind of graphene-based antibacterial, wear-resisting dual-component coating, it is characterised in that：Component A is：With acrylic acid series polymeric compounds moisture
Dispersion liquid is matrix, and it is antiseptic and the 2- propylene oxygen ethyl tributyl chlorinations containing fluoroalkyl to add graphene-supported titanium dioxide
Phosphorus-trimethoxyvinyl silicon oligomer and other auxiliary agents；B component is ketimide；The mass ratio of component A and B component is
100:0.5-3。
2. graphene-based antibacterial according to claim 1, wear-resisting dual-component coating, it is characterised in that：The acrylic acid series
Aqueous polymer dispersion by the butyl acrylate of 20-25 parts by weight, the methyl acrylate of 5-10 parts by weight, 5-8 parts by weight ring
Oxypropylene acid esters, the hydroxy-ethyl acrylate of 3-8 parts by weight, the acrylic acid -2- phenethyl esters of 12-16 parts by weight, 3-10 parts by weight
Calcium carbonate, the glass microballoon of 5-20 parts by weight, the silane coupling agent of 0.5-3 parts by weight, 1-5 parts by weight surfactant,
The initiator of 0.5-3 parts by weight and the water of 100-200 parts by weight.
3. graphene-based antibacterial according to claim 1, wear-resisting dual-component coating, it is characterised in that：The graphene is born
Carrying of titanium dioxide be 1-10 microns graphene oxide, 10-50 nanometers of titanium dioxide granule and silane coupling agent in water
Be uniformly dispersed, through reduction, drying and other steps, to obtain the final product.
4. graphene-based antibacterial according to claim 3, wear-resisting dual-component coating, it is characterised in that：The graphite oxide
The weight ratio of alkene, titanium dioxide granule and silane coupling agent is 10：5-15：0.5-1.
5. graphene-based antibacterial according to claim 1, wear-resisting dual-component coating, it is characterised in that：Graphene-supported two
Titanium oxide is the 0.5-1wt% that antiseptic addition is acrylic acid series polymeric compounds aqueous dispersions, the 2- propylene oxygen second containing fluoroalkyl
Base tributyl phosphorus chloride-trimethoxyvinyl silicon oligomer addition is the 0.2- of acrylic acid series polymeric compounds aqueous dispersions
1.2wt%。
6. graphene-based antibacterial according to claim 5, wear-resisting dual-component coating, it is characterised in that：Graphene-supported two
The mass ratio of titanium oxide and 2- propylene oxygen ethyl tributyls phosphorus chloride-trimethoxyvinyl silicon oligomer containing fluoroalkyl is
0.5-1.5：1, both total additions are not more than the 1wt% of acrylic acid series polymeric compounds aqueous dispersions.
7. graphene-based antibacterial according to claim 1, wear-resisting dual-component coating, it is characterised in that：Further also contain
10-100 nanometers of graphene, addition are the 0.01-0.5wt% of acrylic acid series polymeric compounds aqueous dispersions.
8. the graphene-based antibacterials of any one of claim 1-7, the preparation method of wear-resisting dual-component coating, it is characterised in that：
The preparation of component A：
A, acrylic acid series polymeric compounds aqueous dispersions are prepared；
B, it is antiseptic and the 2- propylene oxygen ethyl tributyls phosphorus chloride-three containing fluoroalkyl to add graphene-supported titanium dioxide
Methoxy-ethylene base silicon oligomer, stirs evenly；
C, other auxiliary agents are added, are uniformly mixed '
The preparation of B component：B component is directly packed for ketimide.
9. the graphene-based antibacterials of any one of claim 1-7, application of the wear-resisting dual-component coating in external and internal wall brushing.
10. the graphene-based antibacterials of any one of claim 1-7, the application method of wear-resisting dual-component coating, it is characterised in that：Make
Used time, component A and B component are with 100:The mass ratio of 0.5-3 is uniformly mixed, and mixed process is controlled in 5min, is uniformly mixed laggard
The brushing of row wall.
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