CN117322430A - Antibacterial material, particles, toothbrush and preparation method thereof - Google Patents
Antibacterial material, particles, toothbrush and preparation method thereof Download PDFInfo
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- CN117322430A CN117322430A CN202311569287.5A CN202311569287A CN117322430A CN 117322430 A CN117322430 A CN 117322430A CN 202311569287 A CN202311569287 A CN 202311569287A CN 117322430 A CN117322430 A CN 117322430A
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- shell
- toothbrush
- chitosan
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000002245 particle Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001661 Chitosan Polymers 0.000 claims abstract description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 235000020637 scallop Nutrition 0.000 claims abstract description 18
- 241000237509 Patinopecten sp. Species 0.000 claims abstract description 17
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- 238000004519 manufacturing process Methods 0.000 claims description 5
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- 238000001020 plasma etching Methods 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000002688 persistence Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 241000894006 Bacteria Species 0.000 description 19
- 235000020639 clam Nutrition 0.000 description 17
- 238000004659 sterilization and disinfection Methods 0.000 description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 241000237502 Ostreidae Species 0.000 description 6
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- 239000011575 calcium Substances 0.000 description 5
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
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- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
- A46D1/006—Antimicrobial, disinfectant bristles, handle, bristle-carrier or packaging
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
- A46D1/02—Bristles details
- A46D1/0207—Bristles characterised by the choice of material, e.g. metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0608—PE, i.e. polyethylene characterised by its density
- B29K2023/0633—LDPE, i.e. low density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0011—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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention relates to an antibacterial material, particles, a toothbrush and a preparation method thereof, wherein the antibacterial material comprises the following components in percentage by mass: 10-30% of at least two of scallop shell, clam shell and sinonovacula constricta lamarck shell, 15-50% of oyster shell and 30-50% of chitosan; the antibacterial toothbrush provided by the invention not only solves the problems of safety, effectiveness and persistence of functional materials, but also solves the problem of large contact angle of a bristle interface, enlarges the contact surface of a sterilizing material, increases water absorption, can effectively enlarge a bacteriostasis zone, and has better sterilizing and bacteriostasis effects.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an antibacterial material, particles, a toothbrush and a preparation method thereof.
Background
After the new toothbrush is used for four weeks, the new toothbrush is mostly placed on a wash table in a bathroom, bacteria are easy to breed due to high air humidity in the bathroom, the toothbrush is polluted, medical clinical researches prove that the number of bacteria carried by the toothbrush can reach hundreds of thousands after the toothbrush is used for about ten days, and the bacteria can be continuously increased to exist on the toothbrush along with the increase of the service time of the toothbrush, so that the new toothbrush is a potential threat to the health of a human body, and is an important factor for causing diseases, especially for people with an unhealthy immune system and performing organ transplantation operation.
The cleaning and disinfection of the toothbrush is directly related to the sanitation of the oral cavity and the health and safety of human bodies, and consumers are mainly concerned about the fact that the toothbrush is moist, not easy to dry and easy to grow bacteria in the aspect of toothbrush antibacterial. However, the antibacterial technology of toothbrushes on the market is relatively lacking, the antibacterial efficacy is achieved mainly by cleaning toothbrushes, and part of toothbrushes are also applied to single nano antibacterial technology, so that the antibacterial effect is not very remarkable, and the requirements of consumers on oral health are difficult to meet.
Accordingly, in view of the above shortcomings, there is a need to provide a new antibacterial toothbrush regimen.
Disclosure of Invention
The invention aims to solve the technical problems that the existing toothbrush is complicated and unsuitable in external sterilization, the conventional antibacterial materials and methods have insignificant effects, so that the antibacterial effect of the toothbrush is insignificant, and a novel toothbrush with antibacterial function is required to be provided, and the novel toothbrush has the effects of reliable materials, lasting effects, safety and no toxicity so as to solve the problems.
In order to solve the technical problems, in a first aspect, the invention provides an antibacterial material, which is characterized by comprising the following components in percentage by mass: 10-30% of at least two of scallop shell, clam shell and Sinonovacula constricta lamarck shell, 15-50% of oyster shell and 30-50% of chitosan.
The antibacterial material provided by the invention has the first sterilization mechanism that the molecular structure of active calcium oxide generated by shell calcination is changed, so that the ratio of the active calcium oxide to calcium oxide can not generate heat, the stability is stronger, and the antibacterial effect is more remarkable. The pH value is about 12.5, the calcined shell powder can cause charge change of bacterial cell membranes, influence the absorption of cells on nutrient substances or penetration of the cells into microbial cells, adsorb negatively charged cytoplasm in the cells, and generate flocculation, and disturb normal physiological activities of the cells so as to kill bacteria; secondly, the shell powder is calcined and adsorbed on the surface of microbial cells to form a layer of molecular film, so that nutrient substances are prevented from being transported to the cells, and the effects of sterilization and bacteriostasis are achieved; thirdly, the propagation of bacteria is inhibited by changing the pH value of the bacteria growing environment, so that the bacteriostasis effect is rapid and strong; and fourthly, calcium treatment improves the extracellular calcium level, compensates the loss of calcium in the cell wall area, and plays a role in maintaining and regulating the structure and the function of the cell wall and the cell membrane, so that the cell maintains a separation state, and further has a regulation and control effect on the whole metabolic process. The calcium has direct regulation and control effect on enzymes related to respiration, so that the respiration intensity of the calcium is reduced, and finally the antibacterial effect is achieved.
The antibacterial material provided by the invention can be carried on the surface of the material and can easily grow bacteria when the antibacterial material is in daily contact with media such as water. The antibacterial material provided by the invention can produce an antibacterial effect when bacteria or other pollutants are stained on the material. For example, when imported cold chain foods are cleared, bacteria or viruses are transmitted during transportation, and the materials can further prevent the transmission of bacteria or viruses by being added into low-pressure polyethylene packaging materials through good sterilization.
The molecular structure of the scallop shell, the clam shell, the Sinonovacula constricta shell and the oyster shell is specially changed through a high-temperature manufacturing process, and the main components are that calcium carbonate is converted into active calcium oxide and carbon dioxide. The pH value of the active calcium oxide is equal to 12.5, and the more important difference is that the active calcium oxide has higher stability, does not generate heat when meeting water, and has better and longer antibacterial effect.
The calcium oxide generated by the high-temperature treatment of different shells has different bactericidal effects, the antibacterial effects of scallops and oyster Sinonovacula constricta on gram-positive bacteria are obvious, and the antibacterial effects of clams and mussels on gram-negative bacteria are obvious. In the invention, only a plurality of shell raw materials are organically compounded, and the effects of sterilization and bacteriostasis can be complemented. One of the shells is singly used, and the sterilization effect is not obvious.
Preferably, the chitosan has a degree of deacetylation of 70% to 95%, for example, 70%, 75%, 80%, 85%, 90% or 95%.
Preferably, the molecular weight of the chitosan is less than 5000.
In the invention, chitosan and derivatives thereof mainly destroy the normal physiological functions of bacteria by acting on the cytoplasmic membranes of the bacteria so as to achieve the antibacterial effect. The cell wall of the gram-positive bacteria can be thinned, so that the enhancement of the synergistic sterilization effect of the activated calcium oxide is promoted, the cytoplasm of the gram-negative bacteria is concentrated, and the increase of the gaps is convenient for the formation of a molecular film to block the nutrient absorption of bacteria.
In the present invention, chitosan molecular chains have a compliant concept when the degree of deacetylation of chitosan is generally greater than 70%, especially greater than 75%. Since the acetyl base has larger steric hindrance, the hydrophobicity is strong, and the decrease of the deacetylation degree can cause the increase of the rigidity of the molecular chain and the enhancement of the hydrophobic effect. Therefore, when the deacetylation degree is 70%, particularly more than 75%, the viscosity of the chitosan is increased, the proportion of the glucosamine structural units exceeding 95% is higher, stronger intermolecular and intramolecular hydrogen bonds are generated, and the viscosity of the chitosan is also improved.
In a second aspect, the present invention provides a method for preparing the antibacterial material according to the first aspect, the method comprising: at least two of scallop shell, clam shell and Sinonovacula constricta shell are subjected to primary calcination, cooled and ground into powder, subjected to secondary calcination, and then mixed with oyster shell and chitosan to obtain the antibacterial material.
The above calcination was followed by pulverization to form 200 mesh powder.
Preferably, the temperature of the primary calcination is 200 to 400 ℃, and for example, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ or the like can be used.
Preferably, the time of the primary calcination is 1 to 2 hours.
Preferably, the temperature of the secondary calcination is 1000 to 1200 ℃, and for example, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or the like can be used.
Preferably, the time of the secondary calcination is 2 to 3 hours.
In the preparation process of the antibacterial material, oyster shells are generally calcined at 200 ℃.
In a third aspect, the present invention provides an antibacterial particle, wherein the antibacterial particle comprises, by mass, 10% -30% of the antibacterial material described in the first aspect, for example, 10%, 15%, 20%, 25% or 30%, and the low-density polyethylene 70% -90%, for example, 70%, 75%, 80%, 85% or 90%.
In a fourth aspect, the present invention provides a method for preparing the antibacterial particles according to the third aspect, the method comprising: and (3) putting the antibacterial material and the low-density polyethylene into an extrusion granulator, and extruding and granulating to obtain the antibacterial particles.
Preferably, the temperature of the extrusion granulator is 90 to 170 ℃, and may be 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or the like, for example.
Preferably, the diameter of the antibacterial particles is 2-3 mm.
In a fifth aspect, the present invention provides an antibacterial toothbrush, the antibacterial toothbrush comprising 10% -30% of the antibacterial particles according to the third aspect, for example 10%, 15%, 20%, 25% or 30% etc., and 70% -90% of polypropylene, for example 70%, 75%, 80%, 85% or 90% etc.
In a sixth aspect, the present invention provides a method for preparing an antibacterial toothbrush according to the fifth aspect, the method comprising: and (3) carrying out injection molding on the antibacterial particles and polypropylene to obtain the antibacterial toothbrush.
Preferably, in the injection molding of the brush head of the antibacterial toothbrush, the brush head is subjected to plasma etching.
Before the brush head is used for planting the hair, the plasma surface treatment is carried out on the hair planting position, a direct current plasma surface treatment machine is selected, the air pressure of the air nozzle is 30-200Pa, the discharge current is 50-100mA, and the ionization time is 0.2-3 seconds. The partial surface contact angle is between 30 and 45 degrees, and the surface pit roughness is caused by plasma etching, so that the bioactive substances have better sterilization and bacteriostasis effects.
In a seventh aspect, the present invention provides the use of an antimicrobial particle as described in the third aspect for the preparation of a plastic article.
The plastic product of the invention can be a children plastic toy, an infant car, an elevator button, a soft packaging bag, a plastic pipe, a beverage bottle, a mineral water bottle, an edible oil bottle, a plastic tableware, a disposable plastic cutlery box and the like.
The implementation of the invention has the following beneficial effects:
according to the antibacterial toothbrush provided by the invention, according to the problems that the toothbrush is stored in a toilet for a long time in the using process, the root parts of the bristles are wet, and the oral residues are more likely to accumulate in the bristles and are more likely to breed and reproduce, the antibacterial toothbrush not only solves the problems of safety, effectiveness and persistence of functional materials, but also solves the problem of large contact angle of the interface of the bristles, enlarges the contact surface of the antibacterial materials, increases the water absorption, can more effectively enlarge the antibacterial ring, and has better antibacterial effect.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The scallop shell, the clam shell, the Sinonovacula constricta shell and the oyster shell used in the invention can be purchased through conventional commercial channels.
Example 1
The present embodiment provides an antibacterial material
Total of scallop shell and clam shell is 20%, oyster shell is 50% and chitosan is 30%. The mass ratio of scallop shell to clam shell is 1:1.
The preparation method comprises the following steps: the scallop shell and clam shell are calcined for the first time at 300 ℃; the time is 1 hour; cooling, grinding, performing secondary calcination at 1000 ℃ for 3 hours, and mixing with the calcined oyster shell powder and chitosan to obtain the antibacterial material.
Example 2
The present embodiment provides an antibacterial material
The total amount of the fan shell and the Sinonovacula constricta shell is 30%, the oyster shell is 40%, and the chitosan is 30%. The mass ratio of the scallop shell to the Sinonovacula constricta lamarck shell is 2:1.
The preparation method comprises the following steps: the primary calcination temperature of the scallop shell and the Sinonovacula constricta shell is 200 ℃; the time is 2 hours; cooling, grinding, performing secondary calcination at 1200 ℃ for 2 hours, and mixing with the calcined oyster shell powder and chitosan to obtain the antibacterial material.
Example 3
The present embodiment provides an antibacterial material
The total amount of the clam shells is 10%, the oyster shells are 50% and the chitosan is 40%. The mass ratio of the clam shell to the Sinonovacula constricta lamarck shell is 1:2.
The preparation method comprises the following steps: the temperature of primary calcination of the clam shells is 400 ℃; the time is 2 hours; cooling, grinding, performing secondary calcination at 1000 ℃ for 1 hour, and mixing with the calcined oyster shell powder and chitosan to obtain the antibacterial material.
Example 4
The present embodiment provides an antibacterial material
The total amount of scallop shell, clam shell and Sinonovacula constricta shell is 30%, oyster shell is 30% and chitosan is 40%. The mass ratio of the scallop shell to the clam shell to the Sinonovacula constricta shell is 1:1:1.
The preparation method comprises the following steps: calcining scallop shell, clam shell and Sinonovacula constricta shell at 400 ℃; the time is 2 hours; cooling, grinding, performing secondary calcination at 1000 ℃ for 1 hour, and mixing with the calcined oyster shell powder and chitosan to obtain the antibacterial material.
Comparative example 1
The comparative example differs from example 1 in that only 20% of scallop shells were used in the comparative example, and the remainder were the same as example 1.
Comparative example 2
This comparative example differs from example 1 in that only 20% of clam shell was used in this comparative example, and the remainder was the same as example 1.
Comparative example 3
The difference between this comparative example and example 1 is that only 20% of Sinonovacula constricta lamarck shell was used in this comparative example, and the remainder was the same as example 1.
Comparative example 4
The comparative example is different from example 1 in that oyster shell was not used in the comparative example, the mass fraction of chitosan was 80%, and the rest was the same as example 1.
Comparative example 5
The comparative example differs from example 1 in that chitosan was not used, the oyster shell mass fraction was 80%, and the rest was the same as example 1.
Comparative example 6
The difference between this comparative example and example 1 is that the mass fraction of oyster shell in this comparative example is 70% and chitosan is 30%.
The antibacterial materials provided in examples 1 to 4 and comparative examples 1 to 6 above were mixed with a low density polyethylene in an amount of 20% by mass: 80% of the antibacterial agent is mixed and compounded in equal proportion, and is put into an extrusion granulator, the temperature is 150 ℃, and the diameter of extrusion particles is designed to be 3mm, so that the antibacterial particles are obtained.
The prepared antibacterial particles are subjected to performance test, and the specific test method comprises the following steps:
1. the antibacterial particles prepared in examples 1 to 4 and comparative examples 1 to 6 were subjected to secondary ultrafine grinding to 200 mesh and sieving for use.
2. Preparing antibacterial liquid. The antibacterial particles screened in the step 1 are respectively prepared into four solutions with the concentration of 0.05%,0.1%,0.5% and 1.0%.
3. Taking colibacillus and yellow grape ballsThe active bacteria of bacteria and salmonella can reach 5 multiplied by 10 5 ～5×10 6 CFU/mL was placed in 100 mL of nutrient broth and incubated in an incubator at 37℃for 24 hours.
4. The colony number is calculated on the test bacterial plate without any treatment, and each sample is measured and calculated for four concentrations to obtain the average antibacterial effect value. Calculating antibacterial effect, measuring the size of the antibacterial zone, and measuring and calculating antibacterial percentage.
The specific test results are shown in table 1 below:
TABLE 1
The experimental data obtained can be seen:
the scallop and oyster calcined has relatively similar sterilizing function, obvious effect on inhibiting gram-positive bacteria, and obvious effect on inhibiting gram-negative bacteria. Comparative example 1 has no obvious bactericidal and bacteriostatic effects on parahaemolyticus and salmonella.
In comparative example 2, the antibacterial effect against salmonella and escherichia coli was poor after calcination and compounding of clams and oysters.
In comparative example 3, the antibacterial effect against E.coli and Salmonella bacteria was poor after calcination and compounding of clam and oyster.
In comparative example 4, the antibacterial and bactericidal effects on staphylococcus aureus were not obvious.
The experiment in comparative example 5 proves that the organic acid generated by pathogenic bacteria around the teeth of the oral cavity such as streptococcus in the oral cavity lacks the neutralization balance effect, and the sterilization and bacteriostasis effects of the calcined shell cannot be fully exerted.
The antibacterial particles prepared by using the antibacterial material of example 1 are mixed with a polypropylene material according to the mass percentage of 20%: mixing the components in 80 percent, and performing injection molding to prepare the antibacterial toothbrush.
As the chitosan is the natural polysaccharide with positive charges, has good film forming property and antibacterial property and has the function of healing wounds, 1 to 2 percent of chitosan is selected to be added in the test to neutralize the organic acid generated by streptococcus stomatitis, the pH value of the oral cavity is improved, and the bacterial growth can be prevented after long-term use.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The antibacterial material is characterized by comprising the following components in percentage by mass: 10-30% of at least two of scallop shell, clam shell and Sinonovacula constricta lamarck shell, 15-50% of oyster shell and 30-50% of chitosan.
2. The antimicrobial material of claim 1, wherein the chitosan has a degree of deacetylation of 70% to 95%; the molecular weight of the chitosan is less than 5000.
3. The method for producing an antibacterial material according to claim 1 or 2, characterized in that the production method is: at least two of scallop shell, clam shell and Sinonovacula constricta shell are subjected to primary calcination, cooled and ground into powder, subjected to secondary calcination, and then mixed with oyster shell and chitosan to obtain the antibacterial material.
4. The method according to claim 3, wherein the temperature of the primary calcination is 200 to 400 ℃; the time of the primary calcination is 1-2 hours; the temperature of the secondary calcination is 1000-1200 ℃; the secondary calcination time is 2-3 hours.
5. An antibacterial particle, which is characterized in that the antibacterial particle is prepared from the antibacterial material 10-30% and low-density polyethylene 70-90% by mass percent according to any one of claims 1-2.
6. The method of producing an antibacterial particle according to claim 5, wherein the method of producing is: and (3) putting the antibacterial material and the low-density polyethylene into an extrusion granulator, and extruding and granulating to obtain the antibacterial particles.
7. The method according to claim 6, wherein the temperature of the extrusion granulator is 90 to 170 ℃; the diameter of the antibacterial particles is 2-3 mm.
8. An antibacterial toothbrush is characterized in that the raw materials for preparing the antibacterial toothbrush comprise 10-30% of antibacterial particles and 70-90% of polypropylene according to claim 5.
9. The method of manufacturing an antibacterial toothbrush according to claim 8, characterized in that the method of manufacturing is: injection molding the antibacterial particles and polypropylene to obtain the antibacterial toothbrush; in the injection molding of the brush head of the antibacterial toothbrush, the brush head is subjected to plasma etching.
10. Use of the antibacterial particles according to claim 5 for the preparation of plastic articles.
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