CN103242644B - 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 Antibacterial polyurethane toothbrush and preparation method thereof.
Background technology
Toothbrush is a kind of oral cleaning tool indispensable in our daily life, and from 19th century, DuPont Chemicals has released with since the toothbrush of synthon (majority is nylon) for bristle, on 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 is high, fusion range is narrow, poor heat stability, first need be processed into nylon wire, be fixed on brush holder by traditional mao technique of planting again, this makes the overall manufacturing process of toothbrush comparatively complicated, and there is the deposition that seam easily causes bacterium, dirt at hair root place.Therefore, need badly to develop and a kind ofly not only there is good mechanical strength, higher thermostability and be easy to the performances such as machine-shaping, but also possess the thermoplasticity toothbrush material of strong germ resistance.
Urethane is the polymkeric substance general name containing carbamate groups (-NHCOO-) on molecule main chain, it has good wear resistance, high intensity and elongation at break, is easy to the features such as forming process, has now been widely used in the fields such as weaving, packaging, food-processing and health care.If polyurethane material to be used for the preparation of bristles, the shortcoming and defect of above-mentioned nylon material self performance and its preparation technology can be overcome.But conventional polyurethanes does not have germ resistance, at life-time service and deposit in process, very easily Growth and reproduction bacterium, the preparation using it for bristles can not meet the needs of HUMAN HEALTH, still needs to carry out antibacterial modified to polyurethane material for this reason.
At present, domestic and international report is a lot of for the preparation of the method for antibacterial polyurethane material, as Chinese patent CN 101760000 B discloses " a kind of antibacterial nano-silver composite polyurethane material and preparation method ", soluble silver salt solution is added in the polyurethane stock solution of different concns, silver ions obtains nano silver-polyurethane colloidal sol after reduction, and this kind of material has good germ resistance.Hsu Shan-hui etc. directly by Nano silver solution and polyurethane dispersing liquid blended, prepare a kind of antibacterial polyurethane-argentum nano composite material, this material has good biocompatibility and anti-microbial property (Biomaterials, 2010 (31), 6796-6808).
Chinese patent CN 101880371 B discloses " a kind of organic polymer material manufacturing technology with antibacterial ", and the method adds two hydroxyl quaternary ammonium salt at the precondensation stage of synthesis of polyurethane material, obtains the urethane with good antibacterial effect.Chinese patent CN 1583853 A, discloses and utilizes modified chitosan and urethane to prepare semiinterpenetrating polymer network resilient material by solution reaction, and this material modified mechanical property compared with original polyurethane and biocompatibility are all significantly improved.With regard to existing report, these method of modifying are respectively by having the inorganic nano silver particles of germ resistance or being incorporated in urethane containing the material of quaternary ammonium salt function base, improve its anti-microbial property.
But, there is not yet and to combine the report adding to simultaneously and improve its anti-microbial property in urethane by inorganic nano-silver with containing the material of quaternary ammonium salt function base.Therefore, if the two combination is incorporated in urethane simultaneously, then not only can have played the quantum size effect of nanometer silver, but also the strong persistence antimicrobial effect of quaternary ammonium material can have been played.With this kind of antibacterial thermoplastic polyurethane for raw material, can obtain the germ resistance toothbrush of bristle and brush one after injection moulding moulded section, the appearance of this kind of novel toothbrush product will play importantly pushing effect to the development of toothbrush industry.
Summary of the invention
The invention provides a kind of preparation method of Antibacterial polyurethane toothbrush, the toothbrush adopting this preparation method to obtain has good mechanical property and anti-microbial property.
A preparation method for Antibacterial polyurethane toothbrush, comprises the steps:
(1) glycosaminoglycan, silver nitrate aqueous solution and acetic acid aqueous solution are mixed, heating lucifuge stirs after 30 ~ 120 minutes, add sodium borohydride aqueous solution again and carry out reduction reaction, after reacting completely, obtain through aftertreatment glycosaminoglycan-nano silver composite antibacterial agent that median size is 30 ~ 80nm;
The structure of described glycosaminoglycan is as shown in formula I:
In formula I, the scope of n is 2 ~ 50;
(2) the pre-fusion mixing under 50 ~ 85 ° of C by aromatic diols and aromatic diisocyanate, then react 2 ~ 10 hours under 60 ~ 100 ° of C, obtain fragrant base polyurethane prepolymer for use as;
(3) glycosaminoglycan-nano silver composite antibacterial agent that step (1) obtains is scattered in the fragrant base polyurethane prepolymer for use as that aliphatic dialcohol and step (2) obtain and carries out chain extending reaction, carry out granulation after having reacted and obtain antibacterial thermoplastic polyurethane pellet;
(4) the antibacterial thermoplastic polyurethane pellet that step (3) obtains is placed in injection moulding machine and carries out pressing mold injection moulding, then after the segmentation demoulding, obtain the Antibacterial polyurethane toothbrush of a kind of bristle and brush one.
In the present invention, the antibacterial thermoplastic polyurethane inside of preparation, containing polysaccharide structures, makes the mechanical property such as tensile strength and elongation at break be improved; This antibacterial thermoplastic polyurethane is both containing generated in-situ inorganic nano-silver simultaneously, again containing the antibacterial group of quaternary ammonium salt, the two combination is incorporated in urethane simultaneously, not only play the quantum size effect of nanometer silver, but also play the strong persistence antimicrobial effect of quaternary ammonium material, thus make this antibacterial thermoplastic polyurethane have superpower anti-microbial property, adopt the obtained toothbrush of this antibacterial thermoplastic polyurethane to have better mechanical property and anti-microbial property.
In step (1), heating lucifuge stirs and silver ions can be made fully to be reduced to nanometer silver, and the hydroxyl of this nanometer silver and glycosaminoglycan or amino fully combine, improve the anti-microbial property of the finished product Antibacterial polyurethane toothbrush, as preferably, the molecular weight of described glycosaminoglycan is that the molecular weight in 1000 ~ 20000 Da(the present invention refers to number-average molecular weight), the too high meeting of molecular weight of glycosaminoglycan causes the size of particles of gained complex antimicrobials excessive, bad dispersibility, reduce the anti-microbial property of Antibacterial polyurethane toothbrush, the too low mechanical property that can reduce gained Antibacterial polyurethane toothbrush of molecular weight of glycosaminoglycan.
As preferably, in 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 in the present invention calculates 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 that the content of Nano silver grain and quaternary ammonium salt group in antiseptic-germicide can be made suitable, and complex antimicrobials is fully disperseed, anti-microbial property is enhanced.
As preferably, the concentration of the silver nitrate aqueous solution described in step (1) is 0.5 ~ 2.5wt%, and adopt this concentration silver nitrate aqueous solution that nano silver particles in obtained complex antimicrobials can be made to be uniformly dispersed, anti-microbial property is enhanced; As further preferred, the concentration of the sodium borohydride aqueous solution described in step (1) is 1 ~ 3.5wt %, and adopt this concentration sodium borohydride aqueous solution that reduction reaction can be made abundant, anti-microbial property is enhanced.
In step (1), the concentration of described acetic acid aqueous solution is 1 ~ 10wt%.
In step (1), the temperature of described reduction reaction is 70 ~ 120 ° of C, and after 2 ~ 8 hours, this reduction reaction can fully complete.
In step (1), described aftertreatment comprises: the reaction solution obtained after having reacted is cooled to room temperature, with acetone precipitation, filters, washing, dry under 35 ~ 65 ° of C, obtains granular glycosaminoglycan-nano silver composite antibacterial agent.Adopt acetone to precipitate, be conducive to the precipitation of granular glycosaminoglycan-nano silver composite antibacterial agent.
In step (2), described aromatic diols is preferably phenylglycol, 1, the mixture of one or more in 2-diphenylethyleneglycol and Beta-methyl phenyl-ethylene glycol, these aromatic diols are cheaply easy to get, and the mechanical property of the final Antibacterial polyurethane toothbrush formed is good.
In 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 4-'-diphenylmethane diisocyanate, these aromatic diisocyanates are cheaply easy to get, and the mechanical property of the final Antibacterial polyurethane toothbrush formed is good.
In step (2), described aromatic diols and the mass ratio of aromatic diisocyanate are 1 ~ 25:5 ~ 50, more preferably 10:5 ~ 50.
As preferably, in step (3), described aliphatic dialcohol is the mixture of one or more in BDO, 1,6-hexylene glycol and cyclohexanedimethanol, and these aliphatic dialcohols are cheaply easy to get, and the mechanical property of the final Antibacterial polyurethane toothbrush formed is good.
In 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 by above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and aliphatic dialcohol volume pump are injected in screw extrusion press with the input speed of 15 ~ 25Kg/ hour and carry out chain extending reaction, the barrel zone temperature of forcing machine, 145 ~ 165 ° of C are followed successively by from material inlet, 170 ~ 185 ° of C, 200 ~ 215 ° of C, 225 ~ 235 ° of C, 205 ~ 220 ° of C, screw speed is 125 ~ 175 revs/min, extrusion pressure is 20 ~ 40Kg/cm
2, average retention time is 3 ~ 6 minutes, urethane is from spinning nozzle ejection, with tablets press obtained thermoplastic polyurethane pellet 15 ~ 35 ° of C water.
In 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 step (4), in pressing mold injection molding process, injection pressure is 50-70MPa, injection temperature is 160 ~ 200 DEG C, adopt this temperature and pressure and antibacterial thermoplastic polyurethane pellet fit, the injection moulding of Antibacterial polyurethane toothbrush can be convenient to, otherwise the mechanical property of Antibacterial polyurethane toothbrush can be reduced.
As further preferred, in step (2), described aromatic diols is Beta-methyl phenyl-ethylene glycol, and described aromatic diisocyanate is 2,4-'-diphenylmethane diisocyanate;
In step (3), described aliphatic dialcohol is BDO; Mechanical property and the antibacterial effect of the Antibacterial polyurethane toothbrush now obtained are better.
Present invention also offers and a kind ofly prepare Antibacterial polyurethane toothbrush by above-mentioned preparation method.This Antibacterial polyurethane toothbrush has better mechanical property and stronger anti-microbial property.
Compared with the existing technology, these preparation method's raw materials wide material sources, preparation technology is easy to control, with low cost, products obtained therefrom has very strong anti-microbial property, effect is lasting, good springiness, toughness are good, is specially adapted to the preparation of integrated through injection molding toothbrush, has good industrial applications prospect.
Accompanying drawing explanation
Fig. 1 is the injection molding process schema of Antibacterial polyurethane toothbrush of the present invention.
Fig. 2 is the structural representation of Antibacterial polyurethane 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 Antibacterial polyurethane toothbrush of the present invention, is described in further detail the present invention below in conjunction with embodiment, but the present invention is not by the restriction of these embodiments.
Embodiment 1
Be the glycosaminoglycan of 1000Da by the molecular weight of 1g, the acetic acid aqueous solution of the 0.5wt% silver nitrate aqueous solution of 5g, the 2wt% of 100g mixes, after under 60 ° of C, lucifuge stirs 30 minutes, add the 1wt% sodium borohydride aqueous solution of 10g, react under 70 ° of C after 2 hours, be cooled to room temperature, with acetone precipitation, filter, wash, dry under 35 ° of C, obtain glycosaminoglycan-nano silver composite antibacterial agent that median size is 30nm; By the pre-fusion mixing under 50 ° of C of the phenylglycol of 1g and the 2,4 toluene diisocyanate of 5g, then in the reaction kettle for reaction 2 hours of 60 ° of C, obtain fragrant base polyurethane prepolymer for use as; According to the mass ratio of 10:0.01:0.05 by above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1,4-butyleneglycol volume pump is injected in screw extrusion press with the input speed of 15Kg/ hour and carries out chain extending reaction, the barrel zone temperature of forcing machine, from material inlet, be followed successively by 145 ° of C, 170 ° of C, 200 ° of C, 225 ° of C, 205 ° of C, screw speed is 125 revs/min, extrusion pressure is 20Kg/cm
2, average retention time is 3 minutes.Urethane sprays from spinning nozzle, 15 ° of C water, obtain thermoplastic polyurethane pellet with tablets press; Above-mentioned thermoplastic polyurethane pellet is placed in injection moulding machine and carries out bristle and brush single injection-molded, wherein, injection pressure is 50MPa, and injection temperature is 160 DEG C, and after the segmentation demoulding, obtain a kind of Antibacterial polyurethane toothbrush, its structure as shown in Figures 2 and 3.The performance test results of this kind of toothbrush is: tensile strength 25MPa, elongation at break 350%, and monofilament bends recovery rate 78%, to the germ-killing efficiency 98.97% of streptococcus aureus.
Glycosaminoglycan used in 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 is herein the glycosaminoglycan in the application; Or
" safety research of chitosan ", Chinese Sea medicine, 2000,25-27.
Mechanical property (tensile strength and elongation at break) in the present invention is tested according to the requirement of GB GB/T1040.2; Anti-microbial property (germ-killing efficiency to streptococcus aureus) is tested according to the requirement of " QB/T2591 antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect " standard; Monofilament bends the method that recovery rate specifies according to 5.5.5 in GB19342-2003 to carry out.
Embodiment 2
Be the glycosaminoglycan of 20000Da by the molecular weight of 50g, the acetic acid aqueous solution of the 2.5wt% silver nitrate aqueous solution of 20g, the 2wt% of 1000g mixes, after under 100 ° of C, lucifuge stirs 120 minutes, add the 3.5wt% sodium borohydride aqueous solution of 30g, react under 120 ° of C after 8 hours, be cooled to room temperature, with acetone precipitation, filter, wash, dry under 65 ° of C, obtain glycosaminoglycan-nano silver composite antibacterial agent that median size is 80nm; By the pre-fusion mixing under 85 ° of C of 1, the 2-diphenylethyleneglycol of 25g and 4, the 4-'-diphenylmethane diisocyanates of 50g, then in the reaction kettle for reaction 10 hours of 100 ° of C, obtain fragrant base polyurethane prepolymer for use as; According to the mass ratio of 10:0.5:1 by above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1,6-hexylene glycol volume pump is injected in screw extrusion press with the input speed of 25Kg/ hour and carries out chain extending reaction, the barrel zone temperature of forcing machine, from material inlet, be followed successively by 165 ° of C, 185 ° of C, 215 ° of C, 235 ° of C, 220 ° of C, screw speed is 175 revs/min, extrusion pressure is 40Kg/cm
2, average retention time is 6 minutes.Urethane sprays from spinning nozzle, 35 ° of C water, obtain thermoplastic polyurethane pellet with tablets press; Above-mentioned thermoplastic polyurethane pellet is placed in injection moulding machine and carries out brush once shaped, then itself and bristle are carried out post forming, wherein, injection pressure is all 60MPa, and injection temperature is all 170 DEG C, after the segmentation demoulding, obtains a kind of Antibacterial polyurethane toothbrush.The performance test results of this kind of toothbrush material is: tensile strength 28MPa, elongation at break 450%, and monofilament bends recovery rate 82%, to the germ-killing efficiency 99.97% of streptococcus aureus.
Embodiment 3
Be the glycosaminoglycan of 10000Da by the molecular weight of 30g, the acetic acid aqueous solution of the 2.5wt% silver nitrate aqueous solution of 10g, the 2wt% of 1000g mixes, after under 80 ° of C, lucifuge stirs 60 minutes, add the 2.5wt% sodium borohydride aqueous solution of 15g, react under 100 ° of C after 6 hours, be cooled to room temperature, with acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; By the pre-fusion mixing under 65 ° of C of 1, the 2-diphenylethyleneglycol of 25g and 4, the 4-'-diphenylmethane diisocyanates of 15g, then in the reaction kettle for reaction 8 hours of 80 ° of C, obtain fragrant base polyurethane prepolymer for use as; According to the mass ratio of 10:0.1:0.1 by above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1,6-hexylene glycol volume pump is injected in screw extrusion press with the input speed of 25Kg/ hour and carries out chain extending reaction, the barrel zone temperature of forcing machine, from material inlet, be followed successively by 165 ° of C, 185 ° of C, 215 ° of C, 235 ° of C, 220 ° of C, screw speed is 175 revs/min, extrusion pressure is 40Kg/cm
2, average retention time is 6 minutes.Urethane sprays from spinning nozzle, 25 ° of C water, obtain thermoplastic polyurethane pellet with tablets press; Above-mentioned thermoplastic polyurethane pellet is placed in injection moulding machine and carries out brush once shaped, then itself and bristle are carried out post forming, wherein, injection pressure is all 70MPa, and injection temperature is all 170 DEG C, after the segmentation demoulding, obtains a kind of Antibacterial polyurethane toothbrush.The performance test results of this kind of toothbrush material is: tensile strength 25MPa, elongation at break 550%, and monofilament bends recovery rate 77%, to the germ-killing efficiency 99.99% of streptococcus aureus.
Embodiment 4
Be the glycosaminoglycan of 20000Da by the molecular weight of 35g, the acetic acid aqueous solution of the 3.5wt% silver nitrate aqueous solution of 20g, the 2wt% of 1000g mixes, after under 80 ° of C, lucifuge stirs 60 minutes, add the 2.5wt% sodium borohydride aqueous solution of 30g, react under 100 ° of C after 6 hours, be cooled to room temperature, with acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; By the pre-fusion mixing under 65 ° of C of 2, the 6-tolylene diisocyanates of the phenylglycol of 25g and 15g, then in the reaction kettle for reaction 8 hours of 80 ° of C, obtain fragrant base polyurethane prepolymer for use as; 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 volume pump be injected in screw extrusion press with the input speed of 25Kg/ hour and carry out chain extending reaction, the barrel zone temperature of forcing machine, from material inlet, be followed successively by 160 ° of C, 180 ° of C, 210 ° of C, 230 ° of C, 210 ° of C, screw speed is 150 revs/min, extrusion pressure is 30Kg/cm
2, average retention time is 4 minutes.Urethane sprays from spinning nozzle, 25 ° of C water, obtain thermoplastic polyurethane pellet with tablets press; Above-mentioned thermoplastic polyurethane pellet is placed in injection moulding machine and carries out bristle and brush single injection-molded, wherein, injection pressure is 70MPa, and injection temperature is 200 DEG C, after the segmentation demoulding, obtains a kind of Antibacterial polyurethane toothbrush.The performance test results of this kind of toothbrush material is: tensile strength 35MPa, elongation at break 450%, and monofilament bends recovery rate 76%, to the germ-killing efficiency 99.99% of streptococcus aureus.
Embodiment 5
Be the glycosaminoglycan of 10000Da by the molecular weight of 35g, the acetic acid aqueous solution of the 3.5wt% silver nitrate aqueous solution of 20g, the 2wt% of 1000g mixes, after under 80 ° of C, lucifuge stirs 60 minutes, add the 2.5wt% sodium borohydride aqueous solution of 30g, react under 100 ° of C after 6 hours, be cooled to room temperature, with acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; By the pre-fusion mixing under 65 ° of C of 2, the 4-'-diphenylmethane diisocyanates of the Beta-methyl of 25g phenyl-ethylene glycol and 15g, then in the reaction kettle for reaction 8 hours of 80 ° of C, obtain fragrant base polyurethane prepolymer for use as; According to the mass ratio of 10:0.5:1 by above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1,4-butyleneglycol volume pump is injected in screw extrusion press with the input speed of 25Kg/ hour and carries out chain extending reaction, the barrel zone temperature of forcing machine, from material inlet, be followed successively by 160 ° of C, 180 ° of C, 210 ° of C, 230 ° of C, 210 ° of C, screw speed is 150 revs/min, extrusion pressure is 30Kg/cm
2, average retention time is 4 minutes.Urethane sprays from spinning nozzle, 25 ° of C water, obtain thermoplastic polyurethane pellet with tablets press; Above-mentioned thermoplastic polyurethane pellet is placed in injection moulding machine and carries out brush once shaped, then itself and bristle are carried out post forming, wherein, injection pressure is all 70MPa, and injection temperature is all 200 DEG C, after the segmentation demoulding, obtains a kind of Antibacterial polyurethane toothbrush.The performance test results of this kind of toothbrush material is: tensile strength 36MPa, elongation at break 500%, and monofilament bends recovery rate 89%, to the germ-killing efficiency 99.98% of streptococcus aureus.
Embodiment 6
Be the glycosaminoglycan of 20000Da by the molecular weight of 25g, the acetic acid aqueous solution of the 2.5wt% silver nitrate aqueous solution of 10g, the 2wt% of 500g mixes, after under 80 ° of C, lucifuge stirs 60 minutes, add the 2.5wt% sodium borohydride aqueous solution of 15g, react under 100 ° of C after 6 hours, be cooled to room temperature, with acetone precipitation, filter, wash, dry under 65 ° of C, obtain granular glycosaminoglycan-nano silver composite antibacterial agent; By the pre-fusion mixing under 65 ° of C of 1, the 2-diphenylethyleneglycol of 25g and 4, the 4-'-diphenylmethane diisocyanates of 15g, then in the reaction kettle for reaction 8 hours of 80 ° of C, obtain fragrant base polyurethane prepolymer for use as; According to the mass ratio of 10:0.1:0.5 by above-mentioned fragrant base polyurethane prepolymer for use as, glycosaminoglycan-nano silver composite antibacterial agent and 1,6-hexylene glycol volume pump is injected in screw extrusion press with the input speed of 25Kg/ hour and carries out chain extending reaction, the barrel zone temperature of forcing machine, from material inlet, be followed successively by 165 ° of C, 185 ° of C, 215 ° of C, 235 ° of C, 220 ° of C, screw speed is 175 revs/min, extrusion pressure is 40Kg/cm
2, average retention time is 6 minutes.Urethane sprays from spinning nozzle, 25 ° of C water, obtain thermoplastic polyurethane pellet with tablets press; Above-mentioned thermoplastic polyurethane pellet is placed in injection moulding machine and carries out bristle and brush single injection-molded, wherein, injection pressure is 50MPa, and injection temperature is all 200 DEG C, after the segmentation demoulding, obtains a kind of Antibacterial polyurethane toothbrush.The performance test results of this kind of toothbrush material is: tensile strength 30MPa, elongation at break 500%, and monofilament bends recovery rate 81%, to the germ-killing efficiency 99.99% of streptococcus aureus.
Claims (8)
1. a preparation method for Antibacterial polyurethane toothbrush, is characterized in that, comprises the steps:
(1) glycosaminoglycan, silver nitrate aqueous solution and acetic acid aqueous solution are mixed, heating lucifuge stirs after 30 ~ 120 minutes, add sodium borohydride aqueous solution again and carry out reduction reaction, after reacting completely, obtain through aftertreatment glycosaminoglycan-nano silver composite antibacterial agent that median size is 30 ~ 80nm;
The structure of described glycosaminoglycan is as shown in formula I:
In formula I, the scope of n is 2 ~ 50;
(2) the pre-fusion mixing at 50 ~ 85 DEG C by aromatic diols and aromatic diisocyanate, then react 2 ~ 10 hours at 60 ~ 100 DEG C, obtain fragrant base polyurethane prepolymer for use as;
(3) glycosaminoglycan-nano silver composite antibacterial agent that step (1) obtains is scattered in the fragrant base polyurethane prepolymer for use as that aliphatic dialcohol and step (2) obtain and carries out chain extending reaction, carry out granulation after having reacted and obtain antibacterial thermoplastic polyurethane pellet;
(4) the antibacterial thermoplastic polyurethane pellet that step (3) obtains is placed in injection moulding machine and carries out pressing mold injection moulding, then after the segmentation demoulding, obtain the Antibacterial polyurethane toothbrush of a kind of bristle and brush one;
In step (1), the consumption of described glycosaminoglycan, silver nitrate aqueous solution, acetic acid aqueous solution and sodium borohydride aqueous solution is as follows:
In step (2), described aromatic diols is the mixture of one or more in phenylglycol, 1,2-diphenylethyleneglycol and Beta-methyl phenyl-ethylene glycol;
Described aromatic diisocyanate is the mixture of one or more in 2,4 toluene diisocyanate, 2,6-tolylene diisocyanates, ditan-4,4'-vulcabond and ditan-2,4'-vulcabond.
2. the preparation method of Antibacterial polyurethane toothbrush according to claim 1, is characterized in that, in step (1), the molecular weight of described glycosaminoglycan is 1000 ~ 20000Da.
3. the preparation method of Antibacterial polyurethane toothbrush according to claim 1, it is characterized in that, aftertreatment in step (1) comprises: the reaction solution obtained after having reacted is cooled to room temperature, with acetone precipitation, filter, wash, dry at 35 ~ 65 DEG C, obtain described glycosaminoglycan-nano silver composite antibacterial agent.
4. the preparation method of Antibacterial polyurethane toothbrush according to claim 1, is characterized in that, the concentration of the silver nitrate aqueous solution described in step (1) is 0.5 ~ 2.5wt%;
The concentration of the sodium borohydride aqueous solution described in step (1) is 1 ~ 3.5wt%.
5. the preparation method of Antibacterial polyurethane toothbrush according to claim 1, is characterized in that, described aromatic diols and the mass ratio of aromatic diisocyanate are 1 ~ 25:5 ~ 50.
6. the preparation method of Antibacterial polyurethane toothbrush according to claim 1, is characterized in that, in step (3), described aliphatic dialcohol is the mixture of one or more in BDO, 1,6-hexylene glycol and cyclohexanedimethanol.
7. the preparation method of Antibacterial polyurethane toothbrush according to claim 1, is characterized in that, in step (4), in injection molding process, injection pressure is 50-70MPa, and injection temperature is 160 ~ 200 DEG C
8. an Antibacterial polyurethane toothbrush, is characterized in that, is prepared by the preparation method described in any one of claim 1 ~ 7.
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| USD815838S1 (en) | 2016-07-15 | 2018-04-24 | Colgate-Palmolive Company | Toothbrush |
| USD845637S1 (en) | 2017-11-16 | 2019-04-16 | Colgate-Palmolive Company | Oral care implement |
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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 |
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| CN2684634Y (en) * | 2003-06-09 | 2005-03-16 | 苏隽 | Tooth brush |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD815838S1 (en) | 2016-07-15 | 2018-04-24 | Colgate-Palmolive Company | Toothbrush |
| USD845637S1 (en) | 2017-11-16 | 2019-04-16 | Colgate-Palmolive Company | Oral care implement |
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