CN103862988A - Mildew-resistant and antibacterial nano-silver decorative laminated board - Google Patents
Mildew-resistant and antibacterial nano-silver decorative laminated board Download PDFInfo
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Abstract
The invention relates to the field of nano materials and particularly relates to a mildew-resistant and antibacterial nano-silver decorative laminated board. The mildew-resistant and antibacterial nano-silver decorative laminated board is formed by a decorative veneer and a base material which are bonded by an adhesive layer, wherein the decorative veneer and the base material are dipped by nano aqueous solution; the adhesive layer contains nano-silver substances; the decorative veneer and the base material are made of technical wood; the nano-silver aqueous solution is formed by adopting deionized water as a solvent, adopting nano silver as solute to be dissolved into the deionized water, adopting acrylic resin as a complexing agent and a stabilizing agent to be dissolved into the deionized water, and adding a dispersing agent and a first reducing agent simultaneously; the concentration of nano silver in the adhesive is 75-150ppm; the mass content of flour in solution is 18-45%; environmental-friendly glue comprises the following materials in parts by weight: 40-80 parts of acrylic resin solution emulsion with the solid content being 40-55%, 20-40 parts of acrylic resin powder, 5-20 parts of EVA emulsion with the solid content being 40-60%, 1-4 parts of dibutyl phthalate and 7-13 parts of chlorinated polypropylene or polyolefin substrate adhesive-force promoter. The mildew-resistant and antibacterial nano-silver decorative laminated board has the advantages that the stability and the dispersibility are good and the mildew can be fully resisted.
Description
Technical field
The present invention relates to field of nanometer material technology, relate in particular to a kind of Nano Silver decoration veneer of antimildew and antibacterial.
Background technology
Metal nano material is an important branch of nano material, and it wherein obtains maximum concerns because of the wide application prospect of Nano Silver take noble metal gold, silver, copper as representative.Nano Silver can be used in a lot of aspects: in chemical fibre, add a small amount of Nano Silver, can improve some performance of chemical fibre product, and make it have very strong sterilizing ability; The appropriate Nano Silver that adulterates in silicon oxide film, can make the glass that plates this film have certain Photoluminescence.Therefore Nano Silver all has broad application prospects in fields such as anti-biotic material, effective catalyst, lubricant, light absorbing material, coating, sensor, electrocondution slurry, high performance electrode materials, becomes and has the functional material theoretical research of property and the important topic of application and development.
Since the preparation of Nano Silver and improvement technology are initial from nano anti-biotic material, just become the focus of researcher and developers' extensive concern.The preparation of Nano Silver is divided into Physical and chemical method.Chemical method has sol-gal process, galvanoplastic, oxidation-reduction method and vacuum vapour deposition etc.The I of silver-colored particle prepared by chemical method reaches several nanometers, simple to operate, easily controls.Shortcoming is that the silver-colored particle obtaining is difficult for shifting and assembling, and easily comprises impurity, and easily assembles.Physical is mainly vacuum evaporation, sputter plating and ion plating etc.Wherein chemical reduction method obtains fine application because required experiment condition is simple, energy-conservation.
CN200958280Y (2007-10-10) discloses a kind of decoration veneer that contains Nano Silver, but this use is nano silver colloidal sol, fails to give full play to the antimildew and antibacterial effect of Nano Silver.
Summary of the invention
The first object of the present invention be to provide a kind of can effectively resist mould the Nano Silver decoration veneer of antimildew and antibacterial.
The first technical purpose of the present invention is achieved by the following technical programs:
A Nano Silver decoration veneer for antimildew and antibacterial, is cohered and forms through adhesive layer by fancy veneer and base material, and described in it, fancy veneer and base material form through nano aqueous solution dipping, and described adhesive layer contains nano-silver substances; Described fancy veneer and base material are Recombinant Wood;
Described nano-silver water solution is take deionized water as solvent, dissolves in deionized water, take acrylic resin as complexing agent, stabilizing agent adds dispersant and the first reducing agent and form solution after dissolving in deionized water simultaneously take Nano Silver as solute;
Described dispersant is triethanolamine, and described the first reducing agent is the hydrazine hydrate aqueous solution;
The concentration of described Nano Silver is 50-150ppm, and the mass content of described acrylic resin in solution is 1-10%;
Described Nano Silver is prepared from according to following steps:
(1) sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate salting liquid are added in silver nitrate aqueous solution and obtain mixed liquor, the mol ratio of described dodecyl sodium sulfate and silver nitrate is 2-3:1; The mol ratio of described polyoxyethylene alkyl ether sulfate salt and silver nitrate is 0.4-0.6:1;
(2) in described mixed liquor, add crown ether and contain alkali-metal the second reducing agent, the mol ratio of described crown ether and silver nitrate is 1-2:1; The described mol ratio that contains alkali-metal reducing agent and silver nitrate is 0.5-1:1, and controlling pH value is 8-9, obtains Nano Silver;
The described adhesive that contains inorganic nano-silver is for to be evenly applied to Nano Silver in environment-friendly type glue solution, the additive using flour as glue;
The concentration of described Nano Silver in adhesive is 75-150ppm; The mass content of described flour in solution is 18-45%;
Described environment-friendly type glue comprises that the solids content of 40-80 part weight is that 40-55% is chlorinated polypropylene or the polyolefin substrate adhesion promoter of the solids content of acrylic resin powder, 5-20 part weight of emulsion acrylic resin, 20-40 part weight be 40-60% EVA emulsion, 1-4 part dibutyl phthalate and 7-13 part weight;
Described emulsion acrylic resin is synthetic as monomer and emulsifying agent, ammonium persulfate initiator, sodium acid carbonate and deionized water by any one or a few in any one or a few and methacrylic acid in methyl methacrylate, EMA, butyl methacrylate, butyl acrylate, isobutyl methacrylate, dodecylacrylate, acrylic acid stearyl, acrylic acid, acrylamide, acrylonitrile, Methacrylamide, styrene.
Advantage of the present invention is:
Crown ether have hydrophobic external skeletal and hydrophilic can with the inner chamber of metal ion Cheng Jian, can form stable complex with alkali metal ion.Simultaneously; the present invention is engaged in follow-up reduction reaction and adds and contain alkali-metal reducing agent; add after above-mentioned reducing agent, crown ether and alkali metal ion form stable complex, make on the one hand free in reaction system or exposed reduction anion have higher reactivity; Meanwhile, after alkali metal and crown ether generation ligand complex, alkali metal cation is coated in inner chamber by crown ether, just pulls open thus the distance between positive and negative charge in Nano Silver system, make Nano Silver can stable dispersion in the aqueous solution, be difficult for reuniting;
2. the combination of dispersant, the first reducing agent and the stabilizing agent by specific components and proportioning and Nano Silver solute are mixed with the Nano Silver decoration veneer of antimildew and antibacterial, reunion and particle can not occur in depositing grows up, and can be not oxidized, stability and good dispersion;
3. by the particular combinations of environment-friendly type glue solution and Nano Silver, the additive using flour as glue is mixed with the adhesive that contains Nano Silver, and in depositing, can there is not reunion and particle and grow up, and can be not oxidized, stability and good dispersion; Can keep long cohesive; Add adhesion promoter, improved the compatibility between each component, there will not be layering after adhesive is long placed in, and improved to a great extent the adhesive force of glue to Recombinant Wood to be bonded; Thereby can resist extraneous moisture or humidity compared with the shortcoming of glue performance variation in overall situation; And this environment-friendly type glue is preserved without low temperature, store and convenient transportation;
4. the required Nano Silver of Nano Silver decoration veneer that is prepared into preparation antimildew and antibacterial by specific method, nano-Ag particles is more even, stable good with dispersive property, has further improved the stability of the Nano Silver decoration veneer of final required antimildew and antibacterial.
As preferably, the mass content of described dispersant in solution is 1-3%; The content of described the first reducing agent in solution is 0.2-0.4%.
As preferably, described emulsifying agent is several in OPEO, sulfonated castor oil, lauryl sodium sulfate, neopelex.
As preferably, described in to contain alkali-metal the second reducing agent be one or more in sodium borohydride, potassium borohydride, sodium metaphosphate or natrium citricum.
As preferably, the processing method of described fancy veneer is: base material is sent in the vacuum tank that contains nano-silver water solution, be evacuated to vacuum for-0.05MPa～-0.01MPa and keep 15-20min; Then the processing of exerting pressure, applies pressure to 0.2-0.5MPa and keeps 18-28min; Finally carry out microwave treatment, microwave frequency is 400MHz～650MHz, and microwave treatment time is 1～3min, then takes out post processing.
More preferred, described post processing is dry or hot pressing; Described hot pressing pressure is 0.5-1.4MPa, and hot pressing time is 1-5min.
As preferably, described step (2) adds crown ether and contains before alkali-metal the second reducing agent in described mixed liquor, and described mixed liquor is heated to 45-55 ℃; Described step (2) is heated to 70-85 ℃ after adding crown ether in described mixed liquor and containing alkali-metal the second reducing agent, continues to stir 5-8min.
First heating adds crown ether again and contains alkali-metal the second reducing agent, can increase the reactivity of reduction anion that dissociate or exposed in reaction system, promote that alkali metal reacts with crown ether generation ligand complex, further pull open the distance between positive and negative charge in Nano Silver system, make Nano Silver can stable dispersion in the aqueous solution, be difficult for reuniting;
After adding crown ether in described mixed liquor and containing alkali-metal the second reducing agent, continue heating, can further increase the reactivity of reduction anion that dissociate or exposed in reaction system, promote that alkali metal reacts with crown ether generation ligand complex, further pull open the distance between positive and negative charge in Nano Silver system, make Nano Silver can stable dispersion in the aqueous solution, be difficult for reuniting.
As preferably, described step (2) is carried out under microwave vacuum condition, is specifically evacuated to vacuum for-0.02MPa～-0.001MPa, then carries out microwave treatment, and microwave frequency is 100MHz～230MHz, and microwave treatment time is 3～7s.
Adopt microwave to react and can greatly accelerate reaction rate, Reaction time shorten, further improves the stability of nano-silver water solution.
As preferably, described Nano Silver preparation also comprises step (3) ultrafiltration desalination and dry.
Ultrafiltration, except the inorganic salts or the organic salt that generate in dereaction, finally obtains the Nano Silver that particle size range is 20-60nm.
As preferably, described crown ether be bicyclohexane also-18-hat-6.
As preferably, the concrete grammar that fancy veneer and base material cohere is: fancy veneer and base material are cohered by the adhesive that contains Nano Silver, and the glue-spread of the described adhesive containing Nano Silver is 80-150g/m
2; Then send in vacuum tank, be evacuated to vacuum for-0.05MPa～-0.01MPa and keep 15-20min; Then the processing of exerting pressure, applies pressure to 0.2-0.5MPa and keeps 18-28min; Then carry out microwave treatment, microwave frequency is 400MHz～650MHz, and microwave treatment time is 1～3min; Finally take out and cold pressing and hot pressing.
Cold pressing again and hot pressing by continuous vacuumizing, after pressurization, microwave treatment, Nano Silver is effectively infiltrated in Recombinant Wood, fully resist because of the invasion and attack of moisture-induced mould to Recombinant Wood; Further strengthen the adhesive force of adhesive to Recombinant Wood, improve gluing performance.
In sum, the present invention has following beneficial effect: nano-silver water solution stability of the present invention and good dispersion; Can make Nano Silver more effectively infiltrate in Recombinant Wood decoration veneer, fully resist because of the invasion and attack of moisture-induced mould to Recombinant Wood.
The specific embodiment
embodiment mono-
The preparation of Nano Silver:
Sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate salting liquid are added in silver nitrate aqueous solution and obtain mixed liquor, and the mol ratio of dodecyl sodium sulfate and silver nitrate is 2:1; The mol ratio of polyoxyethylene alkyl ether sulfate salt and silver nitrate is 2:5;
Mixed liquor is heated to 45 ℃, under stirring to add in mixed liquor bicyclohexane also-18-hat-6 and sodium borohydride, be heated to 70 ℃, continue to stir 5min; Bicyclohexane also-18-hat-6 is 1:1 with the mol ratio of silver nitrate; The mol ratio of sodium borohydride and silver nitrate is 0.5:1, and controlling pH value is 8, obtains Nano Silver.
The preparation of nano-silver water solution:
Take deionized water as solvent, dissolve in deionized water take Nano Silver as solute, take acrylic resin as complexing agent with stabilizing agent adds dispersant after dissolving in deionized water and the first reducing agent forms solution simultaneously;
Dispersant is triethanolamine, and the mass content in solution is 1%; The first reducing agent is the hydrazine hydrate aqueous solution; Content in solution is 0.2%;
The concentration of Nano Silver is 50ppm, and the mass content of acrylic resin in solution is 1%.
The preparation of the adhesive that contains inorganic nano-silver:
Nano Silver is evenly applied in environment-friendly type glue solution to the additive using flour as glue; The concentration of Nano Silver in adhesive is 75ppm; The mass content of flour in solution is 18%;
Environment-friendly type glue comprises that the solids content of 40 parts of weight is 40% chlorinated polypropylene or polyolefin substrate adhesion promoter for the solids content of emulsion acrylic resin, the acrylic resin powder of 20 parts of weight, 5 parts of weight be 40% EVA emulsion, 1 part of dibutyl phthalate and 7 parts of weight;
Emulsion acrylic resin is synthetic as monomer and OPEO emulsifying agent, ammonium persulfate initiator, sodium acid carbonate and deionized water by methyl methacrylate and acrylamide.
Using method by nano-silver water solution and the adhesive that contains inorganic nano-silver for the preparation of decoration veneer:
1. decorate veneer and the base material of Recombinant Wood material with nano aqueous solution dipping; Concrete dipping method is:
Veneer and base material are sent in the vacuum tank that contains nano-silver water solution, be evacuated to vacuum for-0.05MPaMPa and keep 15min; Then the processing of exerting pressure, applies pressure to 0.2MPa and keeps 18min; Finally carry out microwave treatment, microwave frequency is 300MHz, and microwave treatment time is 1min, then takes out dry;
2. adopt veneer and the base material after the bonding dipping of adhesive that contains nano-silver substances,
The concrete grammar that fancy veneer and base material cohere is: fancy veneer and base material are cohered by the adhesive that contains Nano Silver, then send in vacuum tank, be evacuated to vacuum for-0.05MPa and keep 15min; Then the processing of exerting pressure, applies pressure to 0.2MPa and keeps 18min; Then carry out microwave treatment, microwave frequency is 400MHz, and microwave treatment time is 1min; Finally take out and cold pressing and hot pressing; The pressure of colding pressing is 0.7MPa, and the time of colding pressing is 0.5h; Hot pressing pressure is 0.5MPa, and hot pressing time is 1min.The glue-spread that wherein contains the adhesive of Nano Silver is 80g/m
2.
The decoration veneer that the present embodiment obtains reaches the highest 0 grade of JISZ 2911 standards after testing, decorates popularity bacillus in room, food Trichoderma, stain fungus etc. and has stronger killing action.
embodiment bis-
The preparation of Nano Silver:
Sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate sodium solution are added in silver nitrate aqueous solution and obtain mixed liquor, and the mol ratio of dodecyl sodium sulfate and silver nitrate is 3:1; The mol ratio of polyoxyethylene alkyl ether sulfate salt and silver nitrate is 3:5;
Mixed liquor is heated to 55 ℃, under stirring to add in mixed liquor bicyclohexane also-18-hat-6 and potassium borohydride, be heated to 85 ℃, continue to stir 8min; Bicyclohexane also-18-hat-6 is 1-2:1 with the mol ratio of silver nitrate; The mol ratio of potassium borohydride and silver nitrate is 0.5-1:1, and controlling pH value is 8-9, obtains Nano Silver.
The preparation of nano-silver water solution:
Take deionized water as solvent, dissolve in deionized water take Nano Silver as solute, take acrylic resin as complexing agent with stabilizing agent adds dispersant after dissolving in deionized water and reducing agent forms solution simultaneously;
Dispersant is triethanolamine, and the mass content in solution is 1-3%; The first reducing agent is the hydrazine hydrate aqueous solution; Content in solution is 0.2-0.4%;
The concentration of Nano Silver is 50-150ppm, and the mass content of acrylic resin in solution is 1-10%.
The preparation of the adhesive that contains Nano Silver:
Nano Silver is evenly applied in environment-friendly type glue solution to the additive using flour as glue; The concentration of Nano Silver in adhesive is 150ppm; The mass content of flour in solution is 45%;
Environment-friendly type glue comprises that the solids content of 80 parts of weight is 55% chlorinated polypropylene or polyolefin substrate adhesion promoter for the solids content of emulsion acrylic resin, the acrylic resin powder of 40 parts of weight, 20 parts of weight be 60% EVA emulsion, 4 parts of dibutyl phthalates and 13 parts of weight;
Emulsion acrylic resin is synthetic as monomer and sulfonated castor oil emulsifying agent, ammonium persulfate initiator, sodium acid carbonate and deionized water by dodecylacrylate, acrylic acid stearyl and Methacrylamide, styrene.
Using method by nano-silver water solution and the adhesive that contains inorganic nano-silver for the preparation of decoration veneer:
1. decorate veneer and the base material of Recombinant Wood material with nano aqueous solution dipping; Concrete dipping method is: veneer and base material are sent in the vacuum tank that contains nano-silver water solution, be evacuated to vacuum for-0.05MPa～-0.01MPa and keep 15-20min; Then the processing of exerting pressure, applies pressure to 0.2-0.5MPa and keeps 18-28min; Finally carry out microwave treatment, microwave frequency is 300MHz～950MHz, and microwave treatment time is 1～3min, then takes out dry;
Veneer and base material after the bonding dipping of adhesive that employing contains nano-silver substances, the concrete grammar that fancy veneer and base material cohere is: fancy veneer and base material are cohered by the adhesive that contains Nano Silver, then send in vacuum tank, be evacuated to vacuum for-0.01MPa and keep 20min; Then the processing of exerting pressure, applies pressure to 0.5MPa and keeps 28min; Then carry out microwave treatment, microwave frequency is 650MHz, and microwave treatment time is 3min; Finally take out and cold pressing and hot pressing; The pressure of colding pressing is 0.6MPa, and the time of colding pressing is 3h; Hot pressing pressure is 1.4MPa, and hot pressing time is 5min.The glue-spread that wherein contains the adhesive of Nano Silver is 150g/m
2;
The decoration veneer that the present embodiment obtains reaches the highest 0 grade of JISZ 2911 standards after testing, decorates popularity bacillus in room, food Trichoderma, stain fungus etc. and has stronger killing action.
embodiment tri-
The preparation of Nano Silver:
Sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate sodium solution are added in silver nitrate aqueous solution and obtain mixed liquor, and the mol ratio of dodecyl sodium sulfate and silver nitrate is 2.5:1; The mol ratio of polyoxyethylene alkyl ether sulfate salt and silver nitrate is 1:2;
Mixed liquor is heated to 50 ℃, under stirring to add in mixed liquor bicyclohexane also-18-hat-6 and sodium metaphosphate, be heated to 75 ℃, continue to stir 6min; Bicyclohexane also-18-hat-6 is 1.5:1 with the mol ratio of silver nitrate; The mol ratio of sodium metaphosphate and silver nitrate is 0.8:1, and controlling pH value is 8.5, obtains Nano Silver.
The preparation of nano-silver water solution:
Take deionized water as solvent, dissolve in deionized water take Nano Silver as solute, take acrylic resin as complexing agent with stabilizing agent adds dispersant after dissolving in deionized water and reducing agent forms solution simultaneously;
Dispersant is triethanolamine, and the mass content in solution is 2%; The first reducing agent is the hydrazine hydrate aqueous solution; Content in solution is 0.3%;
The concentration of Nano Silver is 100ppm, and the mass content of acrylic resin in solution is 8%.
The preparation of the adhesive that contains inorganic nano-silver:
Nano Silver is evenly applied in environment-friendly type glue solution to the additive using flour as glue; The concentration of Nano Silver in adhesive is 100ppm; The mass content of flour in solution is 25%;
Environment-friendly type glue comprises that the solids content of 60 parts of weight is 45% chlorinated polypropylene or polyolefin substrate adhesion promoter for the solids content of emulsion acrylic resin, the acrylic resin powder of 30 parts of weight, 15 parts of weight be 50% EVA emulsion, 3 parts of dibutyl phthalates and 9 parts of weight;
Emulsion acrylic resin is synthesized as monomer and neopelex emulsifying agent, ammonium persulfate initiator, sodium acid carbonate and deionized water by butyl acrylate, isobutyl methacrylate and acrylic acid stearyl and acrylonitrile and Methacrylamide.
Using method by nano-silver water solution and the adhesive that contains inorganic nano-silver for the preparation of decoration veneer:
1. decorate veneer and the base material of Recombinant Wood material with nano aqueous solution dipping; Concrete dipping method is: Recombinant Wood is sent in the vacuum tank that contains nano-silver water solution, be evacuated to vacuum for-0.03MPa and keep 18min; Then the processing of exerting pressure, applies pressure to 0.3MPa and keeps 23min; Finally carry out microwave treatment, microwave frequency is 550MHz, and microwave treatment time is 2min, then takes out dry;
Veneer and base material after the bonding dipping of adhesive that employing contains nano-silver substances, the concrete grammar that fancy veneer and base material cohere is: fancy veneer and base material are cohered by the adhesive that contains Nano Silver, then send in vacuum tank, be evacuated to vacuum for-0.04MPa and keep 18min; Then the processing of exerting pressure, applies pressure to 0.3MPa and keeps 22min; Then carry out microwave treatment, microwave frequency is 550MHz, and microwave treatment time is 2min; Finally take out and cold pressing and hot pressing; The pressure of colding pressing is 0.8MPa, and the time of colding pressing is 1.5h; Hot pressing pressure is 1MPa, and hot pressing time is 4min.The glue-spread that wherein contains the adhesive of Nano Silver is 110g/m
2.
The decoration veneer that the present embodiment obtains reaches the highest 0 grade of JISZ 2911 standards after testing, decorates popularity bacillus in room, food Trichoderma, stain fungus etc. and has stronger killing action.
embodiment tetra-
The preparation of Nano Silver:
Sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate sodium solution are added in silver nitrate aqueous solution and obtain mixed liquor, and the mol ratio of dodecyl sodium sulfate and silver nitrate is 2:1; The mol ratio of polyoxyethylene alkyl ether sulfate salt and silver nitrate is 2:5;
To add in mixed liquor bicyclohexane also-18-hat-6 and natrium citricum, bicyclohexane also-18-hat-6 is 1:1 with the mol ratio of silver nitrate; The mol ratio of natrium citricum and silver nitrate is 0.5:1, controlling pH value is 8, put into microwave vacuum tank processes under microwave vacuum condition, specifically being evacuated to vacuum is-0.02MPa, carry out microwave treatment, microwave frequency is 100MHz again, and microwave treatment time is 3s, then ultrafiltration desalination dry, finally obtains the Nano Silver that particle size range is 20-60nm.
The preparation of nano-silver water solution and adhesive and using method thereof are with embodiment mono-, and different is that emulsion acrylic resin is synthetic as monomer and lauryl sodium sulfate emulsifying agent, ammonium persulfate initiator, sodium acid carbonate and deionized water by butyl methacrylate and acrylamide.
embodiment five
The preparation of Nano Silver:
Sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate sodium solution are added in silver nitrate aqueous solution and obtain mixed liquor, and the mol ratio of dodecyl sodium sulfate and silver nitrate is 3:1; The mol ratio of polyoxyethylene alkyl ether sulfate salt and silver nitrate is 3:5;
To add in mixed liquor bicyclohexane also-18-hat-6 and 1:1 combines in molar ratio sodium borohydride and potassium borohydride, bicyclohexane also-mol ratio of 18-hat-6 and silver nitrate is 1-2:1; The mol ratio of sodium borohydride and potassium borohydride and silver nitrate is 1:1, controlling pH value is 9, put into microwave vacuum tank processes under microwave vacuum condition, specifically being evacuated to vacuum is-0.001MPa, carry out microwave treatment, microwave frequency is 230MHz again, and microwave treatment time is 7s, then ultrafiltration desalination dry, finally obtains the Nano Silver that particle size range is 20-60nm.
The preparation of nano-silver water solution and adhesive and using method thereof are with embodiment bis-.
embodiment six
The preparation of Nano Silver:
Sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate sodium solution are added in silver nitrate aqueous solution and obtain mixed liquor, and the mol ratio of dodecyl sodium sulfate and silver nitrate is 2.5:1; The mol ratio of polyoxyethylene alkyl ether sulfate salt and silver nitrate is 1:2;
To add in mixed liquor bicyclohexane also-18-hat-6 and 1:1 combines in molar ratio potassium borohydride and sodium metaphosphate, bicyclohexane also-mol ratio of 18-hat-6 and silver nitrate is 1.5:1; The mol ratio of potassium borohydride and sodium metaphosphate and silver nitrate is 0.8:1, controlling pH value is 8.5, put into microwave vacuum tank processes under microwave vacuum condition, specifically being evacuated to vacuum is-0.01MPa, carry out microwave treatment, microwave frequency is 130MHz again, and microwave treatment time is 5s, then ultrafiltration desalination dry, finally obtains the Nano Silver that particle size range is 20-60nm.
The preparation of nano-silver water solution and using method thereof are with embodiment tri-.
comparing embodiment one
The preparation of Nano Silver:
Sodium dodecyl sulfate solution is added in silver nitrate aqueous solution and obtains mixed liquor, and the mol ratio of dodecyl sodium sulfate and silver nitrate is 1:1;
Under stirring, in mixed liquor, add sodium borohydride, continue to stir 5min; The mol ratio of sodium borohydride and silver nitrate is 2:1, and controlling pH value is 10, obtains Nano Silver.
The preparation of nano-silver water solution:
Take water as solvent, dissolve in water take Nano Silver as solute, take acrylic resin as complexing agent and stabilizing agent add dispersant triethanolamine after dissolving in water simultaneously and form solution;
The mass content of triethanolamine in solution is 1%; Content in solution is 0.2%;
The concentration of Nano Silver is 40ppm, and the mass content of acrylic resin in solution is 0.5%.
Embodiment 1-6 and comparative example are left standstill, the dispersity of observing respectively the Nano Silver of nano-silver water solution system after 1 month and 6 months, observed result is in table 1.
The dispersity of Nano Silver in table 1 nano-silver water solution system
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art are reading after this description and can make to the present embodiment the modification that there is no creative contribution as required, but as long as within the scope of claim of the present invention, are all subject to the protection of Patent Law.
Claims (10)
1. a Nano Silver decoration veneer for antimildew and antibacterial, is cohered and forms through adhesive layer by fancy veneer and base material, it is characterized in that:
Described fancy veneer and base material form through nano aqueous solution dipping, and described adhesive layer contains nano-silver substances; Described fancy veneer and base material are Recombinant Wood;
Described nano-silver water solution is take deionized water as solvent, dissolves in deionized water, take acrylic resin as complexing agent, stabilizing agent adds dispersant and the first reducing agent and form solution after dissolving in deionized water simultaneously take Nano Silver as solute;
Described dispersant is triethanolamine, and described the first reducing agent is the hydrazine hydrate aqueous solution;
The concentration of described Nano Silver is 50-150ppm, and the mass content of described acrylic resin in solution is 1-10%;
Described Nano Silver is prepared from according to following steps:
(1) sodium dodecyl sulfate solution and polyoxyethylene alkyl ether sulfate salting liquid are added in silver nitrate aqueous solution and obtain mixed liquor, the mol ratio of described dodecyl sodium sulfate and silver nitrate is 2-3:1; The mol ratio of described polyoxyethylene alkyl ether sulfate salt and silver nitrate is 0.4-0.6:1;
(2) in described mixed liquor, add crown ether and contain alkali-metal the second reducing agent, the mol ratio of described crown ether and silver nitrate is 1-2:1; The described mol ratio that contains alkali-metal reducing agent and silver nitrate is 0.5-1:1, and controlling pH value is 8-9, obtains Nano Silver;
The described adhesive that contains inorganic nano-silver is for to be evenly applied to Nano Silver in environment-friendly type glue solution, the additive using flour as glue;
The concentration of described Nano Silver in adhesive is 75-150ppm; The mass content of described flour in solution is 18-45%;
Described environment-friendly type glue comprises that the solids content of 40-80 part weight is that 40-55% is chlorinated polypropylene or the polyolefin substrate adhesion promoter of the solids content of acrylic resin powder, 5-20 part weight of emulsion acrylic resin, 20-40 part weight be 40-60% EVA emulsion, 1-4 part dibutyl phthalate and 7-13 part weight;
Described emulsion acrylic resin is synthetic as monomer and emulsifying agent, ammonium persulfate initiator, sodium acid carbonate and deionized water by any one or a few in any one or a few and methacrylic acid in methyl methacrylate, EMA, butyl methacrylate, butyl acrylate, isobutyl methacrylate, dodecylacrylate, acrylic acid stearyl, acrylic acid, acrylamide, acrylonitrile, Methacrylamide, styrene.
2. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 1, it is characterized in that: the processing method of described fancy veneer is: base material is sent in the vacuum tank that contains nano-silver water solution, be evacuated to vacuum for-0.05MPa～-0.01MPa and keep 15-20min; Then the processing of exerting pressure, applies pressure to 0.2-0.5MPa and keeps 18-28min; Finally carry out microwave treatment, microwave frequency is 400MHz～650MHz, and microwave treatment time is 1～3min, then takes out post processing.
3. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 1, it is characterized in that: the concrete grammar that fancy veneer and base material cohere is: fancy veneer and base material are cohered by the adhesive that contains Nano Silver, and the glue-spread of the described adhesive containing Nano Silver is 80-150g/m
2, then send in vacuum tank, be evacuated to vacuum for-0.05MPa～-0.01MPa and keep 15-20min; Then the processing of exerting pressure, applies pressure to 0.2-0.5MPa and keeps 18-28min; Then carry out microwave treatment, microwave frequency is 400MHz～650MHz, and microwave treatment time is 1～3min; Finally take out and cold pressing and hot pressing.
4. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 1, is characterized in that: the mass content of described dispersant in solution is 1-3%; The content of described the first reducing agent in solution is 0.2-0.4%; It is described that to contain alkali-metal the second reducing agent be one or more in sodium borohydride, potassium borohydride, sodium metaphosphate or natrium citricum.
5. according to the Nano Silver decoration veneer of a kind of antimildew and antibacterial described in claim 1-4 any one, it is characterized in that: described emulsifying agent is several in OPEO, sulfonated castor oil, lauryl sodium sulfate, neopelex.
6. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 5, is characterized in that: described step (2) adds crown ether and contains before alkali-metal the second reducing agent in described mixed liquor, and described mixed liquor is heated to 45-55 ℃; Described step (2) is heated to 70-85 ℃ after adding crown ether in described mixed liquor and containing alkali-metal the second reducing agent, continues to stir 5-8min.
7. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 6, it is characterized in that: described step (2) is carried out under microwave vacuum condition, specifically being evacuated to vacuum is-0.02MPa～-0.001MPa, carry out again microwave treatment, microwave frequency is 100MHz～230MHz, and microwave treatment time is 3～7s.
8. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 7, is characterized in that: described crown ether be bicyclohexane also-18-hat-6.
9. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 8, is characterized in that: described Nano Silver preparation also comprises step (3) ultrafiltration desalination and dry.
10. the Nano Silver decoration veneer of a kind of antimildew and antibacterial according to claim 9, for the using method of Recombinant Wood, is characterized in that: described post processing is dry or hot pressing; Described hot pressing pressure is 0.5-1.4MPa, and hot pressing time is 1-5min.
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