CN115353788A - Anti-virus skin touch gloss oil applied to automotive interior membrane and preparation method thereof - Google Patents
Anti-virus skin touch gloss oil applied to automotive interior membrane and preparation method thereof Download PDFInfo
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- CN115353788A CN115353788A CN202211176039.XA CN202211176039A CN115353788A CN 115353788 A CN115353788 A CN 115353788A CN 202211176039 A CN202211176039 A CN 202211176039A CN 115353788 A CN115353788 A CN 115353788A
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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
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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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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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses an antiviral skin touch gloss oil applied to an automotive interior film and a preparation method thereof, wherein the antiviral skin touch gloss oil is prepared from the following raw materials in parts by weight: 30-40 parts of nano copper paste, 30-45 parts of skin touch resin, 0.5-1.2 parts of wetting agent, 4-5 parts of cosolvent, 0.5-1 part of wax assistant, 0.06-0.1 part of defoamer and 9.9-32.92 parts of purified water; the product of the invention not only has the physical tolerance (high adhesive force, excellent water resistance and the like) of the traditional protective gloss oil, but also has the skin touch feeling and the antibacterial and antiviral functions, is a compound water-based gloss oil product, and has wide application prospect in the fields of automobile interior film health care and functional coatings.
Description
Technical Field
The invention relates to water-based gloss oil and a preparation method thereof, in particular to gloss oil with an antibacterial function and skin touch and a preparation method thereof.
Background
Since the outbreak of new crown epidemic situation, people's protection consciousness is gradually strengthened, and the surface of an article contacted by a human body is expected to have the functions of sterilization and virus resistance. Currently, several studies have shown that new coronavirus can survive 24 hours on cardboard surfaces and up to 3 days on plastic and stainless steel surfaces. When scientists drop new coronavirus on the plastic surface, it was found that 50% of the virus died after about 7 hours, half of the remaining virus died after 7 hours, and by the end of day 2, the final residual virus was less than 1% of the total, and the virus remained after 3 days was almost undetectable. For stainless steel surfaces, the half-life of the new coronaviruses is 5-6 hours, whereas for cardboard the half-life is shorter: less than 4 hours.
The shortest survival time of the new coronavirus on the surface of the object is copper, the copper has stronger antibacterial performance, and when the new coronavirus is dripped on the surface of the copper, half of the virus can die within 45 minutes. Copper has a powerful bactericidal function. When the copper surface directly interacts with the bacterial outer membrane, the bacterial outer membrane is broken through two ways of destroying the membrane potential of the bacteria through a short circuit effect and oxidizing destruction formed by oxygen impact of free single copper ions or copper molecules on the cell membrane; then the copper surface acts on the 'broken holes' on the outer membrane of the bacteria, copper ion current can smoothly enter the inside of the cells of the bacteria to block the metabolism of the cells, and the bacteria cannot breathe, eat, digest and generate energy. After killing cells and viruses, copper can still continuously play a role, and the persistence and the drug resistance are realized.
On the other hand, in recent years, with the global improvement of living standard, consumers are showing a tendency to actively search for health care or health protection products. And because taxi commuters get on and off duty every day, people are gradually strengthening consciousness of preventing epidemic diseases in automobiles. The product of the invention introduces copper oxide into an aqueous gloss oil system with skin touch. The nano-copper oxide is a novel antibacterial agent, and the antibacterial effect of the nano-copper oxide is caused by the fact that the nano-copper oxide can react with SH and SS bonds in microorganisms, disturb the physiological reaction of the microorganisms and cause the death of the microorganisms. The product not only has the physical tolerance (high adhesive force, excellent water resistance and the like) of the traditional protective gloss oil, but also has the skin touch and antiviral functions, and is a compound water-based gloss oil product.
Disclosure of Invention
The invention provides an antiviral skin tactility gloss oil applied to an automotive interior film and a preparation method thereof.
The technical scheme of the invention is as follows:
the anti-virus skin touch gloss oil is prepared from the following raw materials in parts by weight:
30-40 parts of nano copper paste, 30-45 parts of skin touch resin, 0.5-1.2 parts of wetting agent, 4-5 parts of cosolvent, 0.5-1 part of wax assistant, 0.06-0.1 part of defoamer and 9.9-32.92 parts of purified water.
The nano copper paste is prepared by the following method:
mixing 8-10 parts of dispersant, 0.1-0.3 part of Levaslip W-461 (Elementis company), 8.5-10.6 parts of purified water and 5-7 parts of nano copper oxide powder, adding into a stirring dispersion tank, stirring at 300rpm, keeping the stirring speed constant, and adding 0.06-0.1 part of nano copper oxide powder
W-074 (Germany Co., ltd.), stirring and mixing uniformly at the speed of 200rpm, transferring to a horizontal sand mill for grinding for 8-10 times until the particle size of the particles reaches below 50nm, and then sequentially filtering by a nylon bag with 500 meshes, a PP filter membrane with 2um aperture, a PP filter membrane with 1um aperture and a glass fiber filter membrane with 0.45um aperture to obtain the nano-copper slurry;
the structural general formula of the dispersant is as follows:
wherein the content of the first and second substances,
MMA is a methyl methacrylate monomer unit;
AA is an acrylic acid monomer unit;
z is C4-C12 alkylthio, C4-C12 alkyl, phenyl or benzyl;
x is an isopropanoyl, acetoxy, 2-nitriloacetoxy or 2-aminoacetoxy group;
methyl propylPolymerizing the methyl acrylate monomer unit and the acrylic acid monomer unit in a block copolymerization mode; n is 1 Is the degree of polymerization of the methyl methacrylate monomer units, n 1 ＝5～10；n 2 Is the degree of polymerization of the acrylic acid monomer unit, n 2 ＝5～20。
Preferred dispersants have the following structure:
the preparation method of the dispersant comprises the following steps:
(1) Preparation of the precursor
Reference is made to the methods of FERGUSON C J, HUGHES R J, NGUYEN D, PHAM B T T, GILBERT R G, SERELIS AK, SUCH C H, HAWKETT B S. Ab initio estimation polymerization by RAFT-controlled selected-assembly [ J ]. Macromolecules,2005,38 (6): 2191-2204. Precursors of the following structure are prepared:
wherein the content of the first and second substances,
z is C4-C12 alkylthio, C4-C12 alkyl, phenyl or benzyl;
x is isopropenyl, acetoxy, 2-nitriloacetoxy or 2-aminoacetoxy;
particularly preferably Z is benzyl and X is isopropenyl;
(2) Preparation of the Polymer (the following parts are by weight)
Mixing 3 parts of precursor, 0.2 part of azodiisonitrilo valeric acid V501 initiator, 4.32-17.28 parts of AA and 106 parts of dioxane, stirring for dissolving, introducing nitrogen for removing oxygen for half an hour, and reacting for 2 hours at 80 ℃; supplementing 6-12 parts of MMA, 0.2 part of azobisisonitrile valeric acid V501 initiator and 32 parts of dioxane into the system, introducing nitrogen, removing oxygen for half an hour, and reacting at 80 ℃ for 12 hours; and then cooling the system to room temperature, precipitating the dispersing agent by using cyclohexane as a precipitator, and drying the obtained precipitate at 45 ℃ in vacuum to constant weight to obtain the dispersing agent with the block structure.
The skin touch resin is prepared by the following method:
(1) Preparing a priming phase:
adding 50 parts of nano copper slurry (prepared by the method), 0.2 part of Emulsogen APG 2019 (Clien company) and an initiator aqueous solution into 30 parts of deionized water, and uniformly stirring at the speed of 300rpm to obtain a bottoming phase;
the initiator aqueous solution is obtained by dissolving 0.25 part of ammonium persulfate in 4 parts of deionized water;
(2) Preparation of dropwise addition phase:
dividing 18 parts of methyl methacrylate monomer, 18 parts of isodecyl acrylate monomer into 9 parts by weight of; 0.1 part of Emulsogen APG 2019 (Clien) and 0.23 part of Emulsogen APG
BL-240/W (Solvay) is mixed and divided into 4 parts by weight, and the parts are marked as 3, 5, 7 and 9 stages of emulsifier in turn;
(3) A polymerization stage:
raising the temperature of the priming phase in the step (1) to 80 ℃, adjusting the stirring speed to 150rpm, keeping the system for 15min after blue light appears, then sequentially dropwise adding monomers in 2 nd, 3 rd, 4 th, 5 th, 6 th, 7 th, 8 th, 9 th and 10 th sections, wherein the dropwise adding time of each section of monomer is 35min, simultaneously dropwise adding emulsifiers in 3 rd, 5 th, 7 th and 9 th sections when the monomers in 3 rd, 5 th, 7 th and 9 th sections are dropwise added, the dropwise adding time of each section of emulsifier is 35min, and after all the monomers and the emulsifiers are dropwise added, keeping the temperature and stirring for 1.5h to obtain a polymerization reaction liquid;
(4) And (3) post-treatment stage:
cooling the polymerization reaction liquid obtained in the step (3) to 75 ℃, adding tert-butyl hydrogen peroxide aqueous solution, keeping the temperature and stirring for 10min, then adding rongalite aqueous solution, keeping the temperature and stirring for 10min, then cooling to room temperature (20-30 ℃), and filtering and discharging through a 300-mesh nylon filter bag to obtain the skin touch resin;
the tert-butyl hydroperoxide aqueous solution is obtained by dissolving 0.038 part of tert-butyl hydroperoxide in 1 part of deionized water;
the rongalite aqueous solution is obtained by dissolving 0.038 parts of rongalite in 1 part of deionized water.
The wetting agent is one or a mixture of more than two of alkyl alcohol ammonium salt wetting agents (such as ANTI-TERRA-250, BYK), acrylic copolymer solution wetting agents (such as DISPERBYK-2012, BYK) and modified polyalkyl oxide wetting agents (such as Levaslip W-461, ELEMENTIS, DW-390, daihai silicon material technology (Shanghai) limited) in any proportion, and particularly preferably ANTI-TERRA-250 (BYK).
The cosolvent of the invention is preferably food grade ethanol (Suzhou European chemical Co., ltd.).
The wax additive is one or a mixture of more than two of oxidized polymer wax and modified polyester wax in any proportion; the oxidized polymer wax is, for example: VISCOCER 1017 (CERONAS), VISCOCER 2016 (CERONAS), MD-2042 (KEIM); the modified polyester type wax is, for example: ADDIMER 696 (cerona corporation), ADDIMER 697 (cerona corporation); VISCOCER 2016 (CERONAS corporation) is particularly preferred.
The defoaming agent is a lower alcohol defoaming agent (such as:
DF 3163, tequila), mineral oil type antifoaming agents (e.g.:
w-074, germany modest;
w-082, germany modest;
w-098, germany modest; ADVANTAGE AM-1512, ASHLAND-AQUALON corporation), silicone-based antifoaming agents (e.g.: g308, milliken chemical group, ltd.) in any proportion; mineral oil-based antifoaming agents are preferred, with particular preference given to
W-098 (Demodesty).
The preparation method of the antiviral skin touch gloss oil comprises the following steps:
according to the formula, nano copper paste, skin touch resin, wetting agent, purified water, wax additive and cosolvent are mixed and added into a stirring dispersion tank, stirring is started at the speed of 400-500 rpm, the stirring speed is kept unchanged, defoaming agent is added, the mixture is uniformly stirred and mixed at the speed of 200-300rpm, and then the mixture is filtered and discharged to obtain the antiviral skin touch gloss oil.
The anti-virus skin touch gloss oil can be coated on an automotive interior film in a conventional gravure printing mode and is applied to the field of printing of the automotive interior film.
Compared with the prior art, the invention has the following advantages:
1. the nano copper paste prepared by the method has fine particle size, the particle size is below 30nm, the prepared finished gloss oil has good stability, and the storage stability exceeds one year;
2. the gloss oil has good water resistance, strong adhesive force and obvious skin touch;
3. the antibacterial property of the gloss oil reaches 99%, and the antiviral effect reaches the high-efficiency grade standard.
The product of the invention not only has the physical tolerance (high adhesive force, excellent water resistance and the like) of the traditional protective gloss oil, but also has the skin touch feeling and the antibacterial and antiviral functions, is a compound water-based gloss oil product, and has wide application prospect in the fields of automobile interior film health care and functional coatings.
Drawings
FIG. 1 is a particle size distribution diagram of nano-copper slurry after four-stage filtration in example 1.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
The particle size and particle size distribution of the nano copper slurry are tested on a Malvern ZETASIZER 3000HAS particle size analyzer, and the closer the particle size distribution is to 0, the more uniform the particle size of the system is.
The water resistance of the gloss oil coating is determined to be qualified according to GB1733-1993, and the water resistance is determined to be qualified when the sample is soaked for 100 hours without phenomena of fading, reduction of glossiness, foaming, falling off and the like, and the longer the soaking time is, the better the water resistance is without the change.
The adhesion test of the gloss oil coating is carried out according to GB/T13217.7-2009, and the adhesion fastness is more than or equal to 95 percent, namely the adhesion fastness of the resin is excellent.
The self-extinction performance of the gloss oil coating film is tested by a 60-degree gloss meter after the gloss oil is dried into a film, and the lower the surface gloss is, the better the self-extinction performance of the gloss oil is.
The skin feel performance of the gloss oil coating film is judged by comparing with the commercially available polyurethane waterborne skin feel coating/resin, the gloss oil coating film is formed on a PVC or PET plastic film under the same condition and is dried in an air-blast drying oven at 60 ℃, and the gloss oil skin feel performance is good if the hand touch feel is close.
The antibacterial performance of the gloss oil was tested according to QB/T2591-2003.
Antiviral efficacy of gloss oil according to ISO 18184-2019 appendix F: the antiviral efficacy is evaluated, and 3.0> antiviral efficacy value Mv >2.0 represents that the antiviral standard of the product is low; mv >3.0 indicates that the antiviral standard of the product is high-efficiency.
The storage stability of the gloss oil means that the gloss oil liquid stands still for 18 days at the temperature of 60 ℃, and the storage stability of the gloss oil is more than 12 months without precipitation and delamination.
In the following examples, the structure of the dispersant used to prepare the nano-copper slurry is as follows:
in example 1Degree of polymerization of MMA monomer n 1 Is 5,AA monomer degree of polymerization n 2 Is 5;
in example 2, the degree of polymerization n of MMA monomer 1 Is 5,AA monomer degree of polymerization n 2 Is 15;
in example 3, the degree of polymerization n of MMA monomer 1 Is 8,AA monomer degree of polymerization n 2 Is 20;
in example 4, the degree of polymerization n of MMA monomer 1 Is 10,AA monomer degree of polymerization n 2 Is 20.
Example 1
The preparation method of the dispersant comprises the following steps:
1) Reference is made to the methods of FERGUSON C J, HUGHES R J, NGUYEN D, PHAM B T T, GILBERT R G, SERELIS A K, SUCH C H, HAWKETT B S. Ab initio polymerization by RAFT-controlled selected-assembly [ J ]. Macromolecules,2005,38 (6): 2191-2204. Precursors of the following structure are prepared: (the precursors of the following examples were prepared identically)
2) Firstly, adding 3g of the precursor obtained in the step 1), 0.2g of azobisisonitrile valeric acid V501 initiator (a national medicine group), 4.32g of AA and 106g of dioxane into a three-neck round-bottom flask, fully stirring and dissolving, introducing nitrogen to remove oxygen for half an hour, and reacting at 80 ℃ for 2 hours; 6g of MAA, 0.2g of azobisisonitrile valeric acid V501 initiator (national medicine group) and 32g of dioxane are added, nitrogen is introduced, oxygen is removed for half an hour, and the mixture reacts for 12 hours at 80 ℃; and then cooling the system to room temperature, finally precipitating the dispersing agent by using cyclohexane as a precipitator, and drying the obtained product at 45 ℃ in vacuum to constant weight to obtain the dispersing agent with the block structure.
Preparing nano copper slurry:
mixing 8g of dispersant, 0.3g of Levaslip W-461 (Elementis Co.), 8.5g of purified water and 5g of high-purity nano copper oxide powder ZH-CuO20N (Hefei Zhonghang nanotechnology development Co., ltd.), adding into a stirring dispersion tank, stirring at 300rpm, keeping the stirring speed constant, and then adding0.06g of
W-074 (Germany Co., ltd.), stirring and mixing uniformly at 200rpm, transferring to a horizontal sand mill (TBM-50, taiyai (Shanghai) industries Co., ltd.) for grinding for 10 times, and sequentially filtering with a 500-mesh nylon bag, a 2 um-aperture PP filter membrane, a 1 um-aperture PP filter membrane and a 0.45 um-aperture glass fiber filter membrane to obtain the nano-copper slurry after the particle size reaches below 50 nm.
The resin with skin touch feeling is prepared by the following method:
(1) Preparing a priming phase:
adding 50g of the prepared nano copper slurry, 0.2g of Emulsogen APG 2019 (Cline company) and an initiator aqueous solution into 30g of deionized water, and stirring and dissolving at the speed of 300rpm to obtain a priming phase;
the initiator aqueous solution is prepared by dissolving 0.25g of ammonium persulfate in 4g of deionized water;
(2) Preparation of dropwise addition phase:
dividing 18g of methyl methacrylate monomer (shanghai and creative chemistry, ltd.), 18g of isodecyl acrylate monomer (shanghai and creative chemistry, ltd.) into 9g of; 0.1g Emulsogen APG 2019 (Klien) and 0.23g
BL-240/W (Solvay) is mixed and divided into 4g according to weight, and the weight is marked as emulsifier in 3 rd, 5 th, 7 th and 9 th stages;
(3) A polymerization stage:
raising the temperature of the bottoming phase in the step (1) to 80 ℃, adjusting the stirring speed to 150rpm, keeping the system for 15min after blue light appears, then sequentially dropwise adding monomers in 2 nd, 3 rd, 4 th, 5 th, 6 th, 7 th, 8 th, 9 th and 10 th sections, wherein the dropwise adding time of each section of monomers is 35min, simultaneously dropwise adding emulsifiers in 3 rd, 5 th, 7 th and 9 th sections when the monomers in 3 rd, 5 th, 7 th and 9 th sections are dropwise added, the dropwise adding time of each section of emulsifiers is 35min, and after all the monomers and the emulsifiers are dropwise added, keeping the temperature and stirring for 1.5h;
(4) And (3) post-treatment stage:
cooling the polymerization reaction liquid obtained in the step (3) to 75 ℃, adding tert-butyl hydrogen peroxide aqueous solution, stirring for 10min under heat preservation, then adding rongalite aqueous solution, stirring for 10min under heat preservation, then cooling to room temperature (20-30 ℃), filtering and discharging through a 300-mesh nylon filter bag to obtain the skin touch resin;
the tert-butyl hydroperoxide aqueous solution is obtained by dissolving 0.038g of tert-butyl hydroperoxide in 1g of deionized water;
the rongalite aqueous solution is obtained by dissolving 0.038g of rongalite in 1g of deionized water.
Preparation of antiviral skin tactility gloss oil:
mixing 30g of nano copper paste, 30g of self-made skin-touch resin, 1g of ANTI-TERRA-250 (BYK), 32.92g of purified water, 1g of VISCOCER 2016 (CERONAS), and 5g of food grade ethanol (Suzhou Ouchi chemical Co., ltd.), adding into a stirring dispersion tank, stirring at 400rpm, and adding 0.08g of ethanol
W-098 (Demodesty), mixed well with stirring at 300rpm and filtered to give an antiviral skin lightening oil.
Example 2
The preparation method of the dispersant comprises the following steps:
firstly, adding 3g of the precursor obtained in the step 1), 0.2g of azobisisonitrile valeric acid V501 initiator (a national medicine group), 12.96g of AA and 106g of dioxane into a three-neck round-bottom flask, fully stirring and dissolving, introducing nitrogen to remove oxygen for half an hour, and reacting at 80 ℃ for 2 hours; 6g of MMA, 0.2g of azobisisonitrile valeric acid V501 initiator (national medicine group) and 32g of dioxane are added, nitrogen is introduced to remove oxygen for half an hour, and the reaction is carried out for 12 hours at 80 ℃; and then cooling the system to room temperature, finally precipitating the dispersing agent by using cyclohexane as a precipitator, and drying the obtained product at 45 ℃ in vacuum to constant weight to obtain the dispersing agent with the block structure.
Preparing nano copper slurry:
mixing 8g of dispersant, 0.2g of Levaslip W-461 (Elementis corporation), 9g of purified water and 5g of high-purity nano copper oxide powder ZH-CuO20N (Naviga nanotechnology development Co., ltd.) into a stirring dispersion tank, stirring at 300rpm, keeping the stirring speed constant, and adding 0.06g of nano copper oxide powder
W-074 (Germany Co., ltd.), stirring and mixing uniformly at 200rpm, transferring to a horizontal sand mill (TBM-50, taiyai (Shanghai) industries Co., ltd.) for grinding for 10 times, and sequentially filtering with a 500-mesh nylon bag, a 2 um-aperture PP filter membrane, a 1 um-aperture PP filter membrane and a 0.45 um-aperture glass fiber filter membrane to obtain the nano-copper slurry after the particle size reaches below 50 nm.
The method for preparing the resin having a skin-touch feeling was the same as in example 1 except that the nano copper paste was replaced with the nano copper paste prepared in this example.
Preparation of antiviral skin tactility gloss oil:
mixing 35g of nano copper paste, 35g of self-made skin-touch resin, 1.2g of ANTI-tera-250 (BYK), 23.94g of purified water, 0.8g of VISCOCER 2016 (cerona) and 4g of food grade ethanol (sovik, ohte chemical limited), adding into a stirring dispersion tank, stirring at 500rpm, and adding 0.06g of the mixture
W-098 (Demodesty), mixed well with stirring at 300rpm and filtered to give an antiviral skin lightening oil.
Example 3
The preparation method of the dispersant comprises the following steps:
firstly, adding 3g of the precursor obtained in the step 1), 0.2g of azobisisonitrile valeric acid V501 initiator (national medicine group), 17.28g of AA and 106g of dioxane into a three-neck round-bottom flask, fully stirring and dissolving, introducing nitrogen to remove oxygen for half an hour, and then reacting for 2 hours at 80 ℃; 9.6g of MMA, 0.2g of azobisisonitrile valeric acid V501 initiator (national medicine group) and 32g of dioxane are added, nitrogen is introduced, oxygen is removed for half an hour, and the mixture reacts at 80 ℃ for 12 hours; and cooling the system to room temperature, finally precipitating the dispersant by using cyclohexane as a precipitator, and drying the obtained product at 45 ℃ in vacuum to constant weight to obtain the dispersant with the block structure.
Preparing nano copper slurry:
mixing 9g of dispersant, 0.1g of Levaslip W-461 (Elementis Co., ltd.), 9.9g of purified water and 6g of high-purity nano copper oxide powder ZH-CuO20N (composite fertilizer Navig nanotechnology development Co., ltd.), adding into a stirring dispersion tank, stirring at 300rpm while keeping the stirring speed constant, and adding 0.08g of nano copper oxide powder ZH-CuO20N
W-074 (Germany Co., ltd.), stirring and mixing uniformly at 200rpm, transferring to a horizontal sand mill (TBM-50, taiyai (Shanghai) industries Co., ltd.) for grinding for 9 times, and sequentially filtering with a 500-mesh nylon bag, a 2 um-aperture PP filter membrane, a 1 um-aperture PP filter membrane and a 0.45 um-aperture glass fiber filter membrane to obtain the nano-copper slurry after the particle size reaches below 50 nm.
The method for preparing the resin having a skin-touch feeling was the same as in example 1 except that the nano copper paste was replaced with the nano copper paste prepared in this example.
Preparation of antiviral skin tactility gloss oil:
mixing 38g of nano copper paste, 36g of self-made skin-touch resin, 0.8g of ANTI-TERRA-250 (BYK), 20.62g of purified water, 0.5g of VISCOCER 2016 (CERONAS), and 4g of food grade ethanol (Suzhou Europe chemical Co., ltd.), adding into a stirring dispersion tank, stirring at 500rpm, and adding 0.08g of the mixture
W-098 (Demodesty) was mixed well with stirring at 200rpm and filtered to give an antiviral shiny oil.
Example 4
The preparation method of the dispersant comprises the following steps:
firstly, adding 3g of the precursor obtained in the step 1), 0.2g of azobisisonitrile valeric acid V501 initiator (a national medicine group), 17.28g of AA and 106g of dioxane into a three-neck round-bottom flask, fully stirring and dissolving, introducing nitrogen to remove oxygen for half an hour, and reacting at 80 ℃ for 2 hours; 12g of MMA, 0.2g of azobisisonitrile valeric acid V501 initiator (a national group of medicines) and 32g of dioxane are added, nitrogen is introduced for removing oxygen for half an hour, and the reaction is carried out for 12 hours at 80 ℃; and cooling the system to room temperature, finally precipitating the dispersant by using cyclohexane as a precipitator, and drying the obtained product at 45 ℃ in vacuum to constant weight to obtain the dispersant with the block structure.
Preparing nano copper slurry:
mixing 10g of dispersant, 0.1g of Levaslip W-461 (Elementis Co.), 10.6g of purified water and 7g of high-purity nano copper oxide powder ZH-CuO20N (Hefei Zhonghang nanotechnology development Co., ltd.), adding into a stirring dispersion tank, stirring at 300rpm, keeping the stirring speed constant, and adding 0.1g of nano copper oxide powder ZH-CuO20N
W-074 (Germany Co., ltd.), stirring and mixing uniformly at 200rpm, transferring to a horizontal sand mill (TBM-50, taiyai (Shanghai) industries Co., ltd.) for grinding for 8 times, and sequentially filtering with a 500-mesh nylon bag, a 2 um-aperture PP filter membrane, a 1 um-aperture PP filter membrane and a 0.45 um-aperture glass fiber filter membrane to obtain the nano-copper slurry after the particle size reaches below 50 nm.
The method for preparing the resin having a skin feel was the same as that of example 1, except that the nano copper paste was replaced with the nano copper paste prepared in this example.
Preparation of antiviral skin tactility gloss oil:
40g of nano-copper slurry and 45g of self-copperThe resin for skin touch, 0.5g of ANTI-TERRA-250 (BYK), 9.9g of purified water, 0.5g of VISCOCER 2016 (CERONAS), and 4g of food grade ethanol (Suzhou Euro speciality chemical Co., ltd.) were mixed, the mixture was charged into a stirring and dispersing tank, stirring was started at 400rpm, the stirring speed was kept constant, and 0.1g of ethanol was added
W-098 (Demodesty) was mixed well with stirring at 200rpm and filtered to give an antiviral shiny oil.
TABLE 1 EXAMPLES 1-4 Performance Table
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the claims.
Claims (7)
1. The anti-virus skin touch gloss oil is characterized by comprising the following raw materials in parts by weight:
30-40 parts of nano copper paste, 30-45 parts of skin touch resin, 0.5-1.2 parts of wetting agent, 4-5 parts of cosolvent, 0.5-1 part of wax assistant, 0.06-0.1 part of defoamer and 9.9-32.92 parts of purified water;
the nano copper slurry is prepared by the following method:
mixing 8-10 parts of dispersant, 0.1-0.3 part of Levaslip W-461, 8.5-10.6 parts of purified water and 5-7 parts of nano copper oxide powder, adding into a stirring dispersion cylinder, starting stirring at the speed of 300rpm, keeping the stirring speed unchanged, and then adding 0.06-0.1 part of nano copper oxide powder
W-074, stirring and mixing evenly at the speed of 200rpm, transferring to a horizontal sand mill for grinding for 8-10 times until the particle size reaches below 50nm,then sequentially carrying out four-stage filtration by using a 500-mesh nylon bag, a 2-um-aperture PP filter membrane, a 1-um-aperture PP filter membrane and a 0.45-um-aperture glass fiber filter membrane to obtain the nano copper slurry;
the structural general formula of the dispersant is as follows:
wherein the content of the first and second substances,
MMA is a methyl methacrylate monomer unit;
AA is an acrylic acid monomer unit;
z is C4-C12 alkylthio, C4-C12 alkyl, phenyl or benzyl;
x is isopropenyl, acetoxy, 2-nitriloacetoxy or 2-aminoacetoxy;
the methyl methacrylate monomer unit and the acrylic acid monomer unit are polymerized in a block copolymerization mode; n is 1 Is the degree of polymerization of the methyl methacrylate monomer units, n 1 ＝5～10；n 2 Is the degree of polymerization, n, of the acrylic acid monomer unit 2 ＝5～20；
The resin with skin touch feeling is prepared by the following method:
(1) Preparing a priming phase:
adding 50 parts of nano copper slurry, 0.2 part of Emulsogen APG 2019 and an initiator aqueous solution into 30 parts of deionized water, and uniformly stirring at the speed of 300rpm to obtain a priming phase;
the initiator aqueous solution is obtained by dissolving 0.25 part of ammonium persulfate in 4 parts of deionized water;
(2) Preparation of dropwise addition phase:
dividing 18 parts of methyl methacrylate monomer and 18 parts of isodecyl acrylate monomer into 9 parts by weight of; 0.1 part of Emulsogen APG 2019 and 0.23 part
Mixing BL-240/W, dividing into 4 parts by weight, and marking as emulsifier in 3 rd, 5 th, 7 th and 9 th sections in sequence;
(3) A polymerization stage:
raising the temperature of the bottoming phase in the step (1) to 80 ℃, adjusting the stirring speed to 150rpm, keeping the system for 15min after blue light appears, then sequentially dropwise adding monomers in 2 nd, 3 rd, 4 th, 5 th, 6 th, 7 th, 8 th, 9 th and 10 th sections, wherein the dropwise adding time of each section of monomers is 35min, simultaneously dropwise adding emulsifiers in 3 rd, 5 th, 7 th and 9 th sections when the monomers in 3 rd, 5 th, 7 th and 9 th sections are dropwise added, the dropwise adding time of each section of emulsifiers is 35min, and after all the monomers and the emulsifiers are dropwise added, keeping the temperature and stirring for 1.5h to obtain a polymerization reaction liquid;
(4) And (3) post-treatment stage:
cooling the polymerization reaction liquid obtained in the step (3) to 75 ℃, adding tert-butyl hydrogen peroxide aqueous solution, stirring for 10min at a constant temperature, then adding rongalite aqueous solution, stirring for 10min at a constant temperature, then cooling to room temperature, and filtering and discharging through a 300-mesh nylon filter bag to obtain the skin touch resin;
the tert-butyl hydroperoxide aqueous solution is obtained by dissolving 0.038 parts of tert-butyl hydroperoxide in 1 part of deionized water;
the rongalite aqueous solution is obtained by dissolving 0.038 parts of rongalite in 1 part of deionized water.
2. The antiviral skin gloss oil of claim 1, wherein the wetting agent is one or a mixture of two or more of an alkylol ammonium salt-based wetting agent, an acrylic acid copolymer solution-based wetting agent, and a (modified) polyalkyl alkane wetting agent in an arbitrary ratio.
3. The antiviral skin gloss oil of claim 1, wherein said co-solvent is food grade ethanol.
4. The antiviral skin gloss oil of claim 1, wherein said wax adjuvant is one or a mixture of two or more of oxidized polymer wax and modified polyester wax in any ratio.
5. The antiviral skin gloss oil according to claim 1, wherein said antifoaming agent is one or a mixture of two or more of lower alcohol antifoaming agents, mineral oil antifoaming agents, and silicone antifoaming agents at any ratio.
6. The method of preparing an antiviral skin gloss oil of claim 1, wherein said method of preparing comprises:
according to the formula, nano copper paste, skin touch resin, a wetting agent, purified water, a wax additive and a cosolvent are mixed, added into a stirring dispersion tank, stirred at the speed of 400-500 rpm, the stirring speed is kept unchanged, a defoaming agent is added, the mixture is uniformly stirred and mixed at the speed of 200-300rpm, and then the mixture is filtered and discharged to obtain the antiviral skin touch gloss oil.
7. Use of the antiviral skin gloss oil according to any one of claims 1 to 5 for printing of automotive interior films.
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