CN117487284A - Dual-antibacterial visible light catalytic fresh-keeping material and preparation method thereof - Google Patents
Dual-antibacterial visible light catalytic fresh-keeping material and preparation method thereof Download PDFInfo
- Publication number
- CN117487284A CN117487284A CN202311495908.XA CN202311495908A CN117487284A CN 117487284 A CN117487284 A CN 117487284A CN 202311495908 A CN202311495908 A CN 202311495908A CN 117487284 A CN117487284 A CN 117487284A
- Authority
- CN
- China
- Prior art keywords
- tio
- antibacterial
- nano
- visible light
- fresh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 68
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 122
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 82
- 239000002131 composite material Substances 0.000 claims abstract description 60
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000004793 Polystyrene Substances 0.000 claims description 36
- 229920002223 polystyrene Polymers 0.000 claims description 35
- 239000004014 plasticizer Substances 0.000 claims description 31
- 239000007822 coupling agent Substances 0.000 claims description 27
- 239000003381 stabilizer Substances 0.000 claims description 23
- 239000000084 colloidal system Substances 0.000 claims description 20
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002086 nanomaterial Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012760 heat stabilizer Substances 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 230000000845 anti-microbial effect Effects 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 38
- 238000007146 photocatalysis Methods 0.000 abstract description 27
- 241000894006 Bacteria Species 0.000 abstract description 13
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000003980 solgel method Methods 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 239000004033 plastic Substances 0.000 description 26
- 229920003023 plastic Polymers 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000008187 granular material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 230000003115 biocidal effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000004298 light response Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical group O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000012632 fluorescent imaging Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- MSFSPUZXLOGKHJ-UHFFFAOYSA-N Muraminsaeure Natural products OC(=O)C(C)OC1C(N)C(O)OC(CO)C1O MSFSPUZXLOGKHJ-UHFFFAOYSA-N 0.000 description 1
- 108010013639 Peptidoglycan Proteins 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/015—Biocides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catalysts (AREA)
Abstract
The application provides a double-antibacterial visible light catalytic fresh-keeping material and a preparation method thereof, wherein a sol-gel method is adopted to prepare TiO (titanium dioxide) 2 Is prepared into nano particles and then is mixed with Ag + Composite preparation of Ag + /Nano‑TiO 2 The composite antibacterial agent adopts PS as matrix resin and Ag + /Nano‑TiO 2 The composite antibacterial agent is a photocatalysis antibacterial agent, so that Ag is prepared + /Nano‑TiO 2 PS composite material, ag ion and anatase type TiO 2 The composite of the nano particles can endow the matrix resin with excellent antibacterial property and effectively improve TiO 2 The photo-response wavelength range of the ultraviolet light has a photo-catalytic effect under the condition of not needing ultraviolet light irradiation, and has stronger antibacterial performance. The prepared double-antibacterial visible light catalytic fresh-keeping material can be used in the visible lightGood photocatalysis antibacterial effect is generated under light, and Ag with positive charge simultaneously + And can also generate electrostatic attraction with negatively charged bacteria to achieve the antibacterial effect.
Description
Technical Field
The application relates to the field of antibacterial materials, in particular to a double-antibacterial visible light catalytic fresh-keeping material and a preparation method thereof.
Background
The refrigerator has a refrigerator freezer or refrigerator which is required to have an antibacterial property in a state where the refrigerator freezer or refrigerator is in a high humidity and closed state and bacteria are liable to grow. The photocatalysis antibacterial technology of the refrigerator mostly utilizes an ultraviolet device to achieve the antibacterial effect, but ultraviolet irradiation can damage skin, eyes and the like of a person, so that the photocatalysis antibacterial technology is not only harmful to human health, but also can damage the aging of parts of the refrigerator, and is not beneficial to the use of the refrigerator.
In recent years, application of photocatalysis antibacterial technology in refrigerator to realize antibacterial function is frequently and frequently used, and TiO 2 As a photocatalyst antibacterial catalyst, the photocatalyst has the characteristics of strong chemical stability, excellent photocatalytic performance, high oxidizing property, safety, no toxicity, no pollution and low price, and has wide application in the fields of antibiosis, mildew prevention and the like. However, tiO 2 The material is a wide forbidden band semiconductor, and photo-generated electrons and holes generated in the material are easy to be combined, so that the quantum efficiency and the catalytic activity are reduced, and the TiO is restricted 2 The application of photocatalysis and antibiosis can not be widely applied to various scenes.
Disclosure of Invention
The application provides a double-antibacterial visible light catalytic fresh-keeping material and a preparation method thereof, which solve the problem of TiO 2 The material has the defects in the aspects of light response range and photocatalysis antibacterial performance, and can not be widely applied to the problems of various scenes.
In one aspect, the application provides a dual antibacterial visible light catalytic fresh-keeping material, which comprises the following components:
130-150 parts of carrier resin, 1-4 parts of modified titanium dioxide composite antibacterial agent, 1-5 parts of plasticizer and 0.5-1 part of stabilizer1-3 parts of a linking agent; wherein the modified titanium dioxide composite antibacterial agent is Ag+/Nano-TiO 2 Nanomaterial, the Ag+/Nano-TiO 2 The grain diameter of the nanometer material is 20-50 nm.
The double antibacterial visible light catalytic fresh-keeping material prepared by the application utilizes Nano-TiO 2 Has photocatalysis characteristic, can further enlarge the photoresponse range after being compounded with Ag ions, achieves the photocatalysis effect under visible light, and further overcomes the defect of TiO 2 The photocatalyst has the defect of photocatalysis effect only under ultraviolet light, and meanwhile, nano-TiO 2 With Ag + Can produce double antibacterial effect after compounding, effectively strengthen the prepared Ag + /Nano-TiO 2 The antibacterial performance of the PS visible light catalytic antibacterial plastic under visible light greatly improves the application possibility of the visible light catalytic antibacterial plastic on household appliances such as refrigerator cabinets and the like.
In some possible implementations, the carrier resin is a polystyrene carrier resin and the plasticizer is a dioctyl terephthalate plasticizer.
In some possible implementations, the stabilizer is a calcium zinc heat stabilizer and the coupling agent is a silane coupling agent.
On the other hand, the application also provides a preparation method of the double-antibacterial visible light catalytic fresh-keeping material, which comprises the following steps:
preparing n-heptanoic acid and ethanol into a first solution, and preparing butyl titanate and ethanol into a second solution;
stirring and mixing the first solution and the second solution at room temperature to obtain TiO 2 A colloid;
the TiO is treated with 2 Removing supernatant by colloid centrifugation, and annealing at high temperature to obtain Nano-TiO 2 A material;
to said Nano-TiO 2 Adding sodium borohydride into the solution obtained by mixing the material and silver nitrate to obtain suspension;
washing the suspension, and vacuum drying to obtain Ag+/Nano-TiO 2 A nanomaterial;
the carrier resin, ag+/Nano-TiO 2 The nano material, the plasticizer, the stabilizer and the coupling agent are uniformly mixed and granulated by a granulator to obtain the double-antibacterial visible light catalytic fresh-keeping material.
In some possible implementations, the volume ratio of n-heptanoic acid to ethanol is 1:500, the volume ratio of butyl titanate to ethanol is 1:6.
in some possible implementations, the TiO is 2 Centrifuging colloid to remove supernatant, and concentrating the TiO 2 The colloid is dried for 5 to 10 hours at the temperature of 50 to 60 ℃.
In some possible implementations, the Nano-TiO is obtained by annealing at high temperature 2 In the material process, the annealing temperature is 500-600 ℃, the annealing time is 1-2 h, and the heating rate is 5-10 ℃/min.
In some possible implementations, the Nano-TiO 2 The mass ratio of the material to sodium borohydride is 2:1.
In some possible implementations, the suspension is washed and then dried in vacuum at a temperature of 80-100 ℃ for 15-20 hours.
In some possible implementations, six times of temperature control are performed in the process of granulating by a granulator to obtain the double-antibacterial visible light catalytic fresh-keeping material; wherein, the temperature of six times temperature control is in proper order: 180-190 ℃, 190-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃.
From the above, the application provides a double-antibacterial visible light catalytic fresh-keeping material and a preparation method thereof, wherein the TiO is prepared by a sol-gel method 2 Is prepared into nano particles and then is mixed with Ag + Composite preparation of Ag + /Nano-TiO 2 The composite antibacterial agent adopts PS as matrix resin and Ag + /Nano-TiO 2 The composite antibacterial agent is a photocatalysis antibacterial agent, so that Ag is prepared + /Nano-TiO 2 PS composite material, ag ion and anatase type TiO 2 The composite of the nano particles can endow the matrix resin with excellent antibacterial property and effectively improve TiO 2 In the light response wavelength range where no ultraviolet irradiation is requiredHas photocatalysis effect under the condition, and can generate strong antibacterial property. Prepared Ag + /Nano-TiO 2 The PS composite plastic has double antibacterial effect, not only can generate good photocatalysis antibacterial effect under visible light, but also can generate Ag with positive charge + And can also generate electrostatic attraction with negatively charged bacteria to achieve the antibacterial effect.
Drawings
In order to more clearly illustrate the technical solutions of the present application, the drawings that are needed in the embodiments will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 shows Ag obtained in example 1 of the examples of this application + /Nano-TiO 2 An electron microscope image of the composite antibacterial agent;
FIG. 2 shows the Ag obtained in example 2 of the examples of this application + /Nano-TiO 2 Fluorescent imaging diagram of the composite antibacterial agent;
FIG. 3 shows the Ag obtained in example 2 of the examples of this application + /Nano-TiO 2 Fluorescent imaging diagram of the composite antibacterial agent.
Detailed Description
In order to facilitate the technical solution of the application, some concepts related to the present application will be described below first.
In recent years, the application of the photocatalytic antibacterial technology is frequent, and in the aspect of household appliances such as refrigerator cabinets, the refrigerator is frozen and refrigerated in a state that bacteria are easy to grow in a sealed manner, so that the photocatalytic antibacterial technology is increasingly used on plastic parts such as refrigerator cabinets, and the household appliances such as refrigerators and the like with antibacterial functions are favored by consumers.
TiO 2 As a photocatalyst antibacterial catalyst, the photocatalyst has the characteristics of strong chemical stability, excellent photocatalytic performance, high oxidizing property, safety, no toxicity, no pollution and low price, and has wide application in the fields of antibiosis, mildew resistance and the like, in particular to anatase type TiO 2 Its performance is most excellent. Anatase TiO 2 While exhibiting excellent photocatalytic performance, there are many limitations in that the range of visible light response is small, and only under ultraviolet light having a light source wavelength of less than 387nm, tiO 2 Can be excited by light, the energy of ultraviolet light is about 4 percent of the energy of sunlight, and the TiO is greatly limited 2 Resulting in a range of use of TiO 2 The material has the defects in the aspects of light response range and photocatalysis antibacterial property, and can not be widely applied to various scenes.
In order to solve the technical problems, the application provides a double-antibacterial visible light catalytic fresh-keeping material and a preparation method thereof, and Nano-TiO is utilized 2 Has photocatalysis characteristic, can further enlarge the photoresponse range after being compounded with Ag ions, achieves the photocatalysis effect under visible light, and further overcomes the defect of TiO 2 The photocatalyst has the defect of photocatalysis effect only under ultraviolet light, and meanwhile, nano-TiO 2 Can produce double antibacterial effect after being compounded with Ag+, effectively enhancing the prepared Ag+/Nano-TiO 2 The antibacterial performance of the PS double-antibacterial visible light catalytic fresh-keeping material under visible light enables the application of the visible light catalytic fresh-keeping material in various scenes.
In some embodiments, the dual antimicrobial visible light catalytic fresh-keeping material provided by the application comprises the following components:
130-150 parts of carrier resin, 1-4 parts of modified titanium dioxide composite antibacterial agent, 1-5 parts of plasticizer, 0.5-1 part of stabilizer and 1-3 parts of coupling agent; wherein the modified titanium dioxide composite antibacterial agent is Ag+/Nano-TiO 2 Nanomaterial, the Ag+/Nano-TiO 2 The grain diameter of the nanometer material is 20-50 nm.
In some embodiments, the carrier resin is a polystyrene carrier resin, the plasticizer is a dioctyl terephthalate plasticizer, the stabilizer is a calcium zinc heat stabilizer, and the coupling agent is a silane coupling agent.
As a thermoplastic engineering resin with excellent performance, polystyrene (PS) has good chemical corrosion resistance, strong rigidity and good fluidity, and is easy to process and form.
The antibacterial effect of the double antibacterial visible light catalytic fresh-keeping material is mainly based on Ag + And anatase type TiO 2 Nanoparticles, the photocatalytic system has the photocatalytic effect of TiO 2 。
(1)Nano-TiO 2 Is used for photocatalysis and antibiosis: ag (silver) + /Nano-TiO 2 Nano-TiO in composite antibacterial agent 2 Active negatively charged electrons and positively charged holes can be generated on the surface of the material under the illumination condition to form electron-hole pairs, and the electron-hole pairs and the surrounding oxygen and air are subjected to catalytic reaction, so that the generated hydroxyl free radicals (OH) and active oxygen free radicals (O) products are subjected to oxidation reaction with organic matters in bacteria to generate CO 2 And H 2 O, to achieve the effect of killing bacteria in a short time.
(2)Ag + Is contacted with the antibacterial mode: when Ag is + Contact with bacterial cells and react with Ag + /Nano-TiO 2 Ag in composite antibacterial agent + The bacteria are positively charged, the bacteria are negatively charged, and the positive and negative charges are attracted to and attached to cell membranes, so that normal physiological metabolic activities of the cells are disturbed, and the bacteria finally die. Ag (silver) + It can also penetrate the bacterial cell membrane to enter the cell, react with the coloured base in the cell, cause the protein in the cell to coagulate, and also kill the bacteria.
In some embodiments, the application also provides a preparation method of the double-antibacterial visible light catalytic fresh-keeping material, firstly preparing Ag + /Nano-TiO 2 Antibacterial agent, then the carrier resin and Ag are added + /Nano-TiO 2 The nano material, the plasticizer, the stabilizer and the coupling agent are mixed and granulated to obtain the double-antibacterial visible light catalytic fresh-keeping material. Wherein the Ag is + /Nano-TiO 2 The preparation method of the composite antibacterial agent comprises the following steps: tiO is prepared by a sol-gel method 2 Preparing into nano particles, and adopting oxidation-reduction method to make Ag + And Nano-TiO 2 And (5) compounding.
Concerning Ag + /Nano-TiO 2 The preparation method of the composite antibacterial agent comprises the following steps:
preparing n-heptanoic acid and ethanol into a first solution, and preparing butyl titanate and ethanol into a second solution; wherein, the volume ratio of the n-heptanoic acid to the ethanol is 1:500, the volume ratio of butyl titanate to ethanol is 1:6, preparing a base material;
stirring and mixing the first solution and the second solution at room temperature to obtain TiO 2 A colloid;
the TiO is treated with 2 Centrifuging the colloid to remove supernatant, and drying the supernatant at 50-60 ℃ for 5-10 h;
drying the TiO 2 Annealing the colloid at high temperature to obtain Nano-Nano-TiO 2 A material; wherein the annealing temperature is 500-600 ℃, the annealing time is 1-2 h, and the heating rate is 5-10 ℃/min;
to said Nano-TiO 2 Adding sodium borohydride into the solution obtained by mixing the material and silver nitrate to obtain suspension; wherein, the nanometer Nano-TiO 2 The mass ratio of the material to the sodium borohydride is 2:1;
washing the suspension, and vacuum drying to obtain Ag + /Nano-TiO 2 A nanomaterial; wherein the temperature of vacuum drying is 80-100 ℃ and the drying time is 15-20 h;
the preparation method of the double-antibacterial visible light catalytic fresh-keeping material comprises the following steps:
the carrier resin and Ag + /Nano-TiO 2 The nano material, the plasticizer, the stabilizer and the coupling agent are uniformly mixed and granulated by a granulator to obtain the double-antibacterial visible light catalytic fresh-keeping material.
Firstly, placing PS granules into a forced air drying oven at 80 ℃ to be dried for 10 hours, and then, proportionally placing the PS granules and Ag + /Nano-TiO 2 Uniformly mixing a composite antibacterial agent, a plasticizer, a stabilizer and a coupling agent, extruding in a double-screw extruder, and granulating the composite material by using a granulator to obtain Ag + /Nano-TiO 2 The PS visible light catalyzed antibacterial plastic is dried by a forced air oven for standby. Wherein the operating temperature of each section of the twin-screw extruder can be controlled so that Ag + /Nano-TiO 2 The antibacterial effect of the composite antibacterial agent can be fully exerted and released, and each group is ensuredThe components can be uniformly mixed and dispersed so as to keep each property of the prepared visible light catalytic antibacterial plastic stable and uniform.
In some embodiments, six times of temperature control are performed in the process of granulating by a granulator to obtain the double antibacterial visible light catalytic fresh-keeping material; wherein, the temperature of six times temperature control is in proper order: 180-190 ℃, 190-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃.
The preparation process of the double antibacterial visible light catalytic fresh-keeping material provided by the application is as follows: first, ag is prepared + /Nano-TiO 2 The composite antibacterial agent is prepared by placing PS granules into a forced air drying oven at 80 ℃ for drying for 10 hours, and then placing PS granules and Ag according to a certain proportion + /Nano-TiO 2 Uniformly mixing the composite antibacterial agent, the plasticizer, the stabilizer and the coupling agent, and granulating in a double-screw extruder to obtain the Ag + /Nano-TiO 2 The PS visible light catalyzed antibacterial plastic is dried by a forced air oven for standby. And finally, putting the mixed materials into a double-screw extruder, and extruding the mixed materials into granules after full melting and compounding, wherein the temperature range of each section of the double-screw extruder is 180-220 ℃.
The double antibacterial visible light catalytic fresh-keeping material prepared by the application utilizes Nano-TiO 2 Has photocatalysis characteristic, can further enlarge the photoresponse range after being compounded with Ag ions, achieves the photocatalysis effect under visible light, and further overcomes the defect of TiO 2 The photocatalyst has the defect of photocatalysis effect only under ultraviolet light, and meanwhile, nano-TiO 2 With Ag + Can produce double antibacterial effect after compounding, effectively strengthen the prepared Ag + /Nano-TiO 2 The antibacterial performance of the PS visible light catalytic antibacterial plastic under visible light greatly improves the application possibility of the visible light catalytic antibacterial plastic on household appliances such as refrigerator cabinets and the like.
Examples of the preparation method of the double antibacterial visible light catalytic fresh-keeping material are provided below.
Example 1
The double antibacterial visible light catalytic fresh-keeping material comprises the following components in parts by weight: carrier tree130g of grease and modified titanium dioxide composite antibacterial agent (Ag) + /Nano-TiO 2 1g of composite antibacterial agent), 1g of plasticizer, 0.5g of stabilizer, 1g of coupling agent, wherein the carrier resin is PS resin, the plasticizer is DOTP plasticizer, the stabilizer is calcium zinc heat stabilizer, and the coupling agent is coupling agent KH550.
The preparation method of the visible light catalytic antibacterial plastic comprises the following specific steps: the PS granules are firstly put into a blast drying oven at 80 ℃ to be dried for 10 hours, and then the PS granules and Ag are dried + /Nano-TiO 2 Uniformly mixing the composite antibacterial agent, the plasticizer, the stabilizer and the coupling agent, stirring and mixing for 30 minutes at 40 ℃, extruding in a double-screw extruder, and granulating the composite material by using a granulator to obtain the Ag + /Nano-TiO 2 The PS visible light catalytic antibacterial plastic is dried by a blast oven for standby, and the temperature ranges of each section of the double-screw extruder are 180-190 ℃, 190-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively.
Ag + /Nano-TiO 2 The preparation of the composite antibacterial agent is as follows:
(1)Nano-TiO 2 preparation
According to 1:500 (v/v) n-heptanoic acid and ethanol to prepare a mixed first solution, butyl titanate and ethanol 1:6 (v/v) preparing a mixed second solution, then rapidly adding the solution B into the solution A under the condition of intense stirring, then adding 8mL of deionized water, and intense stirring for 2h at room temperature to obtain the TiO 2 And (5) colloid. Then TiO is added 2 Continuously centrifuging colloid for 2 times in a high-speed centrifuge, discarding supernatant, washing colloid with anhydrous ethanol, vacuum drying at 60deg.C for 10 hr, annealing at 500deg.C for 2 hr, and heating at a rate of 5deg.C/min to obtain nanometer Nano-TiO 2 。
(2)Ag + /Nano-TiO 2 Preparation of composite antibacterial agent
Taking 1g Nano-TiO 2 And an amount of 0.1mol/L AgNO 3 The solution was mixed in 500mL deionized water and 0.5g NaBH was added 4 Filtering the suspension after 3 hours of reaction, washing the suspension with deionized water and absolute ethyl alcohol for multiple times, and then drying the suspension in vacuum at 80 ℃ for 20 hours to obtainAg + /Nano-TiO 2 A solid composite antimicrobial, as shown in figure 1.
Example 2
The double antibacterial visible light catalytic fresh-keeping material comprises the following components in parts by weight: carrier resin 140g, ag + /Nano-TiO 2 2.5g of composite antibacterial agent, 2.5g of plasticizer, 0.75g of stabilizer, 1.5g of coupling agent, wherein the carrier resin is PS resin, the plasticizer is DOTP plasticizer, the stabilizer is calcium zinc heat stabilizer, and the coupling agent is coupling agent KH550.
The preparation method of the visible light catalytic antibacterial plastic comprises the following specific steps: the PS granules are firstly put into a blast drying oven at 80 ℃ to be dried for 10 hours, and then the PS granules and Ag are dried + /Nano-TiO 2 Uniformly mixing the composite antibacterial agent, the plasticizer, the stabilizer and the coupling agent, stirring and mixing for 30 minutes at 50 ℃, extruding in a double-screw extruder, and granulating the composite material by using a granulator to obtain the Ag + /Nano-TiO 2 The PS visible light catalytic antibacterial plastic is dried by a blast oven for standby, and the temperature ranges of each section of the double-screw extruder are 180-190 ℃, 190-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively.
Ag + /Nano-TiO 2 The preparation of the composite antibacterial agent is as follows:
(1)Nano-TiO 2 preparation
According to 1:500 (v/v) n-heptanoic acid and ethanol to prepare a mixed first solution, butyl titanate and ethanol 1:6 (v/v) preparing a mixed second solution, then rapidly adding the solution B into the solution A under the condition of intense stirring, then adding 8mL of deionized water, and intense stirring for 2h at room temperature to obtain the TiO 2 And (5) colloid. Then TiO is added 2 Continuously centrifuging colloid for 2 times in a high-speed centrifuge, discarding supernatant, washing colloid with anhydrous ethanol, vacuum drying at 60deg.C for 10 hr, annealing at 500deg.C for 2 hr, and heating at a rate of 5deg.C/min to obtain nanometer Nano-TiO 2 。
(2)Ag + /Nano-TiO 2 Preparation of composite antibacterial agent
Taking 1g Nano-TiO 2 And an amount of 0.1mol/L AgNO 3 The solution was mixed in 500mL deionized water and 0.5g NaBH was added 4 Filtering the suspension after 3 hours of reaction, washing the suspension with deionized water and absolute ethyl alcohol for multiple times, and then vacuum drying the suspension for 20 hours at 80 ℃ to obtain Ag + /Nano-TiO 2 Solid composite antibacterial agent. For Ag + /Nano-TiO 2 The solid composite antibacterial agent performs fluorescent imaging of cells by nanoparticle-labeled antibodies, which is a method of binding nanoparticles to specific antibodies, as shown in fig. 2 and 3, and the activity of cells and the localization of biomolecules can be visualized by the above-mentioned sensitive fluorescent signals.
Example 3
The double antibacterial visible light catalytic fresh-keeping material comprises the following components in parts by weight: 150g of carrier resin and Ag + /Nano-TiO 2 4g of composite antibacterial agent, 5g of plasticizer, 1g of stabilizer, 3g of coupling agent, wherein the carrier resin is PS resin, the plasticizer is DOTP plasticizer, the stabilizer is calcium zinc heat stabilizer, and the coupling agent is coupling agent KH550.
The preparation method of the visible light catalytic antibacterial plastic comprises the following specific steps: the PS granules are firstly put into a blast drying oven at 80 ℃ to be dried for 10 hours, and then the PS granules and Ag are dried + /Nano-TiO 2 Uniformly mixing the composite antibacterial agent, the plasticizer, the stabilizer and the coupling agent, stirring and mixing for 30 minutes at 60 ℃, extruding in a double-screw extruder, and granulating the composite material by using a granulator to obtain the Ag + /Nano-TiO 2 The PS visible light catalytic antibacterial plastic is dried by a blast oven for standby, and the temperature ranges of each section of the double-screw extruder are 180-190 ℃, 190-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively.
Ag + /Nano-TiO 2 The preparation of the composite antibacterial agent is as follows:
(1)Nano-TiO 2 preparation
According to 1:500 (v/v) n-heptanoic acid and ethanol to prepare a mixed first solution, butyl titanate and ethanol 1:6 (v/v) to prepare a mixed second solution, then B was rapidly added to the A solution with vigorous stirring, then 8mL of deionized water was addedWater is vigorously stirred for 2 hours at room temperature, thus obtaining TiO 2 And (5) colloid. Then TiO is added 2 Continuously centrifuging colloid for 2 times in a high-speed centrifuge, discarding supernatant, washing colloid with anhydrous ethanol, vacuum drying at 60deg.C for 10 hr, annealing at 500deg.C for 2 hr, and heating at a rate of 5deg.C/min to obtain nanometer Nano-TiO 2 。
(2)Ag + /Nano-TiO 2 Preparation of composite antibacterial agent
Taking 1g Nano-TiO 2 And an amount of 0.1mol/L AgNO 3 The solution was mixed in 500mL deionized water and 0.5g NaBH was added 4 Filtering the suspension after 3 hours of reaction, washing the suspension with deionized water and absolute ethyl alcohol for multiple times, and then vacuum drying the suspension for 20 hours at 80 ℃ to obtain Ag + /Nano-TiO 2 Solid composite antibacterial agent.
Is Ag with + /Nano-TiO 2 The photocatalysis antibacterial plastic prepared by the composite antibacterial agent has the effect comparison, and adopts common unmodified TiO 2 Materials preparation of photocatalytic antimicrobial plastics, comparative examples are as follows:
ordinary TiO 2 The material visible light catalytic antibacterial plastic comprises the following components in parts by weight: carrier resin 160g, tiO 2 5g of material, 5g of plasticizer, 1g of stabilizer, 3g of coupling agent, wherein the carrier resin is PS resin, the plasticizer is DOP plasticizer, the stabilizer is calcium zinc heat stabilizer, and the coupling agent is coupling agent KH550.
TiO 2 The specific preparation steps of the photocatalysis antibacterial plastic are as follows: firstly, placing PS granules in a forced air drying oven at 80 ℃ for drying for 10 hours, then uniformly mixing the PS granules, a plasticizer, a stabilizer and a coupling agent, stirring and mixing for 30 minutes at 60 ℃, extruding in a double-screw extruder, and granulating the composite material by using a granulator to obtain TiO 2 The visible light catalytic antibacterial plastic is dried by a blast oven for standby, and the temperature ranges of each section of the double screw extruder are 180-190 ℃, 190-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃ respectively.
The photocatalytic antibacterial plastics obtained in examples 1, 2 and 3 and comparative example are respectively subjected to corresponding antibacterial performance tests under the conditions of continuous irradiation of visible light (natural light) for 10 hours at room temperature, and the strains selected in the antibacterial tests are escherichia coli and staphylococcus aureus required by national standards, and average values of 4 groups are respectively tested, and the test method is tested according to special requirements of antibacterial, degerming and purifying function antibacterial materials of household and similar-purpose appliances in GB 21551.2-2010, and the results are shown in the following table:
| name \antibacterial rate | Staphylococcus aureus | Coli bacterium |
| Example 1 | 93.8％ | 91.7％ |
| Example 2 | 97.5％ | 96.9％ |
| Example 3 | 99.9％ | 99.5％ |
| Comparative example | 85.9％ | 84.6％ |
As can be seen from the data in the table: using Ag + /Nano-TiO 2 Ag prepared from composite antibacterial agent + /Nano-TiO 2 The PS visible light catalytic antibacterial plastic has the photocatalysis effect under the condition without ultraviolet irradiation, can generate the antibacterial effect under the visible light irradiation, and is more remarkable in that Ag ions and anatase type TiO 2 The nano ion composition can endow the matrix resin with excellent antibacterial property, so that the prepared Ag + /Nano-TiO 2 The PS composite plastic has double antibacterial effect and Nano-TiO under visible light 2 Is used for photocatalysis and antibiosis and Ag with positive charge + Synergistic antibacterial effect with electrostatic attraction of negatively charged bacteria, ag is adopted + /Nano-TiO 2 The antibacterial rate of the antibacterial plastic prepared by the composite antibacterial agent is greatly improved, and the antibacterial plastic is along with Ag + /Nano-TiO 2 The higher the concentration of the compound antibacterial agent, the better the antibacterial effect. Wherein, the antibacterial effect of the strain is less than that of staphylococcus aureus under the influence of a thick peptidoglycan layer cell wall on the surface of escherichia coli.
From the above examples, the present application provides a dual antibacterial visible light catalytic fresh-keeping material and a preparation method thereof, wherein a sol-gel method is adopted to first mix TiO 2 Is prepared into nano particles and then is mixed with Ag + Composite preparation of Ag + /Nano-TiO 2 The composite antibacterial agent adopts PS as matrix resin and Ag + /Nano-TiO 2 The composite antibacterial agent is a photocatalysis antibacterial agent, so that Ag is prepared + /Nano-TiO 2 PS composite material, ag ion and anatase type TiO 2 The composite of the nano particles can endow the matrix resin with excellent antibacterial property and effectively improve TiO 2 Has a photocatalytic effect without ultraviolet irradiation in the light response wavelength range, and can generate strong antibacterial performance. Prepared Ag + /Nano-TiO 2 The PS composite plastic has double antibacterial effect, not only can generate good photocatalysis antibacterial effect under visible light, but also can generate Ag with positive charge + And can also generate electrostatic attraction with negatively charged bacteria to achieve the antibacterial effect.
Claims (10)
1. The double-antibacterial visible light catalytic fresh-keeping material is characterized by comprising the following components:
130-150 parts of carrier resin, 1-4 parts of modified titanium dioxide composite antibacterial agent, 1-5 parts of plasticizer, 0.5-1 part of stabilizer and 1-3 parts of coupling agent; wherein the modified titanium dioxide composite antibacterial agent is Ag + /Nano-TiO 2 Nanomaterial, the Ag + /Nano-TiO 2 The grain diameter of the nanometer material is 20-50 nm.
2. The dual antimicrobial visible light catalytic fresh-keeping material according to claim 1, wherein the carrier resin is a polystyrene carrier resin and the plasticizer is a dioctyl terephthalate plasticizer.
3. The dual antimicrobial visible light catalytic fresh-keeping material according to claim 1, wherein the stabilizer is a calcium zinc heat stabilizer and the coupling agent is a silane coupling agent.
4. The preparation method of the double-antibacterial visible light catalytic fresh-keeping material is characterized by comprising the following steps of:
preparing n-heptanoic acid and ethanol into a first solution, and preparing butyl titanate and ethanol into a second solution;
stirring and mixing the first solution and the second solution at room temperature to obtain TiO 2 A colloid;
the TiO is treated with 2 Removing supernatant by colloid centrifugation, and annealing at high temperature to obtain Nano-TiO 2 A material;
to said Nano-TiO 2 Adding sodium borohydride into the solution obtained by mixing the material and silver nitrate to obtain suspension;
washing the suspension, and vacuum drying to obtain Ag + /Nano-TiO 2 A nanomaterial;
the carrier resin and Ag + /Nano-TiO 2 The nano material, the plasticizer, the stabilizer and the coupling agent are uniformly mixed and granulated by a granulator to obtain the double-antibacterial visible light catalytic fresh-keeping material.
5. The method for preparing the visible light catalytic fresh-keeping material according to claim 4, wherein the volume ratio of n-heptanoic acid to ethanol is 1:500, the volume ratio of butyl titanate to ethanol is 1:6.
6. the method for preparing a fresh-keeping material according to claim 4, wherein the TiO2 colloid is centrifuged to remove supernatant, and the TiO is then dried 2 The colloid is dried for 5 to 10 hours at the temperature of 50 to 60 ℃.
7. The method for preparing the visible light catalytic fresh-keeping material according to claim 6, wherein the Nano-TiO is obtained by annealing at high temperature 2 In the material process, the annealing temperature is 500-600 ℃, the annealing time is 1-2 h, and the heating rate is 5-10 ℃/min.
8. The method for preparing a visible light catalytic fresh-keeping material according to claim 4, wherein the Nano-TiO 2 The mass ratio of the material to sodium borohydride is 2:1.
9. The method for preparing a fresh-keeping material according to claim 4, wherein the temperature of vacuum drying is 80-100 ℃ and the drying time is 15-20 h in the vacuum drying process after washing the suspension.
10. The method for preparing a visible light catalytic fresh-keeping material according to claim 4, wherein the temperature is controlled six times in the process of granulating by a granulator to obtain the double antibacterial visible light catalytic fresh-keeping material; wherein, the temperature of six times temperature control is in proper order: 180-190 ℃, 190-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ and 215-220 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311495908.XA CN117487284A (en) | 2023-11-10 | 2023-11-10 | Dual-antibacterial visible light catalytic fresh-keeping material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311495908.XA CN117487284A (en) | 2023-11-10 | 2023-11-10 | Dual-antibacterial visible light catalytic fresh-keeping material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117487284A true CN117487284A (en) | 2024-02-02 |
Family
ID=89679725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311495908.XA Pending CN117487284A (en) | 2023-11-10 | 2023-11-10 | Dual-antibacterial visible light catalytic fresh-keeping material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117487284A (en) |
-
2023
- 2023-11-10 CN CN202311495908.XA patent/CN117487284A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101731272B (en) | Method for preparing antibacterial nanometer silver colloid | |
| CN110804247B (en) | Chitosan microsphere-loaded nano-silver antibacterial polypropylene material, composite antibacterial agent and preparation method thereof | |
| CN108690263A (en) | A kind of antibacterial polyolefin and preparation method thereof | |
| CN103131030A (en) | Cellulose/sliver/silver chloride composite material and preparation method thereof | |
| CN1729787A (en) | Liquid nanometer simple substance silver antibacterial agent and preparation method thereof | |
| CN112574510A (en) | Antibacterial ultraviolet aging resistant modified PP composite material and preparation method thereof | |
| WO2017092233A1 (en) | Antibacterial polyester fiber based on silver-containing zirconium phosphate, and method for preparation thereof | |
| CN113637232B (en) | Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof | |
| CN111955479B (en) | Silver-containing antibacterial liquid and preparation method thereof | |
| KR100587465B1 (en) | Inorganic antibiotic agent with silver and thermal plastic resin master batch containing its | |
| CN109135054B (en) | Antibacterial flame-retardant polypropylene pipe and preparation method thereof | |
| CN103920517A (en) | Composite visible light photocatalyst and its preparation method | |
| CN114085428A (en) | Antibacterial agent for plastic modification and preparation method thereof | |
| CN112795098A (en) | Antibacterial plastic and preparation method thereof | |
| CN114885957A (en) | Composite antibacterial material | |
| CN102326585B (en) | Slowly-released silver oxide (AgO) microcapsule antimicrobial and preparation method thereof | |
| CN114437442A (en) | Visible light catalytic antibacterial plastic and preparation method thereof | |
| CN110527756A (en) | A kind of environment-friendly highly efficient leather nano antibacterial agent and its preparation method and application | |
| CN117487284A (en) | Dual-antibacterial visible light catalytic fresh-keeping material and preparation method thereof | |
| CN113040170B (en) | Antibacterial agent, preparation method thereof and antibacterial composition | |
| CN103193939A (en) | Preparation method for polyolefin film with anti-bacterial function | |
| CN103012962A (en) | Preparation method of novel nano Ag/TiO2 modified antibacterial and flame resistant polypropylene plastic | |
| CN114158569B (en) | Black talc-based antibacterial agent and preparation method and application thereof | |
| CN109370011A (en) | A kind of food antimicrobial plastic bag material and preparation method thereof | |
| KR20220055637A (en) | Deodorizing antimicrobial plastics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |