CN115926409A - Biological antibacterial master batch for degradable toothbrush and degradable antibacterial toothbrush handle - Google Patents
Biological antibacterial master batch for degradable toothbrush and degradable antibacterial toothbrush handle Download PDFInfo
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
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Abstract
The application provides a biological antibacterial master batch and degradable antibacterial toothbrush handle for degradable toothbrush, the raw materials of the toothbrush handle are composed of PLA and master batch in a proportion of 10-3, wherein the component proportion of the master batch is 75-91 parts of PBAT, 8-20 parts of peony root bark and 1-5 parts of chitosan, PLA does not need to participate in extrusion granulation, the physical properties of PLA can be kept, and the addition of the antibacterial agent and PBAT can be flexibly adjusted to meet the requirements of different product properties, and the master batch is formed first, so that the antibacterial agent can be uniformly dispersed in PBAT, and when the antibacterial agent and PBAT are mixed, the antibacterial agent and PBAT are uniformly dispersed in PLA again, a product with better dispersibility is obtained, the toughness of the product can be obviously improved by adding PBAT, and natural antibacterial agents are used, including plant antibacterial agent peony root bark and animal antibacterial agent chitosan, which are harmless to human bodies.
Description
The invention relates to a biodegradable antibacterial toothbrush and a production process thereof, wherein the application number of the original application is 2020114357486, the application date is 12 months and 10 days in 2020.
Technical Field
The invention belongs to the technical field of toothbrush daily necessities, and particularly relates to a biodegradable antibacterial master batch for a degradable toothbrush and a degradable antibacterial toothbrush handle.
Background
The plastic is known as one of the most powerful inventions in the 21 st century, has the characteristics of light weight, good mechanical property, strong plasticity and the like, has irreplaceable effects in various industries, brings great convenience to our lives even though the appearance of the plastic brings serious environmental problems, and because the plastic can be degraded in natural environment for hundreds of years, the discarded plastic can be accumulated to form white pollution, and the plastic drifting into the sea can also form marine garbage.
The toothbrush is an indispensable daily article in daily life of people, belongs to a fast-moving article, the service life of a common toothbrush is about 3 months, the traditional toothbrush is made of materials such as PP, PETG and PCTA, the materials are non-degradable plastics, serious environmental pollution can be caused after the toothbrush is used and discarded, and the problem can be well solved due to the occurrence of the degradable materials. In recent years, a large number of degradable plastics, such as PLA, PBS, PHA, PVA, PBAT, etc., have been developed, and compared with the conventional plastics, the properties and processing of the degradable materials are greatly different, and the difference in physical properties of the degradable materials causes the limited use thereof, and the difficulty in processing also limits the application thereof.
Therefore, applying degradable materials to a toothbrush still requires solving 2 major problems: (1) the toothbrush is used as an oral care tool, the use environment of the toothbrush needs to be constantly contacted with water, mold is easy to grow on the surface of the material, the degradation of the material is accelerated by the presence of the mold, the service life of the toothbrush is shortened, the physical performance of the toothbrush is affected, and the risk of breakage is caused; (2) PLA is used as a biodegradable material, the mechanical property of the PLA is poorer than that of the traditional material, and the performance of the PLA can be influenced by the difference of injection molding processes.
The invention provides a set of technical scheme, and can solve the problems that the toothbrush handle is easy to breed bacteria and the PLA handle has unstable toughness.
Disclosure of Invention
The invention provides a biological antibacterial master batch for a degradable toothbrush, aiming at solving the technical problems that the existing degradable toothbrush handle is easy to breed mould and has low mechanical property.
It is another object of the present invention to provide a degradable antibacterial toothbrush handle.
A biological antibacterial master batch for a degradable toothbrush comprises 75-91 parts of PBAT, 8-20 parts of peony root bark and 1-5 parts of chitosan by weight;
the preparation of the master batch comprises the following steps: the peony root bark is dried in the sun and ground to 10-100 meshes, PBAT, the ground peony root bark and chitosan are mixed and stirred, and the mixture is melted and granulated after stirring to obtain master batch.
Preferably, the chitosan has a deacetylation degree of 90% and a molecular weight of 7 × 10 4 ～8×10 4 . The chitosan can be combined with lipid protein in cell walls to denature or form a polymer film on the cell surfaces, so that the selective permeation of cells is changed, nutrients cannot enter the cells, and cell death is finally caused. The plant antibacterial agent peony root bark and the animal antibacterial agent chitosan are used in a compounding manner, are natural antibacterial agents, can improve antibacterial efficiency, are safe, non-toxic and environment-friendly, are harmless to human bodies, and are suitable for toothbrush handle manufacturing materials.
Preferably, the weight average relative molecular mass of the PBAT is 6X 10 4 ～7×10 4 . The PBAT has the characteristics of PBA and PBT, has better mechanical property, higher ductility and elongation at break, has excellent biodegradability, is a fully biodegradable plastic with excellent performance, the PBAT is used as a toughening agent of the PLA, the content of the PBAT is preferably 25-35 percent of that of the PLA, when the content of the PBAT is gradually increased, the tensile strength is gradually reduced, the elongation at break is gradually improved, but the degradation effect of the toothbrush is influenced, and when the content is less than 25 percent, the toughness of the toothbrush is reduced, and the mechanical property is poor. Directly add PBAT and PLA, its compatibility is relatively poor, is difficult to mix on the score level, and dispersion effect is relatively poor, can appear splitting phase, and this application is in order to solve the poor problem of dispersibility, makes the master batch earlier, mixes master batch and PLA again to this improves both compatibility, avoids the layering. Preferably, the PBAT is of type C1200 or 7011X, BASF, germany, and has a weight-average relative molecular mass of 6.8X 10 4 g/mol, density 1.25-1.27 g/cm 3 The melting temperature is 115-120 ℃, the glass transition temperature is-30 to-25 ℃, and the molecular mass is 6 multiplied by 10 4 ～7×10 4 Within the range, the comprehensive mechanical property of PBAT is better, as the toughening agent of PLA, can be as master batch filler medium, disperse the antibacterial agent earlier and form the master batch, and then mix with PLA through the master batch and disperse again, in order to improve PLA and antibacterial agent and PBAT's dispersion effect, can avoid the layering that appears in PBAT and PLA dispersion effect difference, and the antibacterial agent produces the reunion in PLA, cause antibacterial property and mechanical properties to descend, obtain the better product of dispersibility, but in addition through the master batch setting accurate control antibacterial agent's addition. The application provides a natural antibacterial biodegradable toothbrush with excellent mechanical property, and solves the problems that mould is easy to breed on the surface of a degradable material, the mechanical property of a toothbrush handle is reduced, and the service life is reduced.
Preferably, the fineness of the peony root bark is 10-100 meshes. The peony root bark is an extract of natural plants, and has an obvious bacteriostatic action on staphylococcus aureus, staphylococcus albus, pseudomonas aeruginosa, bacillus anthracis, proteus, streptococcus A, streptococcus B and other bacteria, the peony root bark is preferably naturally dried at a temperature of less than 60 ℃ and more than 40 ℃, the natural drying can ensure that the content loss of paeonol glycoside components (such as paeonol glycoside, paeonol C and paeonol) is minimum, and when the temperature is higher than 60 ℃, the content of the paeonol volatilized by heating is reduced along with the temperature rise, and the paeonol and the like have a certain inhibitory action on the bacteria. The peony root bark is ground to 10-100 meshes, the peony root bark can be refined and can be better dispersed in PBAT, the micro-dispersibility of the antibacterial agent is improved, the antibacterial master batch with high antibacterial agent concentration is prepared by stirring, melting, extruding and granulating, and then subsequent processing is carried out, in the whole process, the antibacterial agent is dispersed again in the subsequent processing process, so that an antibacterial product with better micro-dispersibility than that of a direct blending method is obtained, the whole dispersibility is good, only a small amount of agglomeration exists, the biodegradable plastic has good degradability, can be naturally decomposed without depending on illumination after being discarded, and the method is suitable for the scene of daily discarded plastics.
The degradable antibacterial toothbrush handle comprises the master batch and PLA in a mass ratio of 1-3, wherein the master batch and the PLA are mixed and dried in the brush handle according to the mass ratio, and the mixture is dried and then is subjected to injection molding to obtain the degradable antibacterial toothbrush handle.
The application provides a biodegradable degradable antibacterial toothbrush handle, the toothbrush handle raw materials are composed of PLA and master batch in a ratio of 10 to 1, wherein the master batch component ratio is 75 to 91 parts of PBAT, 8 to 20 parts of peony root bark and 1 to 5 parts of chitosan, the peony root bark, the chitosan and the PBAT are mixed and then melted and granulated to form the master batch, then the master batch and the PLA are mixed and then injected to obtain the toothbrush handle, because the PLA accounts for more than 70 percent of the total component ratio, the PLA does not need to participate in the extrusion and granulation first, the physical property of the PLA can be kept, the influence of the PLA on the mechanical property due to the secondary processing of the extrusion and granulation is avoided, in addition, the PLA is prepared and added into the master batch, the addition amount of the antibacterial agent and the PBAT can be flexibly adjusted to adapt to different product performance requirements, and the peony root bark, the chitosan and the PBAT are mixed and then melted and granulated to form the master batch, the antibacterial agent can be uniformly dispersed in the PBAT, when the master batch is mixed with the PLA, the antibacterial agent and the PBAT are uniformly dispersed in the PLA again, a product with better dispersibility is obtained, layering caused by poor dispersing effect of the PBAT and the PLA and agglomeration of the antibacterial agent in the PLA can be avoided, antibacterial performance and mechanical performance are reduced, the toughness of the product can be obviously improved by adding the PBAT, and the natural antibacterial agent is used, and comprises plant antibacterial agent peony root bark and animal antibacterial agent chitosan which are harmless to human bodies, and the toothbrush has the advantages of high antibacterial efficiency, safety, no toxicity and environmental protection by compounding.
Preferably, the PLA has a molecular weight of 1.0X 10 5 ～2.0×10 5 The L-polylactic acid of (1). Pla has good biocompatibility and biodegradability, the basic raw material lactic acid is one of inherent physiological substances of human bodies, is nontoxic and harmless to human bodies, has good moisture resistance, grease resistance and impermeability, has stable performance at normal temperature, can be automatically decomposed under the action of oxygen enrichment and microorganisms at the temperature of over 55 ℃, can be completely degraded by microorganisms in the nature after being used, finally generates carbon dioxide and water, does not pollute the environment, is very beneficial to protecting the environment and lacks of environmentThe point is that toughness is not enough, and this application uses PBAT to carry out blending modification to PLA, and prior art is direct to add PBAT in PLA, because both compatibility are relatively poor, is difficult to mix on the molecular level, and dispersion effect is relatively poor, leads to appearing the phenomenon of split phase, and this application is for solving the poor problem of dispersibility, makes the master batch earlier, mixes master batch and PLA again to this improves both compatibility, avoids the layering, carries out toughness modification to PLA through PBAT. Preferably REVODE110 product of Zhejiang Haizang company, or 2003D or 4032D product of Nature works company, the melting temperature is 150-165 ℃, the glass transition temperature is 55-65 ℃, the melt flow rate is 5g/10min, and the density is 1.2-1.3 g/cm 3 1.0X 10 is selected 5 ～2.0×10 5 The levorotatory polylactic acid can form a good blending and dispersing effect with PBAT in the master batch, so that the toughness of the toothbrush is improved, and PLA is modified.
A production process of a biodegradable antibacterial toothbrush comprises the following steps:
(1) Preparing master batch: sun-drying peony root bark, grinding the peony root bark to 10-100 meshes, mixing and stirring 75-91 parts of PBAT, 8-20 parts of ground peony root bark and 1-5 parts of chitosan, and performing melt granulation after stirring to obtain master batches;
(2) Manufacturing a brush handle: and (3) mixing the master batch and the PLA according to the mass ratio of 1-3.
Preferably, the mixing and stirring in step (1) is carried out in a high-speed stirrer at a stirring speed of 70r/min for 10 to 20 minutes. Firstly, peony root bark and chitosan are dispersed in PBAT to prepare master batches, and then the master batches are mixed with PLA for re-dispersion, so that the product dispersibility is improved, and an antibacterial product with better micro-dispersibility than that of a direct blending method is obtained.
Preferably, the melting granulation in the step (1) adopts a double-screw extruder, and the temperature of each section of the double-screw extruder is set as follows: the temperature of the die head is 190-210 ℃, the temperature of the first section is 190-200 ℃, the temperature of the second section is 180-190 ℃, the temperature of the third section is 170-185 ℃ and the temperature of the fourth section is 160-180 ℃.
Preferably, the drying in the step (2) is drying for 3-6 h in a dehumidifying and drying dryer at a drying temperature of 80 ℃.
Preferably, the injection molding in the step (2) adopts an injection molding machine, and the diameter of the screw is 45mm;
the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is 180-210 ℃, the first section is 180-210 ℃, the second section is 180-200 ℃ and the third section is 160-180 ℃; the injection molding pressure is 40-60 Mpa, the injection molding time is 10-20 s, the pressure maintaining pressure is 40-60 Mpa, the pressure maintaining time is 10-20 s, the pressure maintaining speed is 20-35%, the cooling time is 20-60 s, and the cooling water temperature is 20-25 ℃. Solves the technical problem of injection molding processing of the toothbrush handle, provides a production process parameter of the toothbrush, and can well compatibilize PBAT and PLA.
Compared with the prior art, the invention has the following advantages:
the application provides a biological antibacterial master batch and a degradable antibacterial toothbrush handle for a degradable toothbrush, the toothbrush handle raw materials comprise PLA and master batch in a proportion of 10-3, wherein the master batch component proportion is 75-91 parts of PBAT, 8-20 parts of peony root bark and 1-5 parts of chitosan, the peony root bark, the chitosan and the PBAT are mixed and then melted and granulated to form the master batch, then the master batch and the PLA are mixed and then injected to obtain the toothbrush handle, the PLA does not need to participate in extrusion and granulation firstly, the PLA can retain physical properties, the PLA is prevented from influencing mechanical properties due to secondary processing of extrusion and granulation, the PLA is prepared into the master batch and then added into the PLA, the addition of the antibacterial agent and the PBAT can be flexibly adjusted to adapt to different product performance requirements, the PBAT is mixed and then melted and granulated to form the master batch, the antibacterial agent can be uniformly dispersed in the PBAT, the antibacterial agent and the PBAT are uniformly dispersed in the master batch again when the master batch and the PLA are mixed, the antibacterial agent and the PBAT are uniformly dispersed in the master batch, the antibacterial agent can be degraded and the antibacterial agent can be easily degraded on the animal, the environment-friendly antibacterial agent, the environmental protection and the antibacterial agent can be reduced by the advantages of the animal.
The production process of the biodegradable antibacterial toothbrush is simple to process and low in cost, the prepared biodegradable antibacterial toothbrush is applied to daily consumables, the antibacterial performance and durability of products can be improved, the technical problem of injection molding of the toothbrush handle is solved, the production process parameters of the toothbrush are provided, and the production process that bacteria are easily bred in the toothbrush handle and the stability of the PLA toothbrush handle can be solved.
Detailed Description
The following describes a specific embodiment of the present invention with reference to specific examples 1 to 4 and comparative examples 1 to 2:
example 1:
a production process of a biodegradable antibacterial toothbrush comprises the following steps:
(1) Preparing master batch: the peony root bark is naturally dried and ground to 10-100 meshes, PBAT, the peony root bark and chitosan are stirred for 20 minutes at a stirring speed of 70r/min in a high-speed stirrer according to the weight components in the table 1 for mixing and stirring, and a double-screw extruder is used for melting and granulating after stirring, wherein the temperature of each section is as follows: the temperature of a die head is 210 ℃, the temperature of a first section is 190 ℃, the temperature of a second section is 185 ℃, the temperature of a third section is 185 ℃ and the temperature of a fourth section is 170 ℃ to obtain master batches;
(2) Manufacturing a brush handle: mixing the master batch and the PLA according to the mass ratio shown in the table 2, drying the mixture for 4 hours at the drying temperature of 80 ℃ in a dehumidifying and drying dryer, and performing injection molding on an injection molding machine after drying, wherein the diameter of a screw of the injection molding machine is 45mm, and the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is at 200 ℃, the first section is at 200 ℃, the second section is at 190 ℃ and the third section is at 180 ℃; and injection molding pressure of 60Mpa, injection molding time of 10s, pressure maintaining pressure of 50Mpa, pressure maintaining time of 10s, pressure maintaining speed of 30%, cooling time of 50s, and cooling water temperature of 25 ℃ to obtain the brush handle.
Example 2:
a production process of a biodegradable antibacterial toothbrush comprises the following steps:
(1) Preparing master batches: the peony root bark is naturally dried and ground to 10-100 meshes, PBAT, the peony root bark and chitosan are stirred for 15 minutes at a stirring speed of 70r/min in a high-speed stirrer according to the weight components in the table 1 for mixing and stirring, and a double-screw extruder is used for melting and granulating after stirring, wherein the temperature of each section is as follows: the temperature of a die head is 210 ℃, the temperature of a first section is 200 ℃, the temperature of a second section is 185 ℃, the temperature of a third section is 170 ℃ and the temperature of a fourth section is 180 ℃ to obtain master batches;
(2) Manufacturing a brush handle: mixing the master batch and PLA according to the mass ratio shown in Table 2, drying the mixture for 6 hours at the drying temperature of 80 ℃ in a dehumidifying and drying dryer, and performing injection molding on an injection molding machine after drying, wherein the diameter of a screw of the injection molding machine is 45mm, and the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is 210 ℃, the first section is 210 ℃, the second section is 190 ℃ and the third section is 160 ℃; and the injection molding pressure is 50Mpa, the injection molding time is 15s, the pressure maintaining pressure is 60Mpa, the pressure maintaining time is 10s, the pressure maintaining speed is 25%, the cooling time is 40s, and the cooling water temperature is 20 ℃, so that the brush handle is obtained.
Example 3:
a production process of a biodegradable antibacterial toothbrush comprises the following steps:
(1) Preparing master batch: the peony root bark is naturally dried and ground to 10-100 meshes, PBAT, the peony root bark and chitosan are stirred for 10 minutes at a stirring speed of 70r/min in a high-speed stirrer according to the weight components in the table 1 for mixing and stirring, and a double-screw extruder is used for melting and granulating after stirring, wherein the temperature of each section is as follows: the temperature of a die head is 190 ℃, the temperature of a first section is 190 ℃, the temperature of a second section is 180 ℃, the temperature of a third section is 185 ℃ and the temperature of a fourth section is 165 ℃ to obtain master batches;
(2) Manufacturing a brush handle: mixing the master batch and PLA according to the mass ratio shown in Table 2, drying the mixture for 3h at the drying temperature of 80 ℃ in a dehumidifying and drying dryer, and performing injection molding on an injection molding machine after drying, wherein the diameter of a screw of the injection molding machine is 45mm, and the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is 180 ℃, the first section is 180 ℃, the second section is 190 ℃ and the third section is 170 ℃; and injection molding pressure of 40Mpa, injection molding time of 20s, pressure maintaining pressure of 50Mpa, pressure maintaining time of 20s, pressure maintaining speed of 20%, cooling time of 60s, and cooling water temperature of 23 ℃ to obtain the brush handle.
Example 4:
a production process of a biodegradable antibacterial toothbrush comprises the following steps:
(1) Preparing master batch: the peony root bark is naturally dried and ground to 10-100 meshes, PBAT, the peony root bark and chitosan are stirred for 18 minutes at a stirring speed of 70r/min in a high-speed stirrer according to the weight components in the table 1 for mixing and stirring, and a double-screw extruder is used for melting and granulating after stirring, wherein the temperature of each section is as follows: the temperature of the die head is 205 ℃, the temperature of the first section is 190 ℃, the temperature of the second section is 185 ℃, the temperature of the third section is 170 ℃ and the temperature of the fourth section is 165 ℃ to obtain master batch;
(2) Manufacturing a brush handle: mixing the master batch and the PLA according to the mass ratio shown in the table 2, drying the mixture for 5 hours at the drying temperature of 80 ℃ in a dehumidifying and drying dryer, and performing injection molding on an injection molding machine after drying, wherein the diameter of a screw of the injection molding machine is 45mm, and the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is 200 ℃, the first section is 200 ℃, the second section is 1 ℃ and the third section is 170 ℃; and the injection molding pressure is 50Mpa, the injection molding time is 18s, the pressure maintaining pressure is 60Mpa, the pressure maintaining time is 10s, the pressure maintaining speed is 35%, the cooling time is 20s, and the cooling water temperature is 22 ℃, so that the brush handle is obtained.
Comparative example 1:
a production process of a biodegradable antibacterial toothbrush comprises the following steps:
(1) Preparing master batch: the peony root bark is naturally dried and then ground to 10-100 meshes, PBAT, peony root bark, chitosan and PLA are stirred for 20 minutes at a stirring speed of 70r/min in a high-speed stirrer according to the weight components in the table 1 for mixing and stirring, and then a double-screw extruder is used for melting and granulating, wherein the temperature of each section is as follows: the temperature of a die head is 210 ℃, the temperature of a first section is 190 ℃, the temperature of a second section is 185 ℃, the temperature of a third section is 185 ℃ and the temperature of a fourth section is 170 ℃ to obtain master batches;
(2) Manufacturing a brush handle: drying the master batch in a dehumidifying, drying and drying machine at a drying temperature of 80 ℃ for 4h, and performing injection molding on an injection molding machine after drying, wherein the diameter of a screw of the injection molding machine is 45mm, and the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is 200 ℃, the first section is 200 ℃, the second section is 190 ℃ and the third section is 180 ℃; and the brush handle is obtained by injection molding pressure of 60Mpa, injection molding time of 10s, pressure maintaining pressure of 50Mpa, pressure maintaining time of 10s, pressure maintaining speed of 30%, cooling time of 50s and cooling water temperature of 25 ℃.
Comparative example 2:
a production process of a biodegradable antibacterial toothbrush comprises the following steps:
(1) Preparing master batch: the peony root bark is naturally dried and ground to 10-100 meshes, PBAT, the peony root bark and chitosan are stirred for 20 minutes at a stirring speed of 70r/min in a high-speed stirrer according to the weight components in the table 1 for mixing and stirring, and a double-screw extruder is used for melting and granulating after stirring, wherein the temperature of each section is as follows: the temperature of a die head is 210 ℃, the temperature of a first section is 190 ℃, the temperature of a second section is 185 ℃, the temperature of a third section is 185 ℃ and the temperature of a fourth section is 170 ℃ to obtain master batches;
(2) Manufacturing a brush handle: mixing the master batch and the PLA according to the mass ratio shown in the table 2, drying the mixture for 4 hours at the drying temperature of 80 ℃ in a dehumidifying and drying dryer, and performing injection molding on an injection molding machine after drying, wherein the diameter of a screw of the injection molding machine is 45mm, and the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is at 200 ℃, the first section is at 200 ℃, the second section is at 190 ℃ and the third section is at 180 ℃; and injection molding pressure of 60Mpa, injection molding time of 10s, pressure maintaining pressure of 50Mpa, pressure maintaining time of 10s, pressure maintaining speed of 30%, cooling time of 50s, and cooling water temperature of 25 ℃ to obtain the brush handle.
Table 1: weight ratio of each component in the master batches of examples 1 to 4 and comparative examples 1 to 2
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| PBAT | 88 | 75 | 82 | 91 | 88 | 88 |
| Root bark of peony | 10 | 20 | 15 | 8 | 10 | 10 |
| Chitosan | 2 | 5 | 3 | 1 | 2 | 2 |
| PLA | 0 | 0 | 0 | 0 | 500 | 0 |
Table 2: the proportions of the raw material components in the brush handle of the examples 1-4 and the comparative example 2
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 2 |
| Master batch | 2 | 1 | 2.5 | 3 | 0.5 |
| PLA | 10 | 10 | 10 | 10 | 10 |
The toothbrush products prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance tests, the test items included antibacterial performance, impact strength and biodegradability tests, and the test data are shown in table 3;
table 3: results of Performance test of the products of examples 1 to 4 and comparative examples 1 to 2
It can be known from experimental test data that, compared with comparative examples 1 and 2, the toothbrush prepared in examples 1 to 4 of the present application has better antibacterial effect, toughness and decomposition performance, compared with comparative example 1, PLA, PBAT and antibacterial agent are directly extruded and granulated together to form master batches, the present application mixes peony root bark, chitosan and PBAT first and then performs melt granulation to form master batches, then mixes master batches and PLA and performs injection molding to obtain a brush handle, PLA accounts for more than 70% of the total component proportion, PLA does not need to participate in extrusion granulation first, PLA physical properties can be retained, influence on mechanical properties due to secondary processing of extrusion granulation of PLA is avoided, in addition, the master batches are prepared first and added with PLA, antibacterial agent and PBAT addition can be flexibly adjusted to meet different product performance requirements, and peony root bark, chitosan and PBAT are mixed first and then melt granulation is performed to form master batches, so that the antibacterial agent can be uniformly dispersed in PBAT first, then when the master batches are mixed with PLA, the antibacterial agent and the PBAT are uniformly dispersed in the PLA again, while the PBAT and the PLA of the comparative example 1 are not prepared into master batches and then mixed with the PLA, so that the PBAT and the PLA of the comparative example 1 are dispersed and layered, the antibacterial agent is agglomerated in the PLA, and the antibacterial performance and the mechanical performance are reduced, the toothbrush handle raw material of the application is composed of the PLA and the master batches in a ratio of 1-3, wherein the master batches comprise 75-91 parts of the PBAT, 8-20 parts of the peony root bark and 1-5 parts of chitosan, a product with better dispersibility is obtained, the toughness of the product can be obviously improved by adding the PBAT, while the toothbrush handle raw material of the comparative example 2 is composed of the PLA and the master batches in a ratio of 0.5, and the toughness of the finished product of the comparative example 2 and the antibacterial property of the application are not excellent due to the insufficient adding amount of the PBAT, the peony root bark and the chitosan, the natural antibacterial agent is used in the application, comprises the plant antibacterial agent root bark and the animal antibacterial agent chitosan, the biodegradable toothbrush is harmless to human bodies, has the advantages of high antibacterial efficiency, safety, no toxicity and environmental protection through compounding, solves the problems that mildew is easily bred on the surface of a degradable material, the mechanical property of a toothbrush handle is reduced, and the service life is shortened.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A biological antibacterial master batch for a degradable toothbrush is characterized in that the master batch consists of 75-91 parts of PBAT, 8-20 parts of peony root bark and 1-5 parts of chitosan by weight;
the preparation of the master batch comprises the following steps: the peony root bark is dried in the sun and ground to 10-100 meshes, PBAT, the ground peony root bark and chitosan are mixed and stirred, and the mixture is melted and granulated after stirring to obtain master batch.
2. The biological antibacterial masterbatch for degradable toothbrush according to claim 1, characterized in that: the chitosan has deacetylation degree of 90% and molecular weight of 7 × 10 4 ～8×10 4 。
3. The biological antibacterial masterbatch for degradable toothbrush according to claim 1, characterized in that: the weight average relative molecular mass of the PBAT is 6 x 10 4 ～7×10 4 。
4. The biological antibacterial masterbatch for degradable toothbrush according to claim 1, characterized in that: the fineness of the peony root bark is 10-100 meshes.
5. The biological antibacterial masterbatch for degradable toothbrush according to claim 1, characterized in that: the mixing and stirring are carried out in a high-speed stirrer at a stirring speed of 70r/min for 10 to 20 minutes.
6. The biological antibacterial masterbatch for degradable toothbrushes according to claim 1, wherein: the melting granulation adopts a double-screw extruder, and the temperature of each section of the double-screw extruder is set as follows: the temperature of the die head is 190-210 ℃, the temperature of the first section is 190-200 ℃, the temperature of the second section is 180-190 ℃, the temperature of the third section is 170-185 ℃ and the temperature of the fourth section is 160-180 ℃.
7. A degradable antibacterial toothbrush handle is characterized in that: the brush handle comprises the master batch and PLA according to any one of claims 1-6, wherein the mass ratio of the master batch to the PLA is 1-3.
8. The degradable antibacterial toothbrush handle according to claim 7, wherein: the PLA has a molecular weight of 1.0 x 10 5 ～2.0×10 5 The L-polylactic acid of (1).
9. The degradable antibacterial toothbrush handle according to claim 7, wherein: the drying is drying for 3-6 h in a dehumidifying and drying dryer at a drying temperature of 80 ℃.
10. The degradable antibacterial toothbrush handle according to claim 7, wherein: the injection molding adopts an injection molding machine, and the diameter of a screw is 45mm;
the injection molding process parameters are as follows: the injection temperature of each stage was set as: the nozzle is 180-210 ℃, the first section is 180-210 ℃, the second section is 180-200 ℃ and the third section is 160-180 ℃; the injection molding pressure is 40-60 Mpa, the injection molding time is 10-20 s, the pressure maintaining pressure is 40-60 Mpa, the pressure maintaining time is 10-20 s, the pressure maintaining speed is 20-35%, the cooling time is 20-60 s, and the cooling water temperature is 20-25 ℃.
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| CN101074316A (en) * | 2006-05-17 | 2007-11-21 | 张发饶 | Production of super-toughened fire-retardant composite modified nylon mother material |
| CN103910996A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | Antibacterial masterbatch, nano antibacterial super-tough plastic added with antibacterial masterbatch and preparation and application of plastic |
| CN103980686B (en) * | 2014-06-10 | 2016-03-23 | 上海诚壹塑胶制品有限公司 | A kind of biodegradable packaging tube material of germ resistance and flexible pipe preparation method thereof |
| CN104212034B (en) * | 2014-09-04 | 2016-08-24 | 广州索润环保科技有限公司 | A kind of carrier-free plastic master batch and its preparation method and application |
| KR101690091B1 (en) * | 2015-04-16 | 2016-12-27 | 주식회사 쎄코 | Antibacterial primer coating agent for vacuum deposition and method of multi-layered coating by using the same |
| KR20170122455A (en) * | 2016-04-27 | 2017-11-06 | 주식회사 대광티케이 | Toothbrush body manufacturing method and a method of manufacturing a toothbrush body by |
| RO132659A2 (en) * | 2016-12-21 | 2018-06-29 | Institutul De Cercetări Produse Auxiliare Organice S.A. | Pla-based active degradable biocomposites for food packaging |
| CN108102325B (en) * | 2018-01-10 | 2019-11-01 | 三椒口腔健康股份有限公司 | A kind of biodegradable antibacterial toothbrush handle and its preparation process |
| KR102151414B1 (en) * | 2018-12-17 | 2020-09-07 | 위덴 주식회사 | Manufacturing method of toothbrush having annual ring and the toothbrush |
| KR20200091312A (en) * | 2019-01-22 | 2020-07-30 | 주식회사 케이티앤지 | Cartridge having antibacterial function and Aerosol generating device having the same |
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| CN111733474A (en) * | 2020-05-16 | 2020-10-02 | 中国科学院理化技术研究所 | Full-biodegradable dental floss and preparation method thereof |
| CN111777845A (en) * | 2020-07-21 | 2020-10-16 | 苏州环诺新材料科技有限公司 | Food-grade antibacterial antistatic PLA material and preparation method thereof |
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