CN110670387A - Carbon-coated silver microspheres and preparation method thereof, black pigment printing paste and application thereof - Google Patents
Carbon-coated silver microspheres and preparation method thereof, black pigment printing paste and application thereof Download PDFInfo
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- CN110670387A CN110670387A CN201910981819.3A CN201910981819A CN110670387A CN 110670387 A CN110670387 A CN 110670387A CN 201910981819 A CN201910981819 A CN 201910981819A CN 110670387 A CN110670387 A CN 110670387A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/445—Use of auxiliary substances before, during or after dyeing or printing
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5221—Polymers of unsaturated hydrocarbons, e.g. polystyrene polyalkylene
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67383—Inorganic compounds containing silicon
Abstract
The invention belongs to the technical field of fabric printing and dyeing, and particularly discloses a core-shell structure carbon-coated silver microsphere and a preparation method thereof, and black pigment printing paste and application thereof. The particle size of the core-shell structure carbon-coated silver microsphere is 50-200nm, wherein the particle size of the silver particle is 10-40nm, the thickness of the carbon shell layer is 20-90nm, the preparation method comprises the steps of preparing the silver particle, preparing the modified silicon dioxide-coated silver particle microsphere, preparing the silver @ silicon dioxide @ polystyrene particle and preparing the core-shell structure carbon-coated silver microsphere, and the prepared silver microsphere is stable in structure and has a good antibacterial effect. The invention also provides printing paste containing the silver microspheres and application thereof.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of fabric printing and dyeing, in particular to a core-shell structure carbon-coated silver microsphere and a preparation method thereof, and black pigment printing paste and application thereof.
[ background of the invention ]
Pigment printing is a printing process which utilizes an adhesive to adhere color paste paint on fabrics to endow the fabrics with various patterns. With the improvement of the quality of social life, people put forward new requirements on the quality of printed products, namely the printed products are required to have antibacterial performance, and bacterial infection can be reduced to a certain extent. However, the traditional printing paste does not usually contain an antibacterial agent, for example, the printing paste composition and the paste used in the dyeing and coating integrated dye dyeing and printing paste composition of the chinese patent application CN 105970671A do not have antibacterial performance, while the printing paste with antibacterial function at present usually directly uses inorganic metal or chitosan and other organic molecules as the antibacterial agent, but the antibacterial agent has the disadvantages of easy agglomeration and poor stability, for example, the antibacterial textile dye of the chinese patent application CN 109505164A and the antibacterial textile dye of the chinese patent application CN 108071024A both directly use nano silver and/or nano titanium dioxide as the antibacterial agent, and the stability of the used antibacterial agent is poor.
However, there have been some studies on the problems of the above antibacterial agents, and although the problems of easy aggregation and poor stability of the above antibacterial agents are solved, the antibacterial effect is poor. For example, Gong-Yan-Bo, Dajin, etc. research on the preparation and antibacterial properties of Ag-carrying carbon microsphere antibacterial agent [ J ] novel chemical material 2016(4):97-99, provides a method for preparing Ag-carrying carbon microsphere (Ag/CMSs) antibacterial agent by reduction adsorption using carbon microsphere as carrier, but the antibacterial diameter of the antibacterial agent to colibacillus is only 21mm, and the antibacterial effect is not good.
[ summary of the invention ]
The invention aims to: aiming at the existing problems, the core-shell structure carbon-coated silver microspheres are provided as an antibacterial agent, the antibacterial agent has the characteristics of stable structure, difficult agglomeration and good antibacterial effect, and the black coating printing color paste containing the core-shell structure carbon-coated silver microspheres is used for the fabric, so that the antibacterial agent has the characteristics of good film forming property, high fastness and difficult color change, and the treated fabric has the advantages of soft hand feeling, high abrasion resistance and washing fastness, water resistance, good color paste stability and good antibacterial effect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the carbon-coated silver microsphere with the core-shell structure has the particle size of 50-200nm, wherein the particle size of silver particles is 10-40nm, and the thickness of a carbon shell layer is 20-90 nm.
A preparation method of a core-shell structure carbon-coated silver microsphere comprises the following steps:
(1) preparation of silver particles: mixing and stirring 0.01-1g of trisodium citrate and 1-100mL of deionized water until the trisodium citrate is completely dissolved to obtain a trisodium citrate solution; adding 0.01-2g of silver nitrate and 50-800mL of deionized water into the trisodium citrate solution, heating at 100 ℃ for 20-30min, then adding 1-20mL of aqueous solution with trisodium citrate content of 1%, stirring for 20-30min, stopping heating, continuing stirring for 1-1.5, and then centrifuging at 800-; washing a product obtained by centrifugation, and then dispersing the product in 1-20mL of absolute ethyl alcohol to obtain a silver particle mixture;
(2) preparing modified silicon dioxide coated silver particle microspheres: adding 10-160mL of deionized water and 30-500mL of absolute ethanol into the silver particle mixture, adding 0.2-6.5mL of 30% ammonia water under the protection of nitrogen, stirring uniformly, slowly adding 2.5-40mL of ethyl orthosilicate ethanol solution, and reacting for 13-15 h; then slowly dripping 5-10g of gamma-methacryloxypropyltrimethoxysilane at room temperature, and standing for 2-3 days to obtain a mixed product; finally, sequentially centrifuging, washing and cleaning the mixed product to obtain modified silicon dioxide coated silver particle particles;
(3) preparation of silver @ silica @ polystyrene microparticles: mixing the silver particle particles coated with the modified silicon dioxide, 7-120mL of water, 0.0003-0.012g of sodium dodecyl benzene sulfonate and 0.002-0.1g of sodium bicarbonate, and stirring uniformly to obtain a modified mixture; under the protection of nitrogen, heating the modified mixture to 52 ℃, adding 0.27-1.1mL of styrene and 0.003-0.12mL of divinylbenzene when the modified mixture is in an emulsion state, then continuing to heat to 70 ℃, adding 0.001-0.04g of potassium sulfate, and continuing to react for 0.5-1 h; finally, the obtained mixture is dried after being centrifuged, washed by water and washed by ethanol, and the silver @ silicon dioxide @ polystyrene particles are obtained;
(4) preparing the core-shell structure carbon-coated silver microspheres: swelling the silver @ silicon dioxide @ polystyrene particles in 1-20mL of anhydrous carbon tetrachloride for 12-14 h; adding the swelled silver @ silicon dioxide @ polystyrene particles into a reactor, adding 0.014-0.6g of aluminum sulfate initiator into the reactor, reacting for 1d at 72-74 ℃, finally adding acetone and dilute hydrochloric acid to stop the reaction, and filtering, washing and drying the obtained reactant to obtain non-carbonized microspheres; heating the obtained non-carbonized microspheres at the speed of 5 ℃/min in the nitrogen atmosphere, sequentially keeping the temperature at 400 ℃, 600 ℃ and 850 ℃ for 3 hours respectively, then cooling to 400 ℃ at the cooling speed of 2 ℃/min, and naturally cooling to obtain carbonized microspheres; and adding the carbonized microspheres into 1-35mL of ethanol and 1-40mL of hydrofluoric acid, uniformly stirring, and finally, centrifuging, washing with water, washing with ethanol, and drying to obtain the core-shell structure carbon-coated silver microspheres.
Further, the volume ratio of the ethyl orthosilicate to the ethanol in the ethyl orthosilicate ethanol solution is 1: 5.
Further, the core-shell structure carbon-coated silver microspheres take single silver particles or a plurality of silver particles as cores.
The invention also provides a black pigment printing paste containing the core-shell structure carbon-coated silver microspheres.
Further, the black pigment printing paste comprises the following raw material components in parts by weight: 0.01-2 parts of core-shell structure carbon-coated silver microspheres, 2.5-15 parts of carbon black, 0.5-3 parts of red pigment, 0.5-3 parts of yellow pigment, 0.5-3 parts of blue pigment, 0.01-100 parts of waterborne polyurethane emulsion, 0.01-100 parts of waterborne acrylic resin and 10-50 parts of water.
Further, the weight ratio of the carbon black, the red pigment, the yellow pigment and the blue pigment is 5:1:1: 1.
Further, the water-based acrylic resin is an emulsion formed by a copolymer obtained by polymerizing methyl acrylate, ethyl acrylate, butyl acrylate and hydroxypropyl acrylate, and the mass ratio of the methyl acrylate, the ethyl acrylate, the butyl acrylate and the hydroxypropyl acrylate is 2:2:3: 3.
Further, the preparation method of the black pigment printing paste comprises the following steps: and adding the weighed aqueous polyurethane emulsion into a container, then sequentially adding the weighed aqueous acrylic resin, carbon black, red pigment, yellow pigment, blue pigment, carbon-coated silver microspheres, water and thickening agent, and fully stirring to obtain the black pigment printing paste.
The invention also provides application of the black pigment printing paste to fabrics.
Further, the fabric is a synthetic fiber fabric or a cellulose fabric.
Further, the synthetic fiber fabric is terylene, chinlon, acrylic fiber or spandex; the cellulose fabric is cotton, hemp or modal.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) compared with the core-shell structure carbon-coated silver microspheres prepared by the existing method, the core-shell structure carbon-coated silver microspheres are prepared by a stepwise synthesis method, the antibacterial performance of the core-shell structure carbon-coated silver microspheres is effectively improved by controlling the raw materials and the raw material consumption in the preparation process and the relevant parameters in each reaction process, the antibacterial rate is more than 99 percent, the properties are stable, and the prepared carbon-coated silver microspheres cannot agglomerate and have good dispersibility when applied to color paste. The modified silica silver particle microspheres can improve the K/S value of printing paste by over 6.86 percent and have strong tinting strength and hiding power compared with the unmodified silica silver particle microspheres.
(2) The grain diameter of the core-shell structure carbon-coated silver microspheres is controlled to be 50-200nm, and the color paste is best in scrubbing resistance fastness and color fixing rate when being used on fabrics in the grain diameter range, wherein after the scrubbing resistance fastness of the fabrics containing the core-shell structure carbon-coated silver microspheres of 50-200nm is measured to reach 4-5 levels by professionals according to GB/T3920-1997 standards and GB/T2391-2014 standards, and the color fixing rate reaches 64.22%. When the particle size of the carbon-coated silver microspheres with the core-shell structure is less than 50nm, although the adhesion force on the surface of the fabric is strong and the scrubbing fastness is better (3-4 level) due to small particle size, the color fixing rate of the fabric is reduced to below 51.06%; when the particle size of the silver microspheres is larger than 200nm, the adhesion force on the surface of the fabric is strong because of the large particle size, so that the brushing fastness is poor and is only 2-3 grades, and the color fixing rate of the fabric is reduced to a certain extent and is reduced by more than 5.6%.
(3) The black pigment printing paste disclosed by the invention is prepared by matching and mixing the components, so that the film forming property is good, the fastness is high, the color is not easy to change after the black pigment printing paste is used, and the treated fabric is soft in hand feeling, high in abrasion resistance and washing fastness, water-resistant, good in paste stability and good in antibacterial effect. Wherein the weight ratio of the carbon black, the red pigment, the yellow pigment and the blue pigment is controlled to be 5:1:1:1, so that the fabric has high color saturation, wherein the saturation C value of the color of the printed fabric is up to 43.18 when the fabric is tested according to the testing method disclosed in the prior art. When the weight ratio of the carbon black, the red pigment, the yellow pigment and the blue pigment is outside the weight ratio, although the lightness L value and the hue H value of the obtained printed fabric do not change much, the saturation C value is obviously reduced, and is reduced by at least 8.74 percent.
[ description of the drawings ]
FIG. 1 is an SEM image of silver @ silica @ polystyrene microparticles of the present invention.
Fig. 2 is a schematic structural diagram of a core-shell structure carbon-coated silver microsphere of the present invention.
[ detailed description ] embodiments
The invention will now be further described with reference to specific examples.
Example 1
The carbon-coated silver microsphere with the core-shell structure has the particle size of 50nm, wherein the particle size of silver particles is 10nm, and the thickness of a carbon shell layer is 20 nm.
The preparation method of the core-shell structure carbon-coated silver microsphere comprises the following steps:
(1) preparation of silver particles: mixing and stirring 0.01g of trisodium citrate and 1mL of deionized water until the trisodium citrate is completely dissolved to obtain a trisodium citrate solution; adding 0.01g of silver nitrate and 50mL of deionized water into the trisodium citrate solution, heating at 100 ℃ for 20min, then adding 1mL of aqueous solution with trisodium citrate content of 1%, stirring for 20min, stopping heating, continuing stirring for 1, and centrifuging at 800 r/min; washing a product obtained by centrifugation, and then dispersing the product in 1mL of absolute ethyl alcohol to obtain a silver particle mixture;
(2) preparing modified silicon dioxide coated silver particle microspheres: adding 10mL of deionized water and 30mL of absolute ethanol into the silver particle mixture, adding 0.2mL of ammonia water with the concentration of 30% under the protection of nitrogen, stirring uniformly, slowly adding 2.5mL of ethyl orthosilicate ethanol solution (the volume ratio of ethyl orthosilicate to ethanol in the ethyl orthosilicate ethanol solution is 1:5), and reacting for 13 h; then slowly dripping 5g of gamma-methacryloxypropyltrimethoxysilane at room temperature, and standing for 2 days to obtain a mixed product; finally, sequentially centrifuging, washing and cleaning the mixed product to obtain modified silicon dioxide coated silver particle particles;
(3) preparation of silver @ silica @ polystyrene microparticles: mixing and stirring the modified silicon dioxide coated silver particle particles, 7mL of water, 0.0003g of sodium dodecyl benzene sulfonate and 0.002g of sodium bicarbonate until the mixture is uniform to obtain a modified mixture; under the protection of nitrogen, heating the modified mixture to 52 ℃, adding 0.27mL of styrene and 0.003mL of divinylbenzene when the modified mixture is in an emulsion state, then continuously heating to 70 ℃, adding 0.001g of potassium sulfate, and continuously reacting for 0.5 h; finally, the obtained mixture is dried after being centrifuged, washed by water and washed by ethanol, and the silver @ silicon dioxide @ polystyrene particles are obtained;
(4) preparing the core-shell structure carbon-coated silver microspheres: swelling the silver @ silicon dioxide @ polystyrene particles in 1mL of anhydrous carbon tetrachloride for 12 h; adding the swelled silver @ silicon dioxide @ polystyrene particles into a reactor, adding 0.014g of aluminum sulfate initiator into the reactor, reacting for 1d at 72 ℃, finally adding acetone and dilute hydrochloric acid to stop the reaction, and filtering, washing and drying the obtained reactant to obtain the non-carbonized microspheres; heating the obtained non-carbonized microspheres at the speed of 5 ℃/min in the nitrogen atmosphere, sequentially keeping the temperature at 400 ℃, 600 ℃ and 850 ℃ for 3 hours respectively, then cooling to 400 ℃ at the cooling speed of 2 ℃/min, and naturally cooling to obtain carbonized microspheres; and adding the carbonized microspheres into 1mL of ethanol and 1mL of hydrofluoric acid, uniformly stirring, and finally, centrifuging, washing with water, washing with ethanol, and drying to obtain the core-shell structure carbon-coated silver microspheres taking single silver particles or multiple silver particles as cores.
The core-shell structure carbon-coated silver microsphere black coating printing paste comprises the following raw material components in parts by weight: 0.01 part of core-shell structure carbon-coated silver microspheres, 2.5 parts of carbon black, 0.5 part of red pigment, 0.5 part of yellow pigment, 0.5 part of blue pigment, 0.01 part of aqueous polyurethane emulsion, 0.01 part of aqueous acrylic resin and 10 parts of water; the water-based acrylic resin is an emulsion formed by a copolymer obtained by polymerizing methyl acrylate, ethyl acrylate, butyl acrylate and hydroxypropyl acrylate according to the mass ratio of 2:2:3: 3.
The preparation method of the black pigment printing paste comprises the following steps: and adding the weighed aqueous polyurethane emulsion into a container, then sequentially adding the weighed aqueous acrylic resin, carbon black, red pigment, yellow pigment, blue pigment, carbon-coated silver microspheres, water and thickening agent, and fully stirring to obtain the black pigment printing paste.
The method for applying the black pigment printing paste to the fabric comprises the following steps: pouring the black paint printing paste on a printing plate, adopting a blade coating mode to enable the black paint printing paste to permeate into the fabric, and then drying to form a film, thus obtaining the printed fabric.
Example 2
The carbon-coated silver microsphere with the core-shell structure has the particle size of 90nm, wherein the particle size of silver particles is 25nm, and the thickness of a carbon shell layer is 50 nm.
The preparation method of the core-shell structure carbon-coated silver microsphere comprises the following steps:
(1) preparation of silver particles: mixing and stirring 0.5g of trisodium citrate and 60mL of deionized water until the trisodium citrate is completely dissolved to obtain a trisodium citrate solution; adding 1.2g of silver nitrate and 450mL of deionized water into the trisodium citrate solution, heating at 100 ℃ for 25min, adding 15mL of aqueous solution with trisodium citrate content of 1%, stirring for 25min, stopping heating, continuing to stir for 1.2, and centrifuging at 900 r/min; washing a product obtained by centrifugation, and then dispersing the product into 13mL of absolute ethyl alcohol to obtain a silver particle mixture;
(2) preparing modified silicon dioxide coated silver particle microspheres: adding 110mL of deionized water and 380mL of absolute ethanol into the silver particle mixture, adding 3.5mL of 30% ammonia water under the protection of nitrogen, stirring uniformly, slowly adding 25mL of ethyl orthosilicate ethanol solution (the volume ratio of ethyl orthosilicate to ethanol in the ethyl orthosilicate ethanol solution is 1:5), and reacting for 14 h; then slowly dripping 8g of gamma-methacryloxypropyltrimethoxysilane at room temperature, and standing for 2.5 days to obtain a mixed product; finally, sequentially centrifuging, washing and cleaning the mixed product to obtain modified silicon dioxide coated silver particle particles;
(3) preparation of silver @ silica @ polystyrene microparticles: mixing and stirring the modified silicon dioxide coated silver particle particles, 100mL of water, 0.009g of sodium dodecyl benzene sulfonate and 0.08g of sodium bicarbonate to be uniform to obtain a modified mixture; under the protection of nitrogen, heating the modified mixture to 52 ℃, adding 0.58mL of styrene and 0.009mL of divinylbenzene when the modified mixture is in an emulsion state, then continuing to heat to 70 ℃, adding 0.01g of potassium sulfate, and continuing to react for 0.8 h; finally, the obtained mixture is dried after being centrifuged, washed by water and washed by ethanol, and the silver @ silicon dioxide @ polystyrene particles are obtained;
(4) preparing the core-shell structure carbon-coated silver microspheres: swelling the silver @ silicon dioxide @ polystyrene particles in 12mL of anhydrous carbon tetrachloride for 13 h; adding the swelled silver @ silicon dioxide @ polystyrene particles into a reactor, adding 0.2g of aluminum sulfate initiator into the reactor, reacting for 1d at 73 ℃, finally adding acetone and dilute hydrochloric acid to stop the reaction, and filtering, washing and drying the obtained reactant to obtain non-carbonized microspheres; heating the obtained non-carbonized microspheres at the speed of 5 ℃/min in the nitrogen atmosphere, sequentially keeping the temperature at 400 ℃, 600 ℃ and 850 ℃ for 3 hours respectively, then cooling to 400 ℃ at the cooling speed of 2 ℃/min, and naturally cooling to obtain carbonized microspheres; and adding the carbonized microspheres into 23mL of ethanol and 25mL of hydrofluoric acid, uniformly stirring, and finally, centrifuging, washing with water, washing with ethanol, and drying to obtain the core-shell structure carbon-coated silver microspheres taking single silver particles or multiple silver particles as cores.
The core-shell structure carbon-coated silver microsphere black coating printing paste comprises the following raw material components in parts by weight: 1 part of core-shell structure carbon-coated silver microspheres, 10 parts of carbon black, 2 parts of red pigment, 2 parts of yellow pigment, 2 parts of blue pigment, 55 parts of waterborne polyurethane emulsion, 55 parts of waterborne acrylic resin and 25 parts of water; the water-based acrylic resin is an emulsion formed by a copolymer obtained by polymerizing methyl acrylate, ethyl acrylate, butyl acrylate and hydroxypropyl acrylate according to the mass ratio of 2:2:3: 3.
The preparation method of the black pigment printing paste comprises the following steps: and adding the weighed aqueous polyurethane emulsion into a container, then sequentially adding the weighed aqueous acrylic resin, carbon black, red pigment, yellow pigment, blue pigment, carbon-coated silver microspheres, water and thickening agent, and fully stirring to obtain the black pigment printing paste.
The method for applying the black pigment printing paste to the fabric comprises the following steps: pouring the black paint printing paste on a printing plate, adopting a blade coating mode to enable the black paint printing paste to permeate into the fabric, and then drying to form a film, thus obtaining the printed fabric.
Example 3
The carbon-coated silver microsphere with the core-shell structure has the particle size of 200nm, wherein the particle size of silver particles is 40nm, and the thickness of a carbon shell layer is 90 nm.
The preparation method of the core-shell structure carbon-coated silver microsphere comprises the following steps:
(1) preparation of silver particles: mixing and stirring 1g of trisodium citrate and 100mL of deionized water until the trisodium citrate is completely dissolved to obtain a trisodium citrate solution; adding 2g of silver nitrate and 800mL of deionized water into the trisodium citrate solution, heating at 100 ℃ for 30min, adding 20mL of aqueous solution with trisodium citrate content of 1%, stirring for 30min, stopping heating, continuing to stir for 1.5, and centrifuging at 1000 r/min; washing a product obtained by centrifugation, and then dispersing the product in 20mL of absolute ethyl alcohol to obtain a silver particle mixture;
(2) preparing modified silicon dioxide coated silver particle microspheres: adding 160mL of deionized water and 500mL of absolute ethanol into the silver particle mixture, adding 6.5mL of ammonia water with the concentration of 30% under the protection of nitrogen, stirring uniformly, slowly adding 40mL of ethyl orthosilicate ethanol solution (the volume ratio of ethyl orthosilicate to ethanol in the ethyl orthosilicate ethanol solution is 1:5), and reacting for 15 h; then slowly dripping 10g of gamma-methacryloxypropyltrimethoxysilane at room temperature, and standing for 3 days to obtain a mixed product; finally, sequentially centrifuging, washing and cleaning the mixed product to obtain modified silicon dioxide coated silver particle particles;
(3) preparation of silver @ silica @ polystyrene microparticles: mixing the silver particle particles coated with the modified silicon dioxide, 120mL of water, 0.012g of sodium dodecyl benzene sulfonate and 0.1g of sodium bicarbonate, and stirring uniformly to obtain a modified mixture; under the protection of nitrogen, heating the modified mixture to 52 ℃, adding 1.1mL of styrene and 0.12mL of divinylbenzene when the modified mixture is in an emulsion state, then continuously heating to 70 ℃, adding 0.04g of potassium sulfate, and continuously reacting for 1 h; finally, the obtained mixture is dried after being centrifuged, washed by water and washed by ethanol, and the silver @ silicon dioxide @ polystyrene particles are obtained;
(4) preparing the core-shell structure carbon-coated silver microspheres: swelling the silver @ silicon dioxide @ polystyrene particles in 20mL of anhydrous carbon tetrachloride for 14 h; adding the swelled silver @ silicon dioxide @ polystyrene particles into a reactor, adding 0.6g of aluminum sulfate initiator into the reactor, reacting for 1d at 74 ℃, finally adding acetone and dilute hydrochloric acid to stop the reaction, and filtering, washing and drying the obtained reactant to obtain non-carbonized microspheres; heating the obtained non-carbonized microspheres at the speed of 5 ℃/min in the nitrogen atmosphere, sequentially keeping the temperature at 400 ℃, 600 ℃ and 850 ℃ for 3 hours respectively, then cooling to 400 ℃ at the cooling speed of 2 ℃/min, and naturally cooling to obtain carbonized microspheres; and adding the carbonized microspheres into 35mL of ethanol and 40mL of hydrofluoric acid, uniformly stirring, and finally, centrifuging, washing with water, washing with ethanol, and drying to obtain the core-shell structure carbon-coated silver microspheres taking single silver particles or multiple silver particles as cores.
The core-shell structure carbon-coated silver microsphere black coating printing paste comprises the following raw material components in parts by weight: 2 parts of core-shell structure carbon-coated silver microspheres, 15 parts of carbon black, 3 parts of red pigment, 3 parts of yellow pigment, 3 parts of blue pigment, 100 parts of waterborne polyurethane emulsion, 100 parts of waterborne acrylic resin and 50 parts of water; the water-based acrylic resin is an emulsion formed by a copolymer obtained by polymerizing methyl acrylate, ethyl acrylate, butyl acrylate and hydroxypropyl acrylate according to the mass ratio of 2:2:3: 3.
The preparation method of the black pigment printing paste comprises the following steps: and adding the weighed aqueous polyurethane emulsion into a container, then sequentially adding the weighed aqueous acrylic resin, carbon black, red pigment, yellow pigment, blue pigment, carbon-coated silver microspheres, water and thickening agent, and fully stirring to obtain the black pigment printing paste.
The method for applying the black pigment printing paste to the fabric comprises the following steps: pouring the black paint printing paste on a printing plate, adopting a blade coating mode to enable the black paint printing paste to permeate into the fabric, and then drying to form a film, thus obtaining the printed fabric.
Effect verification
1. Testing of antibacterial property of silver microspheres
control group 1: preparing Ag @ SiO by using silver nitrate as a silver source, tetraethoxysilane as a silicon source and formaldehyde and resorcinol as phenolic resin precursors through a sol-gel method2@ RF nano core-shell structure composite microsphere, and carbonizing and washing template to obtain Ag @ C porous carbon composite microsphere (namely Li Jian, Liu Rui. construction and performance research based on RF resin nano core-shell structure composite microsphere [ J]Yunnan chemical industry, 2018(5), 78-81 prepared carbon-coated silver microspheres);
control group 2: silica-coated silver microspheres obtained by coating silver particles with silica only;
control group 3: polystyrene-coated silver microspheres obtained by coating silver particles with polystyrene only;
control group 4: a core-shell structure carbon-coated silver microsphere is prepared by a master academic paper of the Huang Zhi Ke of Zhongshan university, design preparation and performance research of a novel noble metal @ polymer nanosphere with a yolk-eggshell structure (the specific raw material dosage preparation parameters and the like of the method are different from those of the application);
the experimental method comprises the following steps:
(1) inoculating activated Escherichia coli strain, inoculating the bacteria into sterilized nutrient broth, shaking for 18-20h (wherein, the rotation speed is 150rpm, and the air bath temperature is 37 deg.C), recording to obtain bacterial suspension with bacterial concentration of 109CFU/mL, and storing at 4 deg.C.
(2) Taking 18 filter paper sheets with the diameter of 1cm, disinfecting and drying the filter paper sheets, and averagely dividing the filter paper sheets into 6 groups, wherein each group comprises 3 filter paper sheets; respectively putting the filter paper of each group of filter paper sheets on the surface of an agar culture medium plate which is inoculated with bacterial suspension (the concentration of the bacterial suspension is 108CFU/mL) and has the diameter of 15cm after the filter paper of each group is dried, transferring the agar culture medium plate of each group to a constant temperature incubator at 37 ℃ for culturing for 18h, and then observing the size of an inhibition zone of the agar culture medium plate of each group and calculating the antibacterial efficiency (the calculation method is that the antibacterial rate (%) is [ (number of recovered bacteria of positive control group-number of recovered bacteria of test group)/number of recovered bacteria of positive control ] × 100%), and averaging the test results of each group.
The test results are shown in table 1:
TABLE 1 antibacterial property test results of each group of silver microspheres
| Group of | Diameter of antibacterial ring (cm) | Bacteriostatic ratio (%) |
| |
1.7 | 99.1 |
| Experimental group 2 | 2.0 | 99.4 |
| Experimental group 3 | 1.8 | 99.2 |
| |
1.4 | 90.5 |
| Control group 2 | 1.2 | 70.6 |
| Control group 3 | 1.1 | 62.5 |
| Control group 4 | 1.5 | 96.6 |
As can be seen from Table 1, the diameters of the inhibition rings and the antibacterial efficiencies of the silver microspheres of the experimental groups 1 to 3 are obviously superior to those of the silver microspheres of the control groups 1 to 4. From the comparison between the experimental groups 1 to 3 and the control groups 1 and 4, it can be seen that: compared with the silver microspheres in the prior art, the silver microspheres prepared by the invention have better antibacterial effect; as can be seen from the comparison between the experimental groups 1-3 and the control groups 1-2: according to the invention, the Ag @ C microspheres obtained by coating the silver particles with the modified silicon dioxide, then reacting with the polystyrene, finally carbonizing, and washing the template have better antibacterial effect than the silver microspheres obtained by coating only with the silicon dioxide or the silver microspheres obtained by coating with the polystyrene, which indicates that the silicon dioxide and the polystyrene adopted by the invention have a synergistic effect.
2. Performance testing of various sets of printed fabrics
control group 1: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the used core-shell structure carbon-coated silver microspheres are Li Jian and Liu Rui, and the carbon-coated silver microspheres are prepared on the basis of the construction and performance research of RF resin nano core-shell structure composite microspheres [ J ]. Yunnan chemical engineering, 2018(5): 78-81;
control group 2: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the silver microspheres are silicon dioxide coated silver microspheres obtained by only coating silver particles with silicon dioxide;
control group 3: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the core-shell structure carbon-coated silver microspheres are polystyrene-coated silver microspheres obtained by only coating polystyrene on silver particles;
control group 4: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the core-shell structure carbon-coated silver microspheres are prepared in a Master's academic paper of the Huang-Chi department of the university of Zhongshan & lt & gt design preparation and performance research of novel noble metal @ polymer nanospheres with a yolk-eggshell structure.
The printing fabrics of the groups all adopt polyester fabrics, the areas of the used cotton materials are the same, the quality and the concentration of the used color paste are the same, and the processing modes are the same, namely the color paste is different, and the rest are the same.
The following tests were performed on each of the above tissues:
(1) testing the hand feeling of the fabric: selecting 10 groups of professional persons related to the fabric to classify a hand feeling test group, grading the soft hand feeling degree of the fabric of each group, and averaging (10 points of full points);
(2) and (3) testing physical properties: testing the dry rubbing fastness, the wet rubbing fastness, the color fastness to sticking and the color fastness to changing after soaping of each tissue according to the GB/T3920-1997 standard;
(3) and (3) testing antibacterial performance: the bacteria inhibition rate of each tissue for 24h is tested by adopting the standard of JISZ2801 and taking escherichia coli as a tested strain.
The test results are shown in table 2:
table 2 results of property test of each structure
As can be seen from Table 2, the physical properties and antimicrobial properties of the fabrics of examples 1-3 are significantly better than those of controls 1-4. The fastness of the printed fabric reaches above 3-4 levels, and the fastness of the printed fabric of a control group is distributed within 2-4 levels, so that the printing paste is firm in adhesion and good in stability; the bacteriostasis rate of the fabric reaches more than 99.5 percent, which is obviously superior to that of a control group, and the color paste has good antibacterial effect.
3. Test of influence of thickness of carbon layer in core-shell structure carbon-coated silver microsphere on performance of printed fabric
Experimental groups 1-2: printed fabrics obtained by color paste treatment in embodiment 1 and embodiment 3 of the invention;
control group 1: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the thickness of the carbon layer of the core-shell structure carbon-coated silver microspheres is 18 nm;
control group 2: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the thickness of the carbon layer of the core-shell structure carbon-coated silver microspheres is 10 nm;
control group 3: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the thickness of the carbon layer of the core-shell structure carbon-coated silver microspheres is 92 nm;
control group 4: the color paste used by the printed fabric is basically the same as the color paste of the embodiment 1 of the invention, and the difference is that: the thickness of the carbon layer of the silver microsphere coated by the core-shell structure carbon is 100 nm.
The silver microspheres in the above groups have the same total particle size and silver particle size, i.e. only the carbon layer has different thickness.
The following tests were performed on each of the above tissues:
(1) leveling property of fabric: the leveling property of the fabric was expressed by measuring the apparent depth K/S value at the maximum absorption wavelength at any 8 points on the fabric and calculating the average value and the standard deviation Sr (the smaller the standard deviation, the better the leveling property).
(2) K/S value: the test is carried out on a computer color measuring and matching instrument according to the specification, a D65 light source is adopted in the test, the observation angle is 10 degrees, and the size of the test is expressed by a kubelka-Munk formula, namely K/S (1-R)2/2R, and R is the reflectivity at the maximum absorption wavelength.
(3) Dyeing vividness C value: the color is measured by using an SF-300 Cissus computer color measuring instrument, a D65 light source is adopted, an observation angle is 10 degrees, the sample is folded by 4 layers, and a dyeing lightness L value, a dyeing vividness C value and a hue H value under the pH value of 5 are measured by using a computer color measuring instrument.
The test results are shown in table 3:
TABLE 3 test of the effect of thickness of various sets of Microspherical carbon layers on the performance of printed fabrics
| Group of | K/S value | Sr | C value |
| |
3.52 | 0.029 | 43.18 |
| Experimental group 2 | 3.55 | 0.026 | 43.27 |
| |
3.31 | 0.034 | 41.89 |
| Control group 2 | 3.29 | 0.037 | 41.37 |
| Control group 3 | 3.34 | 0.035 | 40.88 |
| Control group 4 | 3.32 | 0.035 | 40.56 |
As can be seen from Table 3, the K/S value and dyeing vividness C value of the printed fabrics of the experimental groups 1 and 2 are higher than those of the control groups 1-4, and the standard deviation Sr is smaller than that of the control groups 1-4, so that the carbon layer thickness of the core-shell structure carbon-coated silver microspheres is controlled to be 20-90nm, the tinting strength and hiding power of the color paste are effectively improved, the leveling property of the fabrics is high, and the vividness of the fabrics is high.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. The carbon-coated silver microsphere with the core-shell structure is characterized in that the particle size of the carbon-coated silver microsphere is 50-200nm, wherein the particle size of silver particles is 10-40nm, and the thickness of a carbon shell layer is 20-90 nm.
2. The preparation method of the core-shell structure carbon-coated silver microsphere according to claim 1, characterized by comprising the following steps:
(1) preparation of silver particles: mixing and stirring 0.01-1g of trisodium citrate and 1-100mL of deionized water until the trisodium citrate is completely dissolved to obtain a trisodium citrate solution; adding 0.01-2g of silver nitrate and 50-800mL of deionized water into the trisodium citrate solution, heating at 100 ℃ for 20-30min, then adding 1-20mL of aqueous solution with trisodium citrate content of 1%, stirring for 20-30min, stopping heating, continuing stirring for 1-1.5, and then centrifuging at 800-; washing a product obtained by centrifugation, and then dispersing the product in 1-20mL of absolute ethyl alcohol to obtain a silver particle mixture;
(2) preparing modified silicon dioxide coated silver particle microspheres: adding 10-160mL of deionized water and 30-500mL of absolute ethanol into the silver particle mixture, adding 0.2-6.5mL of 30% ammonia water under the protection of nitrogen, stirring uniformly, slowly adding 2.5-40mL of ethyl orthosilicate ethanol solution, and reacting for 13-15 h; then slowly dripping 5-10g of gamma-methacryloxypropyltrimethoxysilane at room temperature, and standing for 2-3 days to obtain a mixed product; finally, sequentially centrifuging, washing and cleaning the mixed product to obtain modified silicon dioxide coated silver particle particles;
(3) preparation of silver @ silica @ polystyrene microparticles: mixing the silver particle particles coated with the modified silicon dioxide, 7-120mL of water, 0.0003-0.012g of sodium dodecyl benzene sulfonate and 0.002-0.1g of sodium bicarbonate, and stirring uniformly to obtain a modified mixture; under the protection of nitrogen, heating the modified mixture to 52 ℃, adding 0.27-1.1mL of styrene and 0.003-0.12mL of divinylbenzene when the modified mixture is in an emulsion state, then continuing to heat to 70 ℃, adding 0.001-0.04g of potassium sulfate, and continuing to react for 0.5-1 h; finally, the obtained mixture is dried after being centrifuged, washed by water and washed by ethanol, and the silver @ silicon dioxide @ polystyrene particles are obtained;
(4) preparing the core-shell structure carbon-coated silver microspheres: swelling the silver @ silicon dioxide @ polystyrene particles in 1-20mL of anhydrous carbon tetrachloride for 12-14 h; adding the swelled silver @ silicon dioxide @ polystyrene particles into a reactor, adding 0.014-0.6g of aluminum sulfate initiator into the reactor, reacting for 1d at 72-74 ℃, finally adding acetone and dilute hydrochloric acid to stop the reaction, and filtering, washing and drying the obtained reactant to obtain non-carbonized microspheres; heating the obtained non-carbonized microspheres at the speed of 5 ℃/min in the nitrogen atmosphere, sequentially keeping the temperature at 400 ℃, 600 ℃ and 850 ℃ for 3 hours respectively, then cooling to 400 ℃ at the cooling speed of 2 ℃/min, and naturally cooling to obtain carbonized microspheres; and adding the carbonized microspheres into 1-35mL of ethanol and 1-40mL of hydrofluoric acid, uniformly stirring, and finally, centrifuging, washing with water, washing with ethanol, and drying to obtain the core-shell structure carbon-coated silver microspheres.
3. The preparation method of the core-shell structure carbon-coated silver microsphere according to claim 2, wherein the volume ratio of ethyl orthosilicate to ethanol in the ethanol solution of ethyl orthosilicate is 1: 5.
4. The method for preparing the core-shell structure carbon-coated silver microspheres according to claim 2, wherein the core-shell structure carbon-coated silver microspheres take a single silver particle or a plurality of silver particles as a core.
5. A black pigment printing paste containing the core-shell structure carbon-coated silver microspheres as claimed in claim 1.
6. The black pigment printing paste according to claim 5, which is characterized by comprising the following raw materials in parts by weight: 0.01-2 parts of core-shell structure carbon-coated silver microspheres, 2.5-15 parts of carbon black, 0.5-3 parts of red pigment, 0.5-3 parts of yellow pigment, 0.5-3 parts of blue pigment, 0.01-100 parts of waterborne polyurethane emulsion, 0.01-100 parts of waterborne acrylic resin and 10-50 parts of water.
7. The black pigment printing paste according to claim 6, wherein the aqueous acrylic resin is an emulsion formed by a copolymer obtained by polymerizing methyl acrylate, ethyl acrylate, butyl acrylate and hydroxypropyl acrylate.
8. The black pigment printing paste according to claim 6 or 7, wherein the preparation method of the black pigment printing paste comprises the following steps: and adding the weighed aqueous polyurethane emulsion into a container, then sequentially adding the weighed aqueous acrylic resin, carbon black, red pigment, yellow pigment, blue pigment, carbon-coated silver microspheres, water and thickening agent, and fully stirring to obtain the black pigment printing paste.
9. Use of a black pigment printing paste according to claim 6 or 7 on fabrics.
10. Use according to claim 9, wherein the fabric is a synthetic fibre fabric or a cellulose fabric.
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