CN112500779A - Antibacterial antioxidant aluminum foil protective agent and preparation method thereof - Google Patents
Antibacterial antioxidant aluminum foil protective agent and preparation method thereof Download PDFInfo
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- CN112500779A CN112500779A CN202011187901.8A CN202011187901A CN112500779A CN 112500779 A CN112500779 A CN 112500779A CN 202011187901 A CN202011187901 A CN 202011187901A CN 112500779 A CN112500779 A CN 112500779A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
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Abstract
The invention relates to a bacteriostatic antioxidant aluminum foil protective agent and a preparation method thereof. The aluminum foil protective agent commonly used in the market at present is divided into a solvent type aluminum foil protective agent and a water-based aluminum foil protective agent, but the aluminum foil protective agent has the defect of dark color after long-time use.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a bacteriostatic antioxidant aluminum foil protective agent and a preparation method thereof.
Background
The aluminum foil protective agent commonly used in the market at present is divided into a solvent type aluminum foil protective agent and a water-based aluminum foil protective agent, but the aluminum foil protective agent has the defect of dark color after long-time use.
Disclosure of Invention
The invention aims to provide an aluminum foil protective agent which can meet the application performance of the conventional aluminum foil protective agent and achieve the antibacterial and antioxidant effects and a preparation method thereof, and overcomes the defects in the prior art.
The technical scheme adopted by the invention is as follows:
the method comprises the following steps: preparing antibacterial antioxidant polyurethane emulsion:
adding 10-60 parts of vinyl monomer, 10-35 parts of polyglycol, 6-24 parts of diisocyanate, 0.25-1.5 parts of dihydric alcohol, 1-6 parts of hydrophilic chain extender and 0.06-0.15 part of catalyst into a dry reactor, and reacting at 60-90 ℃ for 1-4 hours to obtain a polyurethane prepolymer;
adding 0.5-3 parts of end-capping reagent into the polyurethane prepolymer for end-capping reaction for 1-2 hours;
cooling the reaction system to room temperature, adding a pH regulator for neutralization reaction for 20-40 minutes until the pH of the reaction system is neutral, adding 45-300 parts of water under high-speed stirring, and stirring and dispersing for 20-40 minutes to obtain a bluish light emulsion;
heating the bluing light emulsion to 60-90 ℃, adding 0.005-0.1 part by mass of antioxidant and 0.001-0.1 part by mass of antibacterial agent under stirring, uniformly dripping an initiator aqueous solution obtained by dissolving 0.12-2.5 parts by mass of initiator in 10-5 parts by mass of water into the reactor within 1-4 hours, and continuing to perform heat preservation reaction for 2-4 hours after finishing dripping to obtain the antibacterial and antioxidant polyurethane emulsion;
step two: putting 45-80 parts of the antibacterial and antioxidant polyurethane emulsion obtained in the step one into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain an antibacterial and antioxidant aluminum foil protective agent;
or putting 45-80 parts of antibacterial and antioxidant polyurethane emulsion, no more than 35 parts of cosolvent, no more than 0.5 part of defoaming agent and no more than 2 parts of anti-scratching agent into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial and antioxidant aluminum foil protective agent.
Further, in the step one:
the vinyl monomer is selected from one or a mixture of any several of methyl methacrylate, ethyl methacrylate, styrene, alpha-methyl styrene, butyl methacrylate, hexyl methacrylate, n-octyl methacrylate and 2-ethylhexyl methacrylate in any proportion;
the polyglycol is selected from one or a mixture of any several of polycaprolactone diol, polycarbonate diol, polytetrahydrofuran diol, polyhexamethylene adipate and polybutylene adipate in any proportion;
the diisocyanate is selected from one or a mixture of any several of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate in any proportion;
the dihydric alcohol is selected from 1, 4-butanediol and diethylene glycol;
the hydrophilic chain extender is selected from dimethylolpropionic acid, dimethylolbutyric acid, dihydroxy sodium propane sulfonate, 2-aminoethyl sodium aminoethyl sulfonate and 2, 4-diaminobenzene sulfonate;
the catalyst is selected from dibutyltin dilaurate, dibutyltin diacetate and stannous octoate.
Further, in the first step, the blocking agent is selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxymethyl acrylamide and methacrylic acid.
Further, in the first step, the antioxidant is selected from one or a combination of ascorbic acid and citric acid; the antibacterial agent is selected from vanillin and ethyl vanillin, or their combination; the initiator is selected from potassium persulfate, ammonium persulfate, hydrogen peroxide and azodiisobutyl amidine hydrochloride.
Further, the cosolvent is selected from one or a combination of not less than two of ethanol, isopropanol and n-butanol.
Further, in the second step, the defoaming agent is selected from one or the combination of not less than two of BYK-034, BYK-035, BYK-037 and BYK-038 which are produced by Germany BYK company;
further, in the second step, the anti-scratching agent is selected from one or a combination of not less than two of polyethylene emulsifying wax, polyether modified organic silicon and silica sol.
The invention has the following advantages:
(1) environmental protection and cost advantage:
the preparation method has the advantages of simple preparation process, easy control in production, no use of any toxic and harmful volatile organic solvent in the whole preparation process, environmental protection and no pollution, and avoids the cost rise of the organic solvent and the environmental protection problem.
(2) The quality is stable:
the self-prepared waterborne polyurethane emulsion is used as a main film forming substance, so that the problems of stability, resin compatibility and the like caused by compounding of different resins are solved.
(3) Introduce antibacterial and antioxidant components
Compared with the prior art, the antibacterial and antioxidant component is introduced, the problem that the color of the existing aluminum foil protective agent becomes dark after long-time use can be effectively solved, and the antibacterial component is introduced aiming at food-grade and medicinal-grade aluminum foils, so that the breeding of microorganisms can be inhibited, and the aluminum foil protective agent is more beneficial to body health.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example 1:
(1) adding 50 parts of ethyl methacrylate, 30 parts of polycarbonate diol, 20 parts of hexamethylene diisocyanate, 1.1 parts of 1, 4-butanediol, 5.6 parts of 2, 4-diaminobenzene sodium sulfonate and 0.06 part of dibutyltin dilaurate into a dry reactor, and reacting at 60 ℃ for 2.5 hours to obtain a polyurethane prepolymer; 2.6 parts of hydroxyethyl methacrylate is added into the polyurethane prepolymer for end-capping reaction, and the reaction time is 2 hours; cooling the reaction system to room temperature, adding 4 parts of ammonia water for neutralization, carrying out neutralization reaction for 25 minutes, adding 290 parts of water under high-speed stirring, and stirring and dispersing for 28 minutes to obtain a bluish light emulsion; and heating the emulsion system to 80 ℃, adding 0.001 part of vanillin and 0.005 part of ascorbic acid, uniformly dripping an initiator aqueous solution (1.2 parts of hydrogen peroxide is dissolved in 18 parts of water) into the reactor within 2.5 hours, and continuing to perform heat preservation reaction for 3 hours after dripping is finished to obtain the waterborne polyurethane emulsion.
(2) Preparing materials according to the following weight formula:
(3) and (3) putting the raw materials in the step (2) into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial antioxidant aluminum foil protective agent.
Example 2:
(1) adding 37 parts of alpha-methyl styrene, 15 parts of butyl acrylate, 13 parts of polyhexamethylene adipate, 15 parts of diphenylmethane diisocyanate, 1.3 parts of diethylene glycol, 5 parts of dimethylolbutyric acid and 0.1 part of dibutyltin diacetate into a dry reactor, and reacting for 2 hours at the temperature of 85 ℃ to obtain a polyurethane prepolymer; 2.1 parts of hydroxypropyl methacrylate is added into the polyurethane prepolymer for end-capping reaction, and the reaction time is 1.2 hours; cooling the reaction system to room temperature, adding 7.5 parts of dimethylethanolamine for neutralization, carrying out neutralization reaction for 30 minutes, adding 160 parts of water under high-speed stirring, and stirring and dispersing for 25 minutes to obtain a bluish light emulsion; and heating the emulsion system to 75 ℃, adding 0.1 part of ethyl vanillin and 0.005 part of citric acid, uniformly dripping an initiator aqueous solution (1.8 parts of ammonium persulfate is dissolved in 20 parts of water) into the reactor within 3 hours, and continuing to perform heat preservation reaction for 2.5 hours after the dripping is finished to obtain the waterborne polyurethane emulsion.
(2) Preparing materials according to the following weight formula:
(3) and (3) putting the raw materials in the step (2) into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial antioxidant aluminum foil protective agent.
Example 3:
(1) adding 12 parts of n-octyl methacrylate, 10 parts of polycaprolactone diol, 6 parts of isophorone diisocyanate, 0.25 part of 1, 4-butanediol, 1 part of dihydroxy sodium propane sulfonate and 0.07 part of stannous octoate into a dry reactor, and reacting for 2 hours at 77 ℃ to obtain a polyurethane prepolymer; adding 0.5 part of hydroxyethyl methacrylate into the polyurethane prepolymer for end-capping reaction, wherein the reaction time is 1 hour; cooling the reaction system to room temperature, adding 1.1 parts of dimethylethylamine for neutralization, carrying out neutralization reaction for 20 minutes, adding 45 parts of water under high-speed stirring, and stirring and dispersing for 20 minutes to obtain a bluish light emulsion; and heating the emulsion system to 60 ℃, adding 0.005 part of vanillin and 0.1 part of ascorbic acid, uniformly dripping an initiator aqueous solution (0.12 part of potassium persulfate is dissolved in 10 parts of water) into the reactor within 1 hour, and continuing to perform heat preservation reaction for 4 hours after dripping is finished to obtain the waterborne polyurethane emulsion.
(2) Preparing materials according to the following weight formula:
(3) and (3) putting the raw materials in the step (2) into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial antioxidant aluminum foil protective agent.
Example 4:
(1) adding 50 parts of ethyl methacrylate, 10 parts of butyl methacrylate, 35 parts of polytetrahydrofuran diol, 24 parts of toluene diisocyanate, 1.5 parts of diethylene glycol, 6 parts of dimethylolbutyric acid and 0.15 part of dibutyltin dilaurate into a dry reactor, and reacting at 90 ℃ for 1.5 hours to obtain a polyurethane prepolymer; adding 3 parts of hydroxymethyl acrylamide into the polyurethane prepolymer for end-capping reaction for 2 hours; cooling the reaction system to room temperature, adding 10 parts of triethanolamine for neutralization, adding 300 parts of water under high-speed stirring, and stirring and dispersing for 40 minutes to obtain a bluish emulsion; and heating the emulsion system to 60 ℃, adding 0.008 part of ethyl vanillin and 0.05 part of citric acid, uniformly dripping an initiator aqueous solution (2.5 parts of azodiisobutyl amidine hydrochloride is dissolved in 25 parts of water) into the reactor within 4 hours, and continuing to perform heat preservation reaction for 4 hours after dripping is finished to obtain the waterborne polyurethane emulsion.
(2) Preparing materials according to the following weight formula:
(4) and (3) putting the raw materials in the step (2) into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial antioxidant aluminum foil protective agent.
Comparative example 1:
(1) adding 50 parts of ethyl methacrylate, 10 parts of butyl methacrylate, 35 parts of polytetrahydrofuran diol, 24 parts of toluene diisocyanate, 1.5 parts of diethylene glycol, 6 parts of dimethylolbutyric acid and 0.15 part of dibutyltin dilaurate into a dry reactor, and reacting at 90 ℃ for 1.5 hours to obtain a polyurethane prepolymer; adding 3 parts of hydroxymethyl acrylamide into the polyurethane prepolymer for end-capping reaction for 2 hours; cooling the reaction system to room temperature, adding 10 parts of triethanolamine for neutralization, adding 300 parts of water under high-speed stirring, and stirring and dispersing for 40 minutes to obtain a bluish emulsion; and heating the emulsion system to 60 ℃, adding 0.008 part of ethyl vanillin, uniformly dripping an initiator aqueous solution (2.5 parts of azodiisobutyl amidine hydrochloride is dissolved in 25 parts of water) into the reactor within 4 hours, and continuing to perform heat preservation reaction for 4 hours after dripping is finished to obtain the waterborne polyurethane emulsion.
(2) Preparing materials according to the following weight formula:
(3) and (3) putting the raw materials in the step (2) into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial antioxidant aluminum foil protective agent.
Comparative example 2:
(1) adding 50 parts of ethyl methacrylate, 10 parts of butyl methacrylate, 35 parts of polytetrahydrofuran diol, 24 parts of toluene diisocyanate, 1.5 parts of diethylene glycol, 6 parts of dimethylolbutyric acid and 0.15 part of dibutyltin dilaurate into a dry reactor, and reacting at 90 ℃ for 1.5 hours to obtain a polyurethane prepolymer; adding 3 parts of hydroxymethyl acrylamide into the polyurethane prepolymer for end-capping reaction for 2 hours; cooling the reaction system to room temperature, adding 10 parts of triethanolamine for neutralization, adding 300 parts of water under high-speed stirring, and stirring and dispersing for 40 minutes to obtain a bluish emulsion; and heating the emulsion system to 60 ℃, adding 0.05 part of citric acid, uniformly dripping an initiator aqueous solution (2.5 parts of azodiisobutyl amidine hydrochloride is dissolved in 25 parts of water) into the reactor within 4 hours, and continuing to perform heat preservation reaction for 4 hours after dripping is finished to obtain the waterborne polyurethane emulsion.
(2) Preparing materials according to the following weight formula:
(3) and (3) putting the raw materials in the step (2) into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial antioxidant aluminum foil protective agent.
Comparative example 3:
(1) adding 50 parts of ethyl methacrylate, 10 parts of butyl methacrylate, 35 parts of polytetrahydrofuran diol, 24 parts of toluene diisocyanate, 1.5 parts of diethylene glycol, 6 parts of dimethylolbutyric acid and 0.15 part of dibutyltin dilaurate into a dry reactor, and reacting at 90 ℃ for 1.5 hours to obtain a polyurethane prepolymer; adding 3 parts of hydroxymethyl acrylamide into the polyurethane prepolymer for end-capping reaction for 2 hours; cooling the reaction system to room temperature, adding 10 parts of triethanolamine for neutralization, adding 300 parts of water under high-speed stirring, and stirring and dispersing for 40 minutes to obtain a bluish emulsion; and heating the emulsion system to 60 ℃, uniformly dripping an initiator aqueous solution (2.5 parts of azodiisobutyl amidine hydrochloride is dissolved in 25 parts of water) into the reactor within 4 hours, and continuing to perform heat preservation reaction for 4 hours after the dripping is finished to obtain the waterborne polyurethane emulsion.
(2) Preparing materials according to the following weight formula:
(3) and (3) putting the raw materials in the step (2) into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial antioxidant aluminum foil protective agent.
The aqueous aluminum foil protective agent prepared according to the formulation in the above specific examples was subjected to application tests, coating experiments in aluminum foil for packaging:
1) the coating process of the water-based aluminum foil protective agent comprises the following steps:
(1) the process flow comprises the following steps: uncoiling → degreasing → washing → drying → roller coating of aqueous aluminum foil protective agent → baking and curing coating → coiling.
(2) The using method comprises the following steps: adding pure water or ethanol to dilute according to process conditions to obtain optimal appearance, and directly using.
(3) Coating thickness: 1 +/-0.1 g/square meter (dry film)
(4) Curing temperature: 120 ℃ C. and 130 ℃ C
2) Test results of the aqueous aluminum foil protectant:
table 1 results of performance testing
The performance test results of the water-based aluminum foil protective agent are shown in table 1, and the product is emulsion-shaped, does not contain mechanical impurities, does not break emulsion when coexisting with ethanol, and can be dissolved in color paste by using ethanol as a diluting solvent, so that the leveling property and the adhesive force of the product on a base material are improved. The coating film has transparent and smooth appearance, the drying time at 120 ℃ is 12 seconds, the coating film accords with the regulation during printing, the glossiness of the coating film reaches 85 degrees, the coating film accords with the requirements of cigarette and wine packaging, and the heat resistance and the adhesive force are excellent.
3) Comparative test
Table 2 comparative testing results
Table 2 shows the results of comparative example 1 without adding antioxidant, comparative example 2 without adding antioxidant, and comparative test results of common aqueous aluminum foil protective agent, which show that the addition of bacteriostatic agent and antioxidant can effectively improve the problem of gloss reduction of aluminum foil after long-term use, and has a certain effect of inhibiting the growth of microorganisms. The antibacterial antioxidant aluminum foil protective agent can be widely applied to the pharmaceutical and food industries and has wide application prospect.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (8)
1. A preparation method of a bacteriostatic antioxidant aluminum foil protective agent is characterized by comprising the following steps:
the method is realized by the following steps:
the method comprises the following steps: preparing antibacterial antioxidant polyurethane emulsion:
adding 10-60 parts of vinyl monomer, 10-35 parts of polyglycol, 6-24 parts of diisocyanate, 0.25-1.5 parts of dihydric alcohol, 1-6 parts of hydrophilic chain extender and 0.06-0.15 part of catalyst into a dry reactor, and reacting at 60-90 ℃ for 1-4 hours to obtain a polyurethane prepolymer;
adding 0.5-3 parts of end-capping reagent into the polyurethane prepolymer for end-capping reaction for 1-2 hours;
cooling the reaction system to room temperature, adding ammonia water for neutralization reaction for 20-40 minutes until the pH of the reaction system is neutral, adding 45-300 parts of water under high-speed stirring, and stirring and dispersing for 20-40 minutes to obtain a bluish light emulsion;
heating the bluing light emulsion to 60-90 ℃, adding 0.005-0.1 part by mass of antioxidant and 0.001-0.1 part by mass of antibacterial agent under stirring, uniformly dripping an initiator aqueous solution obtained by dissolving 0.12-2.5 parts by mass of initiator in 10-5 parts by mass of water into the reactor within 1-4 hours, and continuing to perform heat preservation reaction for 2-4 hours after finishing dripping to obtain the antibacterial and antioxidant polyurethane emulsion;
step two: putting 45-80 parts of the antibacterial and antioxidant polyurethane emulsion obtained in the step one into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain an antibacterial and antioxidant aluminum foil protective agent;
or putting 45-80 parts of antibacterial and antioxidant polyurethane emulsion, no more than 35 parts of cosolvent, no more than 0.5 part of defoaming agent and no more than 2 parts of anti-scratching agent into a reaction kettle, uniformly stirring, and filtering to remove insoluble substances to obtain the antibacterial and antioxidant aluminum foil protective agent.
2. The preparation method of the bacteriostatic antioxidant aluminum foil protective agent as claimed in claim 1, which is characterized in that:
in the first step:
the vinyl monomer is selected from one or a mixture of any several of methyl methacrylate, ethyl methacrylate, styrene, alpha-methyl styrene, butyl methacrylate, hexyl methacrylate, n-octyl methacrylate and 2-ethylhexyl methacrylate in any proportion;
the polyglycol is selected from one or a mixture of any several of polycaprolactone diol, polycarbonate diol, polytetrahydrofuran diol, polyhexamethylene adipate and polybutylene adipate in any proportion;
the diisocyanate is selected from one or a mixture of any several of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate in any proportion;
the dihydric alcohol is selected from 1, 4-butanediol and diethylene glycol;
the hydrophilic chain extender is selected from dimethylolpropionic acid, dimethylolbutyric acid, dihydroxy sodium propane sulfonate, 2-aminoethyl sodium aminoethyl sulfonate and 2, 4-diaminobenzene sulfonate;
the catalyst is selected from dibutyltin dilaurate, dibutyltin diacetate and stannous octoate.
3. The preparation method of the bacteriostatic antioxidant aluminum foil protective agent as claimed in claim 1, which is characterized in that:
in the first step, the blocking agent is selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxymethyl acrylamide and methacrylic acid.
4. The preparation method of the bacteriostatic antioxidant aluminum foil protective agent as claimed in claim 1, which is characterized in that:
in the first step, the antioxidant is selected from one or the combination of ascorbic acid and citric acid;
the antibacterial agent is selected from vanillin and ethyl vanillin, or their combination;
the initiator is selected from potassium persulfate, ammonium persulfate, hydrogen peroxide and azodiisobutyl amidine hydrochloride.
5. The preparation method of the bacteriostatic antioxidant aluminum foil protective agent as claimed in claim 1, which is characterized in that:
in the second step, the cosolvent is selected from one or the combination of not less than two of ethanol, isopropanol and n-butanol.
6. The preparation method of the bacteriostatic antioxidant aluminum foil protective agent as claimed in claim 1, which is characterized in that:
in the second step, the defoaming agent is selected from one or the combination of not less than two of BYK-034, BYK-035, BYK-037 and BYK-038 which are produced by Germany BYK company.
7. The preparation method of the bacteriostatic antioxidant aluminum foil protective agent as claimed in claim 1, which is characterized in that:
in the second step, the anti-scratching agent is selected from one or the combination of not less than two of polyethylene emulsifying wax, polyether modified organic silicon and silica sol.
8. The bacteriostatic antioxidant aluminum foil protective agent prepared by the preparation method of the bacteriostatic antioxidant aluminum foil protective agent according to claim 1.
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| CN202011187901.8A CN112500779A (en) | 2020-10-29 | 2020-10-29 | Antibacterial antioxidant aluminum foil protective agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960233A (en) * | 2021-03-25 | 2021-06-15 | 宁波时代铝箔科技股份有限公司 | Antibacterial aluminum foil meal box and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105907223A (en) * | 2016-07-05 | 2016-08-31 | 陕西科技大学 | Environment-friendly waterborne aluminium foil protective agent and preparation method thereof |
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2020
- 2020-10-29 CN CN202011187901.8A patent/CN112500779A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105907223A (en) * | 2016-07-05 | 2016-08-31 | 陕西科技大学 | Environment-friendly waterborne aluminium foil protective agent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960233A (en) * | 2021-03-25 | 2021-06-15 | 宁波时代铝箔科技股份有限公司 | Antibacterial aluminum foil meal box and preparation method thereof |
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