CN103242644A - Antibacterial polyurethane toothbrush and preparation method thereof - Google Patents
Antibacterial polyurethane toothbrush and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial polyurethane toothbrush and a preparation method thereof. The preparation method comprises the following steps of: firstly preparing a composite antibacterial agent through in-situ reduction of glycosaminoglycans and nano-silver, then dispersing the composite antibacterial agent in polyatomic alcohol for carrying out chain extension reaction with a polyurethane of aromatic polyurethane to prepare antibacterial thermoplastic polyurethane granules, and finally placing the antibacterial thermoplastic polyurethane granules in an injection molding machine for compression molding, thus obtaining the brushing hair and brush head integrated antibacterial polyurethane toothbrush. The preparation method is characterized in that the raw materials are wide in source, and the preparation technology is easy to control and low in cost. The obtained antibacterial polyurethane toothbrush of which brushing hair and a brush head are integrated has very strong antibacterial property, long-lasting effect and good elasticity and toughness as well as good industrialization prospect.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of germ resistance urethane toothbrush and preparation method thereof.
Background technology
Toothbrush is a kind of oral cavity cleaning instrument indispensable in our daily life, from 19th century chemical company of Du Pont release be the toothbrush of bristle with synthon (majority is nylon) since, on the market for the manufacture of the material of bristles always based on nylon.Nylon is a kind of crystalline material with higher-strength, its fusing point height, narrow, the poor heat stability of fusion range, need be processed into nylon wire earlier, be fixed on the brush holder by traditional mao technology of planting again, this makes that the whole manufacturing process of toothbrush is comparatively complicated, and there is the deposition that seam easily causes bacterium, dirt at the hair root place.Therefore, need badly to develop and a kind ofly not only had good mechanical intensity, higher thermostability and be easy to performances such as machine-shaping, but also possess the thermoplasticity toothbrush material of strong germ resistance.
Urethane is to contain carbamate groups (polymkeric substance general name NHCOO-) on the molecule main chain, it has good wear resistance, high intensity and elongation at break, is easy to characteristics such as forming process, now has been widely used in fields such as weaving, packing, food-processing and health care.Polyurethane material if can be used for the preparation of bristles, can overcome above-mentioned nylon material self performance and its preparation technology's shortcoming and defect.But conventional polyurethanes does not have germ resistance, at life-time service and depositing in the process, very easily grows and breed bacterium, and the preparation of using it for bristles can not be satisfied the needs of HUMAN HEALTH, and still need carry out antibacterial modified to polyurethane material for this reason.
At present, report is a lot of for the preparation of the method for antibacterial polyurethane material both at home and abroad, " a kind of antibacterial nano-silver composite polyurethane material and preparation method " disclosed as Chinese patent CN 101760000 B, in the polyurethane stock solution of different concns, add the silver soluble salts solution, silver ions obtains nano silver-polyurethane colloidal sol after reduction, this kind material has good antibacterial property.Hsu Shan-hui etc. have prepared a kind of antibacterial polyurethane-argentum nano composite material directly with Nano silver solution and polyurethane dispersing liquid blend, this material have excellent biological compatibility and anti-microbial property (Biomaterials, 2010 (31), 6796-6808).
Chinese patent CN 101880371 B disclose " a kind of organic polymer material manufacturing technology with antibacterial ", and this method is to add two hydroxyl quaternary ammonium salts in the pre-polymerization stage of synthesis of polyurethane material, has obtained having the urethane of good antibacterial effect.Chinese patent CN 1583853 A disclose and have utilized modified chitosan and urethane to prepare the semiinterpenetrating polymer network resilient material by solution reaction, and mechanical property and the biocompatibility of this material modified more original urethane all are significantly improved.Existing report just, these method of modifying are that the material that will have the inorganic nano silver particles of germ resistance respectively or contain the quaternary ammonium salt functional group is incorporated in the urethane, improve its anti-microbial property.
Yet not seeing as yet combines inorganic nano-silver and the material that contains the quaternary ammonium salt functional group adds the report that improves its anti-microbial property in the urethane simultaneously to.Therefore, if can be with the two in conjunction with being incorporated in the urethane simultaneously, then not only can bring into play nanometer silver quantum size effect, but also can bring into play the strong persistence antimicrobial effect of quaternary ammonium salt material.Be raw material with the antibiotic thermoplastic polyurethane of this kind, can obtain the germ resistance toothbrush of bristle and brush one after injection moulding moulded section, the appearance of this class novel toothbrush product will be played importantly pushing effect to the development of toothbrush industry.
Summary of the invention
The invention provides a kind of preparation method of germ resistance urethane toothbrush, the toothbrush that adopts this preparation method to make has mechanical property and anti-microbial property preferably.
A kind of preparation method of germ resistance urethane toothbrush comprises the steps:
(1) glycosaminoglycan, silver nitrate aqueous solution and acetic acid aqueous solution are mixed, the heating lucifuge stirred after 30～120 minutes, add sodium borohydride aqueous solution again and carry out reduction reaction, obtain the glycosaminoglycan that median size is 30～80nm-nano silver composite antibacterial agent through aftertreatment after reacting completely;
The structure of described glycosaminoglycan is shown in formula I:
The scope of n is 2～50 in the formula I;
(2) pre-fusion under 50～85 ° of C mixes with aromatic diols and aromatic diisocyanate, reacts 2～10 hours under 60～100 ° of C again, obtains the fragrant base polyurethane prepolymer for use as;
(3) glycosaminoglycan that step (1) is obtained-nano silver composite antibacterial agent is scattered in the fragrant base polyurethane prepolymer for use as that aliphatic dialcohol and step (2) obtain and carries out chain extending reaction, carries out granulation after reaction is finished and obtains antibiotic thermoplastic polyurethane pellet;
(4) the antibiotic thermoplastic polyurethane pellet that step (3) is obtained places injection moulding machine to carry out the pressing mold injection moulding, pass through the segmentation demoulding again after, obtain the germ resistance urethane toothbrush of a kind of bristle and brush one.
Among the present invention, polysaccharide structures is contained in the antibiotic thermoplastic polyurethane inside of preparation, and mechanical properties such as tensile strength and elongation at break are improved; This antibiotic thermoplastic polyurethane had both contained generated in-situ inorganic nano-silver simultaneously, contain the antibiotic group of quaternary ammonium salt again, the two combination is incorporated in the urethane simultaneously, not only brought into play nanometer silver quantum size effect, but also brought into play the strong persistence antimicrobial effect of quaternary ammonium salt material, thereby make this antibiotic thermoplastic polyurethane have superpower anti-microbial property, the toothbrush that adopts this antibiotic thermoplastic polyurethane to make has better mechanical property and anti-microbial property.
In the step (1), the heating lucifuge stirs and can make silver ions fully be reduced to nanometer silver, and the hydroxyl of this nanometer silver and glycosaminoglycan or amino fully combination, improve the anti-microbial property of the finished product germ resistance urethane toothbrush, as preferably, the molecular weight of described glycosaminoglycan is that the molecular weight among 1000～20000 Da(the present invention refers to number-average molecular weight), the too high meeting of the molecular weight of glycosaminoglycan causes the size of particles of gained complex antimicrobials excessive, bad dispersibility, reduce the anti-microbial property of germ resistance urethane toothbrush, the molecular weight of glycosaminoglycan is crossed the low mechanical property that can reduce gained germ resistance urethane toothbrush.
As preferably, in the step (1), the consumption of described glycosaminoglycan, silver nitrate aqueous solution, acetic acid aqueous solution and sodium borohydride aqueous solution is as follows:
Glycosaminoglycan 1～50 mass parts;
Silver nitrate aqueous solution 1～25 mass parts;
Acetic acid aqueous solution 100～1000 mass parts;
Sodium borohydride aqueous solution 10～30 mass parts.
Mass parts among the present invention is calculated with the quality of solution.
As preferably, the consumption of described glycosaminoglycan, silver nitrate aqueous solution, acetic acid aqueous solution and sodium borohydride aqueous solution is as follows:
Glycosaminoglycan 25 mass parts;
Silver nitrate aqueous solution 1～25 mass parts;
Acetic acid aqueous solution 100～1000 mass parts;
Sodium borohydride aqueous solution 10～30 mass parts.
Adopt the composition of this weight part can make in the antiseptic-germicide content of Nano silver grain and quaternary ammonium salt group suitable, and complex antimicrobials can fully be disperseed, anti-microbial property is enhanced.
As preferably, the concentration of the silver nitrate aqueous solution described in the step (1) is 0.5～2.5wt%, adopts this concentration silver nitrate aqueous solution can make that nano silver particles is uniformly dispersed in the prepared complex antimicrobials, and anti-microbial property is enhanced; As further preferred, the concentration of the sodium borohydride aqueous solution described in the step (1) is 1～3.5wt %, adopts this concentration sodium borohydride aqueous solution can make reduction reaction abundant, and anti-microbial property is enhanced.
In the step (1), the concentration of described acetic acid aqueous solution is 1～10wt%.
In the step (1), the temperature of described reduction reaction is 70～120 ° of C, and this reduction reaction can fully be finished after 2～8 hours.
In the step (1), described aftertreatment comprises: the reaction solution that obtains after reaction is finished is cooled to room temperature, uses acetone precipitation, filters, washs, and is dry under 35～65 ° of C, obtains granular glycosaminoglycan-nano silver composite antibacterial agent.Adopt acetone to precipitate, be conducive to separating out of granular glycosaminoglycan-nano silver composite antibacterial agent.
In the step (2), described aromatic diols is preferably phenylglycol, 1, the mixture of one or more in 2-diphenylethyleneglycol and the Beta-methyl phenyl-ethylene glycol, these aromatic diols cheaply are easy to get, and the mechanical property of the final germ resistance urethane toothbrush that forms is good.
In the step (2), described aromatic diisocyanate is preferably 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-'-diphenylmethane diisocyanate and 2, the mixture of one or more in the 4-'-diphenylmethane diisocyanate, these aromatic diisocyanates cheaply are easy to get, and the mechanical property of the final germ resistance urethane toothbrush that forms is good.
In the step (2), the ratio of the quality of described aromatic diols and aromatic diisocyanate is 1～25:5～50, more preferably 10:5～50.
As preferably, in the step (3), described aliphatic dialcohol is 1,4-butyleneglycol, 1, the mixture of one or more in 6-hexylene glycol and the cyclohexanedimethanol, and these aliphatic dialcohols cheaply are easy to get, and the mechanical property of the final germ resistance urethane toothbrush that forms is good.
In the step (3), the process that described chain extending reaction carries out is as follows: according to the mass ratio of 10:0.01:0.05～10:0.5:1 with above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and aliphatic dialcohol are injected into 15～25Kg/ hour input speed with volume pump and carry out chain extending reaction in the screw extrusion press, the barrel zone temperature of forcing machine, be followed successively by 145～165 ° of C from material inlet, 170～185 ° of C, 200～215 ° of C, 225～235 ° of C, 205～220 ° of C, screw speed are 125～175 rev/mins, extrusion pressure is 20～40Kg/cm
2, average retention time is 3～6 minutes, urethane is from the spinning nozzle ejection, make the thermoplastic polyurethane pellet with tablets press 15～35 ° of C water.
In the step (4), described pressing mold injection moulding can be bristle and brush single injection-molded or brush and carry out post forming with bristle again after once shaped.
As preferably, in the step (4), in the pressing mold injection molding process, injection pressure is 50-70MPa, injection temperature is 160～200 ℃, adopt this temperature and pressure and antibiotic thermoplastic polyurethane pellet fit, can be convenient to the injection moulding of germ resistance urethane toothbrush, otherwise can reduce the mechanical property of germ resistance urethane toothbrush.
As further preferred, in the step (2), described aromatic diols is Beta-methyl phenyl-ethylene glycol, and described aromatic diisocyanate is 2,4-'-diphenylmethane diisocyanate;
In the step (3), described aliphatic dialcohol is 1,4-butyleneglycol; Mechanical property and the antibacterial effect of the germ resistance urethane toothbrush that obtain this moment are better.
The present invention also provides a kind of and has prepared germ resistance urethane toothbrush by above-mentioned preparation method.This germ resistance urethane toothbrush has better mechanical property and stronger anti-microbial property.
Compare with prior art, the used starting material wide material sources of this preparation method, preparation technology is easy to control, with low cost, products obtained therefrom has that very strong anti-microbial property, effect are lasting, good springiness, toughness are good, is specially adapted to the preparation of integrated through injection molding toothbrush, has the favorable industrial application prospect.
Description of drawings
Fig. 1 is the injection molding process schema of germ resistance urethane toothbrush of the present invention.
Fig. 2 is the structural representation of germ resistance urethane toothbrush of the present invention;
Fig. 3 is the A place enlarged view of Fig. 2.
Embodiment
Fig. 1 is the injection molding process schema of germ resistance urethane toothbrush of the present invention, do further detailed description below in conjunction with the present invention of embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
The acetic acid aqueous solution of 2wt% that with the molecular weight of 1g is 0.5wt% silver nitrate aqueous solution, the 100g of glycosaminoglycan, the 5g of 1000Da mixes, after lucifuge under 60 ° of C stirs 30 minutes, the 1wt% sodium borohydride aqueous solution that adds 10g, after reacting 2 hours under 70 ° of C, be cooled to room temperature, use acetone precipitation, filter, wash, dry under 35 ° of C, obtaining median size is glycosaminoglycan-nano silver composite antibacterial agent of 30nm; 2,4 toluene diisocyanate pre-fusion under 50 ° of C of the phenylglycol of 1g and 5g is mixed, in the reaction kettle for reaction of 60 ° of C 2 hours, obtain the fragrant base polyurethane prepolymer for use as again; According to the mass ratio of 10:0.01:0.05 with above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1, the 4-butyleneglycol is injected into 15Kg/ hour input speed with volume pump and carries out chain extending reaction in the screw extrusion press, the barrel zone temperature of forcing machine, be followed successively by 145 ° of C, 170 ° of C, 200 ° of C, 225 ° of C, 205 ° of C from material inlet, screw speed is that 125 rev/mins, extrusion pressure are 20Kg/cm
2, average retention time is 3 minutes.Urethane sprays, makes the thermoplastic polyurethane pellet with tablets press 15 ° of C water from spinning nozzle; Place injection moulding machine to carry out bristle and brush single injection-molded above-mentioned thermoplastic polyurethane pellet, wherein, injection pressure is 50MPa, and injection temperature is 160 ℃, after the segmentation demoulding, obtains a kind of germ resistance urethane toothbrush, and its structure as shown in Figures 2 and 3.The The performance test results of this kind toothbrush is: tensile strength 25MPa, and elongation at break 350%, the crooked recovery rate 78% of monofilament is to the germ-killing efficiency 98.97% of streptococcus aureus.
Glycosaminoglycan used among the present invention can be prepared with reference to following document:
" development of oligo-glucosamine ", Chinese Journal of Pharmaceuticals, 1999,30,481-493, oligo-glucosamine herein is the glycosaminoglycan among the application; Or
" safety research of chitosan ", Chinese marine drug, 2000,25-27.
Mechanical property among the present invention (tensile strength and elongation at break) is according to the requirement test of GB GB/T1040.2; Anti-microbial property (to the germ-killing efficiency of streptococcus aureus) is according to the requirement test of " QB/T2591 antibiotic plastic-anti-microbial property test method and antibacterial effect " standard; The crooked recovery rate of monofilament is carried out according to the method for 5.5.5 regulation among the GB19342-2003.
Embodiment 2
The acetic acid aqueous solution of 2wt% that with the molecular weight of 50g is 2.5wt% silver nitrate aqueous solution, the 1000g of glycosaminoglycan, the 20g of 20000Da mixes, after lucifuge under 100 ° of C stirs 120 minutes, the 3.5wt% sodium borohydride aqueous solution that adds 30g, after reacting 8 hours under 120 ° of C, be cooled to room temperature, use acetone precipitation, filter, wash, dry under 65 ° of C, obtaining median size is glycosaminoglycan-nano silver composite antibacterial agent of 80nm; With 1 of 25g, 4 of 2-diphenylethyleneglycol and 50g, 4-'-diphenylmethane diisocyanate pre-fusion under 85 ° of C mixes, and in the reaction kettle for reaction of 100 ° of C 10 hours, obtains the fragrant base polyurethane prepolymer for use as again; According to the mass ratio of 10:0.5:1 with above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1, the 6-hexylene glycol is injected into 25Kg/ hour input speed with volume pump and carries out chain extending reaction in the screw extrusion press, the barrel zone temperature of forcing machine, be followed successively by 165 ° of C, 185 ° of C, 215 ° of C, 235 ° of C, 220 ° of C from material inlet, screw speed is that 175 rev/mins, extrusion pressure are 40Kg/cm
2, average retention time is 6 minutes.Urethane sprays, makes the thermoplastic polyurethane pellet with tablets press 35 ° of C water from spinning nozzle; Place injection moulding machine to carry out the brush once shaped above-mentioned thermoplastic polyurethane pellet, again itself and bristle are carried out post forming, wherein, injection pressure all is 60MPa, and injection temperature all is 170 ℃, after the segmentation demoulding, obtains a kind of germ resistance urethane toothbrush.The The performance test results of this kind toothbrush material is: tensile strength 28MPa, and elongation at break 450%, the crooked recovery rate 82% of monofilament is to the germ-killing efficiency 99.97% of streptococcus aureus.
Embodiment 3
The acetic acid aqueous solution of 2wt% that with the molecular weight of 30g is 2.5wt% silver nitrate aqueous solution, the 1000g of glycosaminoglycan, the 10g of 10000Da mixes, after lucifuge under 80 ° of C stirs 60 minutes, the 2.5wt% sodium borohydride aqueous solution that adds 15g, after reacting 6 hours under 100 ° of C, be cooled to room temperature, use acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; With 1 of 25g, 4 of 2-diphenylethyleneglycol and 15g, 4-'-diphenylmethane diisocyanate pre-fusion under 65 ° of C mixes, and in the reaction kettle for reaction of 80 ° of C 8 hours, obtains the fragrant base polyurethane prepolymer for use as again; According to the mass ratio of 10:0.1:0.1 with above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1, the 6-hexylene glycol is injected into 25Kg/ hour input speed with volume pump and carries out chain extending reaction in the screw extrusion press, the barrel zone temperature of forcing machine, be followed successively by 165 ° of C, 185 ° of C, 215 ° of C, 235 ° of C, 220 ° of C from material inlet, screw speed is that 175 rev/mins, extrusion pressure are 40Kg/cm
2, average retention time is 6 minutes.Urethane sprays, makes the thermoplastic polyurethane pellet with tablets press 25 ° of C water from spinning nozzle; Place injection moulding machine to carry out the brush once shaped above-mentioned thermoplastic polyurethane pellet, again itself and bristle are carried out post forming, wherein, injection pressure all is 70MPa, and injection temperature all is 170 ℃, after the segmentation demoulding, obtains a kind of germ resistance urethane toothbrush.The The performance test results of this kind toothbrush material is: tensile strength 25MPa, and elongation at break 550%, the crooked recovery rate 77% of monofilament is to the germ-killing efficiency 99.99% of streptococcus aureus.
Embodiment 4
The acetic acid aqueous solution of 2wt% that with the molecular weight of 35g is 3.5wt% silver nitrate aqueous solution, the 1000g of glycosaminoglycan, the 20g of 20000Da mixes, after lucifuge under 80 ° of C stirs 60 minutes, the 2.5wt% sodium borohydride aqueous solution that adds 30g, after reacting 6 hours under 100 ° of C, be cooled to room temperature, use acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; With 2 of the phenylglycol of 25g and 15g, the pre-fusion under 65 ° of C of 6-tolylene diisocyanate mixes, and in the reaction kettle for reaction of 80 ° of C 8 hours, obtains the fragrant base polyurethane prepolymer for use as again; According to the mass ratio of 10:0.5:1 above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and cyclohexanedimethanol are injected into 25Kg/ hour input speed with volume pump and carry out chain extending reaction in the screw extrusion press, the barrel zone temperature of forcing machine, be followed successively by 160 ° of C, 180 ° of C, 210 ° of C, 230 ° of C, 210 ° of C from material inlet, screw speed is that 150 rev/mins, extrusion pressure are 30Kg/cm
2, average retention time is 4 minutes.Urethane sprays, makes the thermoplastic polyurethane pellet with tablets press 25 ° of C water from spinning nozzle; Place injection moulding machine to carry out bristle and brush single injection-molded above-mentioned thermoplastic polyurethane pellet, wherein, injection pressure is 70MPa, and injection temperature is 200 ℃, after the segmentation demoulding, obtains a kind of germ resistance urethane toothbrush.The The performance test results of this kind toothbrush material is: tensile strength 35MPa, and elongation at break 450%, the crooked recovery rate 76% of monofilament is to the germ-killing efficiency 99.99% of streptococcus aureus.
Embodiment 5
The acetic acid aqueous solution of 2wt% that with the molecular weight of 35g is 3.5wt% silver nitrate aqueous solution, the 1000g of glycosaminoglycan, the 20g of 10000Da mixes, after lucifuge under 80 ° of C stirs 60 minutes, the 2.5wt% sodium borohydride aqueous solution that adds 30g, after reacting 6 hours under 100 ° of C, be cooled to room temperature, use acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; With 2 of Beta-methyl phenyl-ethylene glycol of 25g and 15g, the pre-fusion under 65 ° of C of 4-'-diphenylmethane diisocyanate mixes, and in the reaction kettle for reaction of 80 ° of C 8 hours, obtains the fragrant base polyurethane prepolymer for use as again; According to the mass ratio of 10:0.5:1 with above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1, the 4-butyleneglycol is injected into 25Kg/ hour input speed with volume pump and carries out chain extending reaction in the screw extrusion press, the barrel zone temperature of forcing machine, be followed successively by 160 ° of C, 180 ° of C, 210 ° of C, 230 ° of C, 210 ° of C from material inlet, screw speed is that 150 rev/mins, extrusion pressure are 30Kg/cm
2, average retention time is 4 minutes.Urethane sprays, makes the thermoplastic polyurethane pellet with tablets press 25 ° of C water from spinning nozzle; Place injection moulding machine to carry out the brush once shaped above-mentioned thermoplastic polyurethane pellet, again itself and bristle are carried out post forming, wherein, injection pressure all is 70MPa, and injection temperature all is 200 ℃, after the segmentation demoulding, obtains a kind of germ resistance urethane toothbrush.The The performance test results of this kind toothbrush material is: tensile strength 36MPa, and elongation at break 500%, the crooked recovery rate 89% of monofilament is to the germ-killing efficiency 99.98% of streptococcus aureus.
Embodiment 6
The acetic acid aqueous solution of 2wt% that with the molecular weight of 25g is 2.5wt% silver nitrate aqueous solution, the 500g of glycosaminoglycan, the 10g of 20000Da mixes, after lucifuge under 80 ° of C stirs 60 minutes, the 2.5wt% sodium borohydride aqueous solution that adds 15g, after reacting 6 hours under 100 ° of C, be cooled to room temperature, use acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; With 1 of 25g, 4 of 2-diphenylethyleneglycol and 15g, 4-'-diphenylmethane diisocyanate pre-fusion under 65 ° of C mixes, and in the reaction kettle for reaction of 80 ° of C 8 hours, obtains the fragrant base polyurethane prepolymer for use as again; According to the mass ratio of 10:0.1:0.5 with above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1, the 6-hexylene glycol is injected into 25Kg/ hour input speed with volume pump and carries out chain extending reaction in the screw extrusion press, the barrel zone temperature of forcing machine, be followed successively by 165 ° of C, 185 ° of C, 215 ° of C, 235 ° of C, 220 ° of C from material inlet, screw speed is that 175 rev/mins, extrusion pressure are 40Kg/cm
2, average retention time is 6 minutes.Urethane sprays, makes the thermoplastic polyurethane pellet with tablets press 25 ° of C water from spinning nozzle; Place injection moulding machine to carry out bristle and brush single injection-molded above-mentioned thermoplastic polyurethane pellet, wherein, injection pressure is 50MPa, and injection temperature all is 200 ℃, after the segmentation demoulding, obtains a kind of germ resistance urethane toothbrush.The The performance test results of this kind toothbrush material is: tensile strength 30MPa, and elongation at break 500%, the crooked recovery rate 81% of monofilament is to the germ-killing efficiency 99.99% of streptococcus aureus.
Claims (10)
1. the preparation method of a germ resistance urethane toothbrush is characterized in that, comprises the steps:
(1) glycosaminoglycan, silver nitrate aqueous solution and acetic acid aqueous solution are mixed, the heating lucifuge stirred after 30～120 minutes, add sodium borohydride aqueous solution again and carry out reduction reaction, obtain the glycosaminoglycan that median size is 30～80nm-nano silver composite antibacterial agent through aftertreatment after reacting completely;
The structure of described glycosaminoglycan is suc as formula shown in (I):
The scope of n is 2～50 in the formula (I);
(2) aromatic diols and aromatic diisocyanate are mixed 50～85 ℃ of following pre-fusions, reacted 2～10 hours down at 60～100 ℃ again, obtain the fragrant base polyurethane prepolymer for use as;
(3) glycosaminoglycan that step (1) is obtained-nano silver composite antibacterial agent is scattered in the fragrant base polyurethane prepolymer for use as that aliphatic dialcohol and step (2) obtain and carries out chain extending reaction, carries out granulation after reaction is finished and obtains antibiotic thermoplastic polyurethane pellet;
(4) the antibiotic thermoplastic polyurethane pellet that step (3) is obtained places injection moulding machine to carry out the pressing mold injection moulding, pass through the segmentation demoulding again after, obtain the germ resistance urethane toothbrush of a kind of bristle and brush one.
2. the preparation method of germ resistance urethane toothbrush according to claim 1 is characterized in that, in the step (1), the molecular weight of described glycosaminoglycan is 1000～20000Da.
3. the preparation method of germ resistance urethane toothbrush according to claim 1 is characterized in that, in the step (1), the consumption of described glycosaminoglycan, silver nitrate aqueous solution, acetic acid aqueous solution and sodium borohydride aqueous solution is as follows:
4. the preparation method of germ resistance urethane toothbrush according to claim 1, it is characterized in that, aftertreatment in the step (1) comprises: the reaction solution that obtains after reaction is finished is cooled to room temperature, use acetone precipitation, filter, wash, dry under 35～65 ℃, obtain described glycosaminoglycan-nano silver composite antibacterial agent.
5. the preparation method of germ resistance urethane toothbrush according to claim 1 is characterized in that, the concentration of the silver nitrate aqueous solution described in the step (1) is 0.5～2.5wt%;
The concentration of the sodium borohydride aqueous solution described in the step (1) is 1～3.5wt%.
6. the preparation method of germ resistance urethane toothbrush according to claim 1, it is characterized in that, in the step (2), described aromatic diols is phenylglycol, 1, the mixture of one or more in 2-diphenylethyleneglycol and the Beta-methyl phenyl-ethylene glycol;
Described aromatic diisocyanate is 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, 4, the mixture of one or more in 4-'-diphenylmethane diisocyanate and 2, the 4-'-diphenylmethane diisocyanate.
7. the preparation method of germ resistance urethane toothbrush according to claim 1 is characterized in that, the ratio of the quality of described aromatic diols and aromatic diisocyanate is 1～25: 5～50.
8. the preparation method of germ resistance urethane toothbrush according to claim 1 is characterized in that, in the step (3), described aliphatic dialcohol is 1,4-butyleneglycol, 1, the mixture of one or more in 6-hexylene glycol and the cyclohexanedimethanol.
9. the preparation method of germ resistance urethane toothbrush according to claim 1 is characterized in that, in the step (4), in injection molding process, injection pressure is 50-70MPa, and injection temperature is 160～200 ℃.
10. a germ resistance urethane toothbrush is characterized in that, each described preparation method prepares by claim 1～9.
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| US10136723B2 (en) | 2015-12-14 | 2018-11-27 | Colgate-Palmolive Company | Oral care implement |
| CN109337040A (en) * | 2018-08-16 | 2019-02-15 | 汕头市宏隆实业有限公司 | It is a kind of for thermo-plastic polyurethane's micelle of toothbrush bristle and its preparation |
| US10213011B2 (en) | 2015-12-14 | 2019-02-26 | Colgate-Palmolive Company | Oral care implement |
| CN109486464A (en) * | 2018-10-30 | 2019-03-19 | 浙江华峰热塑性聚氨酯有限公司 | Clothes antibiotic property thermoplastic polyurethane nethike embrane and preparation method |
| CN110862503A (en) * | 2019-11-29 | 2020-03-06 | 佛山市瑞福物联科技有限公司 | Preparation method of conductive polyurethane prepolymer and conductive adhesive thereof |
| USD882960S1 (en) | 2017-11-16 | 2020-05-05 | Colgate-Palmolive Company | Oral care implement |
| CN115821422A (en) * | 2022-12-02 | 2023-03-21 | 雅香丽化妆用品（深圳）有限公司 | Preparation method of antibacterial toothbrush filaments |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD815838S1 (en) | 2016-07-15 | 2018-04-24 | Colgate-Palmolive Company | Toothbrush |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03231964A (en) * | 1990-02-07 | 1991-10-15 | Inoue Mtp Co Ltd | Antimicrobial polyurethane foam, antimicrobial polyurethane elastomer and antimicrobial polyurethane coating composition |
| CN2684634Y (en) * | 2003-06-09 | 2005-03-16 | 苏隽 | Tooth brush |
-
2013
- 2013-04-28 CN CN201310157595.7A patent/CN103242644B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03231964A (en) * | 1990-02-07 | 1991-10-15 | Inoue Mtp Co Ltd | Antimicrobial polyurethane foam, antimicrobial polyurethane elastomer and antimicrobial polyurethane coating composition |
| CN2684634Y (en) * | 2003-06-09 | 2005-03-16 | 苏隽 | Tooth brush |
Non-Patent Citations (1)
| Title |
|---|
| 安静 等，: "银/壳聚糖-g-甲基丙烯酸甲酯复合物的制备与抗菌性能", 《复合材料学报》, vol. 28, no. 3, 30 June 2011 (2011-06-30) * |
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| US10136723B2 (en) | 2015-12-14 | 2018-11-27 | Colgate-Palmolive Company | Oral care implement |
| US10213011B2 (en) | 2015-12-14 | 2019-02-26 | Colgate-Palmolive Company | Oral care implement |
| US10849417B2 (en) | 2015-12-14 | 2020-12-01 | Colgate-Palmolive Company | Oral care implement |
| CN107692272A (en) * | 2017-07-31 | 2018-02-16 | 浦江县元寿农业科技有限公司 | Clear cherry tomato washing machine with bactericidal device |
| CN107594572A (en) * | 2017-07-31 | 2018-01-19 | 浦江县元寿农业科技有限公司 | A kind of apple cleaning machine of intelligentized control method |
| USD882960S1 (en) | 2017-11-16 | 2020-05-05 | Colgate-Palmolive Company | Oral care implement |
| CN109337040A (en) * | 2018-08-16 | 2019-02-15 | 汕头市宏隆实业有限公司 | It is a kind of for thermo-plastic polyurethane's micelle of toothbrush bristle and its preparation |
| CN109337040B (en) * | 2018-08-16 | 2020-08-21 | 汕头市宏隆实业有限公司 | Thermoplastic polyurethane colloidal particles for toothbrush bristles and preparation thereof |
| CN109486464A (en) * | 2018-10-30 | 2019-03-19 | 浙江华峰热塑性聚氨酯有限公司 | Clothes antibiotic property thermoplastic polyurethane nethike embrane and preparation method |
| CN109486464B (en) * | 2018-10-30 | 2021-05-11 | 浙江华峰热塑性聚氨酯有限公司 | Antibacterial thermoplastic polyurethane net film for clothing and preparation method thereof |
| CN110862503A (en) * | 2019-11-29 | 2020-03-06 | 佛山市瑞福物联科技有限公司 | Preparation method of conductive polyurethane prepolymer and conductive adhesive thereof |
| CN110862503B (en) * | 2019-11-29 | 2022-02-11 | 佛山市瑞福物联科技有限公司 | Preparation method of conductive polyurethane prepolymer and conductive adhesive thereof |
| CN115821422A (en) * | 2022-12-02 | 2023-03-21 | 雅香丽化妆用品（深圳）有限公司 | Preparation method of antibacterial toothbrush filaments |
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