CN107793636A

CN107793636A - High polymer material for antibacterial toothbrush and preparation method thereof

Info

Publication number: CN107793636A
Application number: CN201710879043.5A
Authority: CN
Inventors: 翁德喜
Original assignee: Zhejiang Yu Tak Chi New Mstar Technology Ltd
Current assignee: Zhejiang Yu Tak Chi New Mstar Technology Ltd
Priority date: 2017-09-26
Filing date: 2017-09-26
Publication date: 2018-03-13

Abstract

The invention discloses a kind of high polymer material for antibacterial toothbrush and preparation method thereof, the high polymer material for antibacterial toothbrush is prepared by the raw material of following weight parts：95 99 parts of basic material, 0.5 2 parts of lubricant, 0.2 0.6 parts of coupling agent, 4.75 9.9 parts of Unined RM antiseptics.The Unined RM antiseptics contained for the high polymer material of antibacterial toothbrush of the present invention are prepared using multiple compounds, there is good dispersiveness and compatibility after being mixed with high polymer, it is added to and excellent ageing-resistant ability, mechanical property and hydrophobic performance is shown in high polymer, extend service life, also have and resist common germ, suppress the advantages of resistance venereal bacteria and high-efficient and lasting are water-fastness, environment purification can be played a part of, eliminate peculiar smell, self-cleaning health care, it is free from environmental pollution, have no side effect to human body, more effectively take good care of health.

Description

High polymer material for antibacterial toothbrush and preparation method thereof

Technical field

The invention belongs to feature field of new materials, and in particular to a kind of high polymer material for antibacterial toothbrush and its Preparation method.

Background technology

The brushes such as toothbrush in the market, coated tongue brush are divided into two major classes：One kind is the brush of hair-planted type, and another kind of is note It is moulded into the high polymer brush of type.The brush of hair-planted type is substantially also to be formed by high polymer spinning.Brush holder material is usually The plastics such as duroplasts such as polypropylene, polyester, TPE thermoplastic elastomer (TPE)s flexible glue is equipped with as buffering, improves feel function.These teeth Brush coated tongue brush serves certain cleaning efficacy.But existing technology has certain limitation, these products are without suppression The microbes such as bacterium, antibacterial functions, bacterium, fungi, algae, which accumulate over a long period, to be collected in outer surface or the bristle of product, is produced Peculiar smell and etiology.Particularly bristle and flexible glue part are easier mould growth and algae in the environment of humidity.To people's Health care belt perplexs.

In view of above-mentioned factor, in recent years, the antibiotic property scientific research to high polymer product both at home and abroad gradually increase, it is led To be obtained by adding the method for a small amount of antiseptic in common high polymer.Current antiseptic is broadly divided into single by structure Inorganic, organic and natural three big series.Inorganic antiseptic is using metal ions such as silver, copper, zinc as antiseptic, with phosphate, swollen The porous, inorganic nonmetallic materials such as profit soil are made for carrier, strong with heat resistance, but its is expensive, and the feature of environmental protection is poor, and product is not Wash resistant, long-term use of and product of the touch containing metal ions such as silver, copper, zinc can adversely affect to the liver of human body. Organic antibacterial agent includes quaternary ammonium salts, imidazoles, pyridines, organic metal class etc., although sterilization speed is fast, antibacterial effect shows Write, but be also easy to produce drug resistance, heat endurance is poor, can not coordinate with high polymer, Durability of antimicrobial effect is short, and toxicity is larger.

By comparison, natural antibacterial agent is extracted from plant, animal or biology, and its wide material sources, cost is low, has peace Atoxic, nutritive and health protection components enrich, the advantages that being not likely to produce drug resistance and be environmentally friendly, therefore its application and research are increasingly It is valued by people.But natural antibacterial agent is typically to extract to form from a kind of plant, animal or biology, antimicrobial component list One, antibacterial range is narrow, its poor compatibility between high polymer, the problems such as reunion, scattered uneven be present, and using process Middle antimicrobial component easily separates out, and antibacterial effect can not be lasting, and germ easily develops immunity to drugs to it, antiseptic pair in the market The germ such as methicillin-resistant staphylococcus staphylococcus of drug resistance have been produced without effect.

Prior art is as disclosed in Application No. 201310338071.8《A kind of monoblock type antibacterial toothbrush and its shaping manufacture Technique》It is only by way of seamless implantation bristle and reaches " antibacterial " purpose.Such antibacterial effect is very limited and presence is permitted More disturbing factors, such as greasy to fall at any position of toothbrush all cause microbial growth, the problems such as easily causing courses of infection.

The content of the invention

For above-mentioned technical problem, the present invention provides a kind of high polymer material and its preparation side for antibacterial toothbrush Method, the antibacterial system that the high polymer material for antibacterial toothbrush contains is prepared using multiple compounds, with high polymer There is good dispersiveness and compatibility after mixing, be added to the high polymer such as product such as polypropylene PP, thermoplastic polyurethane TPU In, excellent ageing-resistant ability, more preferable mechanical property and hydrophobic performance had both been shown, service life has been greatly prolonged, has again Resist common germ, suppress resistance venereal bacteria and the water-fastness advantage of high-efficient and lasting, environment purification can be played, peculiar smell is eliminated, be self-cleaning The effect of health care, it is free from environmental pollution, have no side effect to human body, more effectively take good care of health.

The invention provides a kind of high polymer material for antibacterial toothbrush.The present invention adopts the following technical scheme that：

A kind of high polymer material for antibacterial toothbrush, it is prepared by the raw material of following weight parts：Basic material 95-99 parts, lubricant 0.5-2 parts, coupling agent 0.2-0.6 parts, Unined RM antiseptic 4.75-9.9 parts.

Preferably, the basic material is polypropylene plastics resin, POE elastomer, thermoplastic polyurethane One or more of compositions in elastomer, polybutylene terephthalate (PBT).

Preferably, the Unined RM antiseptics are prepared by the raw material of following weight parts：10-15 parts phenols, 1-3 Part isoquercitrin, 2-4 parts N, N- dihydroxyethylglycin, 3-5 parts glycitin, 5-8 part 4- benzoyl -3- methyl isophthalic acids - The pyrazolin-5-one of phenyl -2,0.3-10 parts dispersant, 0.56-22 parts acrylic acid and 10-15 part 2,4,5,6- monoethyls two Formonitrile HCN.

The Antibacterial Mechanism for the Unined RM antiseptics that the present invention contains is mainly the moon with pathogenic microorganism cell membrane surface Ion is combined or reacted with sulfydryl so as to destroy the structure of protein or influence the synthesis of biomembrane, micro- to suppress cause of disease with this The breeding of biology.Its mechanism of action is summarized as：1st, the protease or other biological activity material needed for biochemical reaction are acted on；2、 Act on hereditary material DNA or other hereditary particle structures；3rd, biofilm system or cell membrane are acted on.

The Unined RM antiseptics that the present invention contains are acted on from many kinds of substance coordinated, can be adsorbed and be carried negative electrical charge Pathogenic microorganism, destroy microbial cell wall construction, suppress the effect such as pathogen oxidizing ferment, dehydrogenase；Also it can remove cause of disease Lipid material in microbial film simultaneously makes protein denaturation or interference pathogenic microorganism mitosis process, suppresses the shape of spindle Into influenceing pathogenic microorganism fission process.So as to the effect for reaching long-acting bacteriostatic, sterilizing.

Preferably, the phenols be isopropyl methyl phenol, triclosan, antiphen, clorofene, one kind in chloreresol or Several compositions；The dispersant is A11 type dispersants.

It is further preferred that the preparation method of the Unined RM antiseptics is：

(1) weigh each raw material by weight, by phenols, isoquercitrin, N, N- dihydroxyethylglycins, glycitin, 4- benzoyls -3- methyl isophthalic acids-the pyrazolin-5-one of phenyl -2, dispersant and 2,4,5,6- tetrachloro phthalonitriles are well mixed, It it is 90-95 DEG C in temperature, pressure is that 48-60 hours are stirred under 500-550mm Hgs, obtains mixture；

(2) acrylic acid is added in the mixture obtained to step (1), in temperature is 90-95 DEG C after being well mixed, pressure is 48-72 hours are stirred under 500-550mm Hgs, natural cooling, obtain UninedRM antiseptics.

Preferably, the lubricant is Tissuemat E or aluminum oxide.

Preferably, the lubricant is modified aluminum oxide, and the preparation method of the aluminum oxide of the modification is as follows：Following originals Material is parts by weight, 5-8 part aluminum oxide is added in the ethanol water that 8-15 parts mass fraction is 70%, adds 0.08- 0.12 part of modifying agent, it is 40-65 DEG C, mixture is obtained with 800-1000 revs/min of rotating speed stirring 12-24 hours in temperature, Mixture is crossed into 300-500 mesh sieves, filter residue is dried in vacuo 5-10 hours at 45-65 DEG C, obtains modified aluminum oxide；It is described Modifying agent is the miscellaneous alkane of nitrogen silicon three of chloromethyl, the one kind of M- chlorophenoxy chlorine silicon rather, in hetero nitrogen silicon tricyclic ethylene glycol.

It is further preferred that the modifying agent is the miscellaneous alkane of nitrogen silicon three of chloromethyl.

Preferably, the coupling agent is silane coupler.

Preferably, the coupling agent is amino-acid modified silane coupler, the amino-acid modified silane coupler Preparation method it is as follows：Following raw materials are parts by weight, and 8-16 parts amino acid, 30-60 parts silane coupler are well mixed and added Enter into 300-500 part tetrahydrofurans, after stirring 2-4 hours under condition of ice bath with 50-150 revs/min of rotating speed, add 0.2-1 parts N, N- dicyclohexylcarbodiimide, continue to stir 24-48 under condition of ice bath with 100-300 revs/min of rotating speed 300 mesh sieves are crossed after hour, retain filtrate, tetrahydrofuran is removed by distillation in filtrate, that is, obtains amino-acid modified silane coupled Agent.

It is further preferred that the amino acid is one kind in L-phenylalanine, L-Leu, L-Aspartic acid, it is described Silane coupler is 3- chloropropyls dimethoxymethylsilane, vinyl diethoxymethylsilane, (3- glycidoxies third Base) one kind in methyldimethylsilane.

It is further preferred that 3- chloropropyls dimethoxymethylsilane, L- that the coupling agent, which is L-phenylalanine, to be modified The vinyl diethoxy that (3- glycidoxypropyl groups) methyldiethoxysilane of leucine modification, L-Aspartic acid are modified One or more mixture in methyl-monosilane.

It is further preferred that the coupling agent is the 3- chloropropyls dimethoxymethylsilane and L- that L-phenylalanine is modified The vinyl diethoxymethylsilane that aspartic acid is modified is 1 in mass ratio:The mixture of (3-5).

The present invention also provides the preparation method of the high polymer material for antibacterial toothbrush：Basic material is weighed by weight Material, lubricant, coupling agent, Unined RM antiseptics, basic material, lubricant, coupling agent are put into mixer, in 25-30 DEG C 10-30min is stirred with 100-300 revs/min of rotating speed with mixer, is then fed into double screw extruder main feeding hopper, Simultaneously by Unined RM antiseptics from side spout add, screw speed be 50-150 revs/min, 120-260 DEG C of temperature In 70-120 DEG C of dry 30-180 minute, the high polymer material for toothbrush is made after melting extrusion, cooling, granulation in section Antibacterial matrices.

Beneficial effects of the present invention：The Unined RM contained for the high polymer material of antibacterial toothbrush of the present invention resist Microbial inoculum is prepared using multiple compounds, is had good dispersiveness and compatibility after being mixed with high polymer, is added to height Excellent ageing-resistant ability, mechanical property and hydrophobic performance are shown in polymer, extends service life, is also had anti-common Germ, suppress the advantages of resistance venereal bacteria and high-efficient and lasting are water-fastness, environment purification can be played, eliminate peculiar smell, self-cleaning health care Effect, it is free from environmental pollution, have no side effect to human body, more effectively take good care of health.

On the basis of common sense in the field is met, above-mentioned each optimum condition, it is each preferably can to produce the present invention in any combination Embodiment.

Embodiment

The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business Product specification selects.

In following embodiments, primary raw material and instrument used are as follows：

Polypropylene plastics resin, polypropylene abbreviation PP, the model H12G- that the present invention is produced using Ineos company of the U.S. 00 polypropylene, MI=12g/10min.

POE elastomer, abbreviation POE, the trade mark produced using Mitsui chemical company are DF605's POE elastomer, MI=0.5g/10min.

Polybutylene terephthalate (PBT), abbreviation PBT, the model of the specifically used primary radical innovations Plastics Company production of sand V3500EX polybutylene terephthalate (PBT).

TPUE, abbreviation TPU, the thermoplastic that the trade mark produced using BASF Aktiengesellschaft is 1190A Property elastomer polyurethane elastomer, shore hardness 90A.

Common PP resins, the model of Dushanzi petrochemical industry branch company of PetroChina Company Ltd. production K4912 acrylic resin.

Common POE particles, the trade mark that du pont company produces are 8999 POE elastomer.

General T PU particles, the model T3190 produced using Shandong Inov Polyurethane Co., Ltd. thermoplasticity Polyurethane elastomer particle.

Common PBT particles, the model 1100-600s produced using TaiWan, China Changchun artificial resin limited company Polybutylene terephthalate (PBT).

A11 type dispersants, A11 dispersants, it is polyacrylic acid sodium salt, the model of chemical production is first created using France ProxA11 Sodium Polyacrylate dipersant.

Antiphen, No. CAS：97-23-4, buy from Hebei Hao Yu Chemical Co., Ltd.s.

Isoquercitrin, No. CAS：482-35-9, buy from Henan Tian Fu Chemical Co., Ltd.s.

N, N- dihydroxyethylglycin, be a kind of white crystalline amino acid analogue soluble in water, containing two- OH ,-a COOH, there is good chelant performance.N, N- dihydroxyethylglycin can be synthesized or is commercially available.Synthetic method Reference《The chelating ability of N, N- bicine N- applies (Huaqiao University's journal natural science edition, in the April, 2006 of volume 27 2nd phase, author Chen Junzhi, Feng's white silk are enjoyed, Liu Junhai).The specifically used N of the present invention, N- dihydroxyethylglycins are bought from upper The graceful bio tech ltd of Hypon.

Glycitin, No. CAS：40246-10-4, buy from Nanjing draft source bio tech ltd.

4- benzoyls -3- methyl isophthalic acids-the pyrazolin-5-one of phenyl -2, No. CAS：4551-69-3, buy outstanding permanent from Hangzhou Chemical Co., Ltd..

Acrylic acid, No. CAS：79-10-7, certainly forever magnificent chemical scientific and technological (Jiangsu) Co., Ltd of purchase.

2,4,5,6- tetrachloro phthalonitriles, No. CAS：1897-45-6, purchased from Zhejiang Jie Ma Chemical Co., Ltd.s.

L-phenylalanine, No. CAS：63-91-2, buy from Nanjing draft source bio tech ltd.

L-Leu, No. CAS：61-90-5, buy from Zhengzhou Brian Jacks chemical products Co., Ltd.

L-Aspartic acid, No. CAS：56-84-8, buy from Yangzhou chemical inc.

3- chloropropyl dimethoxymethylsilanes, No. CAS：18171-19-2, buying from Jingzhou City Jiang-Han Area fine chemistry industry has Limit company.

Vinyl diethoxymethylsilane, No. CAS：5507-44-8, buy the limited public affairs of Shandong Wanda's organosilicon new material Department.

(3- glycidoxypropyl groups) methyldimethylsilane, No. CAS：65799-47-5, buy organic from Shandong Wanda Silicon new material Co., Ltd.

Tetrahydrofuran, No. CAS：109-99-9, buy from Shanghai Chu Tai Chemical Industry Science Co., Ltd.

N, N- dicyclohexylcarbodiimide, No. CAS：538-75-0, buy from Hubei Kang Baotai Fine Chemical Co., Ltd.

Tissuemat E, the trade mark that specifically used Honeywell Inc. of the U.S. produces are A-C-6 Tissuemat E.

Aluminum oxide, No. CAS：1344-28-1, purchased from Shanghai jump river titanium white heavy chemicals Co., Ltd, the mesh of particle diameter 800.

The miscellaneous alkane of nitrogen silicon three of chloromethyl, No. CAS：42003-39-4, buy from Shanghai Zhuan Ming new materials Science and Technology Ltd..

M- chlorophenoxy chlorine silicon is peaceful, No. CAS：86825-39-0, buy from Shanghai Chu Qing new materials Science and Technology Ltd..

Hetero nitrogen silicon tricyclic ethylene glycol, No. CAS：56929-77-2, buy from Shanghai Ji Laide new materials Science and Technology Ltd..

Silver-ion antibiotic polypropylene agglomerate, purchased from the friend's new material Co., Ltd of Hangzhou nine, model CYNK62, silver system Inorganic antibacterial powder mass fraction is 12.5%.

Double screw extruder：Nanjing Cole gram extrudes the model SHJ-50 of Equipment Limited production parallel double-screw Extruding granulator, draw ratio 40：1, screw diameter 50.5mm.

Vulcanizing press, the model XLB-D of Renqiu City Jia You Machinery Manufacturing Co., Ltd.s production vulcanizing press.

Spinning-drawing machine, the model MT-50 of Jiangsu Mei Zhilong Machinery Co., Ltd.s production spinneret extruder.

350T injection machines, the production of Mitsubishi Ishikawajima-Harima Heavy Industries Ltd..

The present invention is further illustrated below by the mode of embodiment, used part is parts by weight.

Embodiment 1

For the high polymer material M-PP of antibacterial toothbrush, it is prepared by the raw material of following weight parts：Polypropylene 95 Part, 0.5 part of lubricant, 0.2 part of coupling agent, 4.75 parts of Unined RM antiseptics, i.e. the dosage of Unined RM antiseptics is poly- The 5% of propylene.

The preparation method of the high polymer material M-PP for antibacterial toothbrush is：Weigh by weight PP polypropylene, Lubricant, coupling agent, Unined RM antiseptics, by PP polypropylene, lubricant, coupling agent input mixer, at 25 DEG C with stirring Mix machine and 20min is stirred with 100 revs/min of rotating speed, be then fed into double screw extruder main feeding hopper, while by Unined RM antiseptics are added from side spout, and 30 points are dried at 120 DEG C after melting extrusion, cooling, granulation in double screw extruder Clock, the antibacterial matrices M-PP of the high polymer material for toothbrush is made.The feeding section temperature of double screw extruder is 120-150 DEG C, mixing section temperature is 160-190 DEG C, and extruding zone temperature is 190-230 DEG C, and head temperature is 190-230 DEG C, screw speed For 100 revs/min.

The Unined RM antiseptics are prepared by the raw material of following weight parts：15 parts of phenols, 3 parts of isoquercitrin, 4 Part N, N- dihydroxyethylglycins, 5 parts of glycitins, 8 parts of 4- benzoyls -3- methyl isophthalic acids-pyrazolin-5-ones of phenyl -2, 0.8 part of dispersant, 7 parts of acrylic acid and 12 parts of 2,4,5,6- tetrachloro phthalonitriles.The dispersant is A11 type dispersants.Institute It is antiphen to state phenols.

The preparation method of the Unined RM antiseptics is：

(1) weigh each raw material by weight, by phenols, isoquercitrin, N, N- dihydroxyethylglycins, glycitin, 4- benzoyls -3- methyl isophthalic acids-the pyrazolin-5-one of phenyl -2, dispersant and 2,4,5,6- tetrachloro phthalonitriles are well mixed, Temperature be 90 DEG C, pressure be to stir 50 hours under 525mm Hgs, obtain mixture；

(2) add acrylic acid in the mixture obtained to step (1), it is well mixed after temperature be 90 DEG C, pressure be Stirred 48 hours under 525mm Hgs, natural cooling, obtain Unined RM antiseptics.

The lubricant is Tissuemat E.

The coupling agent is 3- chloropropyl dimethoxymethylsilanes.

Embodiment 2

For the high polymer material M-POE of antibacterial toothbrush, it is prepared by the raw material of following weight parts：Ethene-butylene 95 parts of copolymer elastomer, 0.5 part of lubricant, 0.2 part of coupling agent, 4.75 parts of Unined RM antiseptics, i.e. Unined RM resist The dosage of microbial inoculum is the 5% of ethylene-butene copolymer elastomer.

The preparation method of the high polymer material M-POE for antibacterial toothbrush is：Ethene-fourth is weighed by weight Alkene copolymer elastomer, lubricant, coupling agent, Unined RM antiseptics, by ethylene-butene copolymer elastomer, lubricant, In coupling agent input mixer, 20min is stirred with 100 revs/min of rotating speed with mixer at 25 DEG C, is then fed into twin-screw In extruder main feeding hopper, while Unined RM antiseptics are added from side spout, squeezed in double screw extruder through melting Go out, cool down, be granulated after dried 60 minutes at 70 DEG C, the antibacterial matrices M-POE of the high polymer material for toothbrush is made.Double spiral shells The feeding section temperature of bar extruder is 120-150 DEG C, and mixing section temperature is 140-170 DEG C, and extruding zone temperature is 170-190 DEG C, Head temperature is 190-200 DEG C, and screw speed is 100 revs/min.

The preparation method of the Unined RM antiseptics is：

The lubricant is Tissuemat E.

The coupling agent is 3- chloropropyl dimethoxymethylsilanes.

Embodiment 3

For the high polymer material M-TPU of antibacterial toothbrush, it is prepared by the raw material of following weight parts：Thermoplastic poly ammonia 95 parts of ester elastomer, 0.5 part of lubricant, 0.2 part of coupling agent, 4.75 parts of Unined RM antiseptics, i.e. Unined RM antiseptics Dosage be TPUE 5%.

The preparation method of the high polymer material M-TPU for antibacterial toothbrush is：Thermoplastic poly is weighed by weight Urethane elastomer, lubricant, coupling agent, Unined RM antiseptics, TPUE, lubricant, coupling agent are thrown Enter in mixer, 20min is stirred with 100 revs/min of rotating speed with mixer at 25 DEG C, twin-screw extrusion owner is then fed into and feeds In hopper, while Unined RM antiseptics are added from side spout, in double screw extruder through melting extrusion, cool down, make Dried 60 minutes at 120 DEG C after grain, the antibacterial matrices M-TPU of the high polymer material for toothbrush is made.Double screw extruder Feeding section temperature be 140-150 DEG C, mixing section temperature be 170-180 DEG C, extruding zone temperature be 180-190 DEG C, head temperature For 190-200 DEG C, screw speed is 100 revs/min.

The preparation method of the Unined RM antiseptics is：

The lubricant is Tissuemat E.

The coupling agent is 3- chloropropyl dimethoxymethylsilanes.

Embodiment 4

For the high polymer material M-PBT of antibacterial toothbrush, it is prepared by the raw material of following weight parts：Poly- terephthaldehyde Sour 95 parts of butanediol ester, 0.5 part of lubricant, 0.2 part of coupling agent, 4.75 parts of Unined RM antiseptics, i.e. Unined RM antibacterials The dosage of agent is the 5% of TPUE.

The preparation method of the high polymer material M-PBT for antibacterial toothbrush is：Weigh by weight poly- to benzene two Formic acid butanediol ester, lubricant, coupling agent, Unined RM antiseptics, by polybutylene terephthalate (PBT), lubricant, coupling In agent input mixer, 20min is stirred with 100 revs/min of rotating speed with mixer at 25 DEG C, is then fed into twin-screw extrusion In owner's feeding hopper, at the same by Unined RM antiseptics from side spout add, in double screw extruder through melting extrusion, Cooling, dried 180 minutes at 120 DEG C after being granulated, the antibacterial matrices M-PBT of the high polymer material for toothbrush is made.Double spiral shells The feeding section temperature of bar extruder is 120-150 DEG C, and mixing section temperature is 170-220 DEG C, and extruding zone temperature is 230-260 DEG C, Head temperature is 230-260 DEG C, and screw speed is 100 revs/min.

The preparation method of the Unined RM antiseptics is：

The lubricant is Tissuemat E.

The coupling agent is 3- chloropropyl dimethoxymethylsilanes.

Embodiment 5

Prepared by embodiment 1 is 4 in mass ratio for the high polymer material M-PP of antibacterial toothbrush and common PP resins: Injection molding after the mixing of 96 ratios.It it is 180-230 DEG C in barrel temperature, mold temperature is 25 DEG C, 220 DEG C of nozzle temperature, injection Under conditions of pressure is 100MPa, 4cm × 6cm × 0.1cm plaques are made on 350T injection machines.

In actual use by using for reference present disclosure, PP can be replaced by other plastic resins, as PET-g, ABS, PC, it is considered as comprising within the scope of the present invention.

Embodiment 6

It is in mass ratio for the high polymer material M-POE of antibacterial toothbrush and common POE particles by prepared by embodiment 2 10:Injection molding after the mixing of 90 ratios.It is 180-200 DEG C in barrel temperature, mold temperature is 25 DEG C, injection pressure 65MPa, Under conditions of 190 DEG C of nozzle temperature, 4cm × 6cm × 0.1cm plaques are made on 350T injection machines.

In actual use by using for reference present disclosure, POE can be replaced by other TPE, as TPV, SEBS, TPE, it is considered as comprising within the scope of the present invention.

Embodiment 7

High polymer material M-TPU and general T PU particle for antibacterial toothbrush prepared by embodiment 3 is in mass ratio 6:Injection molding after the mixing of 94 ratios.It it is 180-210 DEG C in barrel temperature, mold temperature is 25 DEG C, 200 DEG C of nozzle temperature, note Under conditions of injection pressure is 60MPa, 4cm × 6cm × 0.1cm plaques are made on 350T injection machines.

In actual use by using for reference present disclosure, TPU can be replaced by other materials, such as TPEE, be considered as Comprising within the scope of the present invention.

Embodiment 8

It is in mass ratio for the high polymer material M-PBT of antibacterial toothbrush and common PBT particles by prepared by embodiment 4 6:After the mixing of 94 ratios under the conditions of spinning temperature is 260 DEG C, length of the wire drawing into a diameter of 0.35-0.4mm on spinneret machine Silk.Long filament is depressed into the plaques that thickness is 0.1cm on vulcanizing press in 240 DEG C of conditions.

In actual use by using for reference present disclosure, PBT can be replaced by plastics such as nylon, is considered as and be included in In protection scope of the present invention.

Comparative example 1

It is 1 in mass ratio by commercially available silver-ion antibiotic polypropylene agglomerate and common PP resins:Noted after the mixing of 62.5 ratios It is moulded into type.It it is 180-230 DEG C in barrel temperature, mold temperature is 25 DEG C, and nozzle temperature is 220 DEG C, injection pressure 100MPa Under conditions of, 4cm × 6cm × 0.1cm plaques are made on 350T injection machines.

Embodiment 9

The preparation method of the Unined RM antiseptics is：

The lubricant is aluminum oxide.

The coupling agent is 3- chloropropyl dimethoxymethylsilanes.

Embodiment 10

The preparation method of the Unined RM antiseptics is：

The lubricant is modified aluminum oxide, the preparation method of the aluminum oxide of the modification：Following raw materials are weight Part, 5 parts of aluminum oxide are added in the ethanol water that 8 parts of mass fractions are 70%, add 0.08 part of modifying agent, be in temperature 40 DEG C, stirred 12 hours with 800 revs/min of rotating speed and obtain mixture, mixture is crossed into 500 mesh sieves, filter residue is true at 45 DEG C Sky is dried 5 hours, obtains modified aluminum oxide；The modifying agent is the miscellaneous alkane of nitrogen silicon three of chloromethyl.

The coupling agent is 3- chloropropyl dimethoxymethylsilanes.

Embodiment 11

It is substantially the same manner as Example 10, differ only in, the modifying agent described in the present embodiment 11 is M- chlorophenoxy chlorine silicon Rather.

Embodiment 12

It is substantially the same manner as Example 10, differ only in, the modifying agent described in the present embodiment 12 is hetero nitrogen silicon tricyclic second two Alcohol.

Embodiment 13

The preparation method of the Unined RM antiseptics is：

The lubricant is modified aluminum oxide, the preparation method of the aluminum oxide of the modification：Following raw materials are weight Part, for 5 parts of aluminum oxide are added in the ethanol water that 8 parts of mass fractions are 70%, 0.08 part of modifying agent is added, in temperature Mixture is obtained for 40 DEG C, with 800 revs/min of rotating speed stirring within 12 hours, mixture is crossed into 500 mesh sieves, by filter residue at 45 DEG C Vacuum drying 5 hours, obtains modified aluminum oxide；The modifying agent is the miscellaneous alkane of nitrogen silicon three of chloromethyl.

The coupling agent is the 3- chloropropyl dimethoxymethylsilanes that L-phenylalanine is modified.The L-phenylalanine changes The preparation method of the 3- chloropropyl dimethoxymethylsilanes of property is as follows：Following raw materials are parts by weight, by 8 parts of L- phenylpropyl alcohol ammonia Acid, 30 parts of 3- chloropropyl dimethoxymethylsilanes be added in 300 parts of tetrahydrofurans, under 0 DEG C of condition of ice bath with 100 turns/ After the rotating speed of minute stirs 2 hours, 0.5 part of N is added, N- dicyclohexylcarbodiimides, is continued under 0 DEG C of condition of ice bath with 200 Rev/min rotating speed stir 24 hours after cross 300 mesh sieves, retain filtrate, tetrahydrofuran is distilled off at 70 DEG C in filtrate, is produced The 3- chloropropyl dimethoxymethylsilanes being modified to L-phenylalanine.

Embodiment 14

It is substantially the same manner as Example 13, differ only in, coupling agent described in the present embodiment 14 is the (3- that L-Leu is modified Glycidoxypropyl group) methyldiethoxysilane.(3- glycidoxypropyl groups) methyl diethyl that the L-Leu is modified The preparation method of TMOS is as follows：Following raw materials are parts by weight, by 8 parts of L-Leus, 30 parts of (3- glycidoxies third Base) methyldiethoxysilane is added in 300 parts of tetrahydrofurans, stirred under 0 DEG C of condition of ice bath with 100 revs/min of rotating speed After mixing 2 hours, 0.5 part of N is added, N- dicyclohexylcarbodiimides, is continued under 0 DEG C of condition of ice bath with 200 revs/min of rotating speed Stirring crosses 300 mesh sieves after 24 hours, retains filtrate, filtrate is distilled off into tetrahydrofuran at 70 DEG C, that is, obtains L-Leu and changes (3- glycidoxypropyl groups) methyldiethoxysilane of property.

Embodiment 15

It is substantially the same manner as Example 13, differ only in, coupling agent described in the present embodiment 15 is what L-Aspartic acid was modified Vinyl diethoxymethylsilane.The preparation method for the vinyl diethoxymethylsilane that the L-Aspartic acid is modified is such as Under：Following raw materials are parts by weight, and 8 parts of L-Aspartic acids, 30 parts of vinyl diethoxymethylsilanes are added into 300 part four In hydrogen furans, after being stirred 2 hours with 100 revs/min of rotating speed under 0 DEG C of condition of ice bath, 0.5 part of N, N- dicyclohexyl carbon are added Diimine, continue to cross 300 mesh sieves after stirring 24 hours with 200 revs/min of rotating speed under 0 DEG C of condition of ice bath, retain filtrate, Tetrahydrofuran is distilled off at 70 DEG C in filtrate, that is, obtains the vinyl diethoxymethylsilane of L-Aspartic acid modification.

Comparative example 2

It is substantially the same manner as Example 13, differ only in, coupling agent described in this comparative example 2 is (3- glycidoxypropyl groups) Methyldiethoxysilane.

Comparative example 3

It is substantially the same manner as Example 13, differ only in, coupling agent described in this comparative example 3 is vinyl diethoxymethyl Silane.

Embodiment 16

It is substantially the same manner as Example 13, differ only in, the coupling agent described in the present embodiment 16 is modified for L-phenylalanine 3- chloropropyls dimethoxymethylsilane and L-Aspartic acid be modified vinyl diethoxymethylsilane be in mass ratio 1:3 mixture.

The preparation method for the 3- chloropropyl dimethoxymethylsilanes that the L-phenylalanine is modified is as follows：Following raw materials are equal For parts by weight, 8 parts of L-phenylalanines, 30 parts of 3- chloropropyl dimethoxymethylsilanes are added in 300 parts of tetrahydrofurans, After being stirred 2 hours with 100 revs/min of rotating speed under 0 DEG C of condition of ice bath, 0.5 part of N of addition, N- dicyclohexylcarbodiimides, Continue to cross 300 mesh sieves after stirring 24 hours with 200 revs/min of rotating speed under 0 DEG C of condition of ice bath, retain filtrate, filtrate is existed 70 DEG C are distilled off tetrahydrofuran, that is, obtain the 3- chloropropyl dimethoxymethylsilanes of L-phenylalanine modification.

The preparation method for the vinyl diethoxymethylsilane that the L-Aspartic acid is modified is as follows：Following raw materials are Parts by weight, 8 parts of L-Aspartic acids, 30 parts of vinyl diethoxymethylsilanes are added in 300 parts of tetrahydrofurans, at 0 DEG C After being stirred 2 hours with 100 revs/min of rotating speed under condition of ice bath, 0.5 part of N is added, N- dicyclohexylcarbodiimides, is continued 300 mesh sieves are crossed after being stirred 24 hours with 200 revs/min of rotating speed under 0 DEG C of condition of ice bath, retain filtrate, by filtrate in 70 DEG C of steamings Tetrahydrofuran is removed in distillation, that is, obtains the vinyl diethoxymethylsilane of L-Aspartic acid modification.

The test result of the present embodiment 16 is：Tearing strength is 89.5KNm^-1, water droplet contact angle is 95.4 °, water absorption rate For 0.27%.

Measure of merit example 1

Anti-microbial property test：According to ISO22196:2011 standards carry out anti-microbial property survey to embodiment 5-8 plaques Examination, test result are the original antibacterial activity of plaques.The strain of experiment is Escherichia coli (ATCC8739), resistance to methoxy west Woods golden yellow staphylococcus (ATCC33591), golden yellow staphylococcus (ATCC6538), Candida albicans (ATCC10231), pneumonia Klebsiella (ATCC4352).Test result is shown in Table 1.

The plaques that other Example 5-8 is obtained, the anti-microbial property test after the warm water that enters to pass through immersion.In experiment sample An aperture is made a call in one end of piece, to be tied down print with a cotton thread, and plaques is totally submerged in water.Sample will be tested Piece is put into 1000ml beaker, adds 1000ml distilled water, heats the water to 50 DEG C, is placed 168 hours；Then the steaming renewed Distilled water 1000ml, 50 DEG C are heated to, placed 168 hours.The experiment will repeat to continue 4320 hours (i.e. 180 days).After 180 days, Plaques are taken out, naturally dry, carry out antibacterial, mould proof, anti-algae performance test, test result is that sample board soaks through warm water Antibacterial activity afterwards.Test result is shown in Table 2.

Table 1：The original antibacterial activity value of plaques

Table 2：Antibacterial activity value of the plaques after warm water soaks

The present invention is prepared for the high polymer material for antibacterial toothbrush containing Unined RM antiseptics, high polymer Stock for polypropylene plastics resin, POE elastomer, polybutylene terephthalate (PBT), thermoplastic poly One kind in urethane elastomer, the high polymer material for antibacterial toothbrush of the invention are added in common high polymer material Excellent antibacterial effect can be played.Unined RM antiseptics can suppress Escherichia coli, methicillin-resistant staphylococcus staphylococcus, gold The growth of yellow staphylococcus, Candida albicans, Friedlander's bacillus, by being combined with the anion on bacterial cell membrane surface Or reacted with sulfydryl so as to destroy the structure of protein or influence the synthesis of biomembrane, it is thin to suppress antibacterial breeding and kill with this The effect of bacterium.The high polymer material antibacterial activity value for antibacterial toothbrush of the present invention is far above 0.5.Used with comparative example 1 Silver-ion antibiotic PP master batches are compared, and the antiseptic of the high polymer material for antibacterial toothbrush of the invention is through warm water immersion test Antibacterial activity value has almost no change afterwards, water-fastness practical, has long-acting lasting bactericidal effect.Especially, it is commercially available Silver-ion antibiotic PP is very poor to the antibacterial effect of Candida albicans and methicillin-resistant staphylococcus staphylococcus, and the present invention contain The high polymer material for antibacterial toothbrush of Unined RM antiseptics has excellent to methicillin-resistant staphylococcus staphylococcus Antibacterial effect, hence it is evident that better than the antibacterial PP of commercially available silver ion.

Measure of merit example 2

Embodiment 9-16, comparative example the 2-3 high polymer material for antibacterial toothbrush being prepared tear by force Degree test, is tested according to the method B test procedures (a) in GB/T529-2008 standards.Test is shown in Table 3.

Table 3：Tearing strength test result table

	Tearing strength/(KNm^-1)
		Embodiment 9	76.5
Embodiment 10	81.6
		Embodiment 11	77.8
Embodiment 12	79.2
		Embodiment 13	85.3
Embodiment 14	82.7
		Embodiment 15	86.4
Comparative example 2	80.2
		Comparative example 3	76.4

As seen from the results in Table 3, with embodiment 9 using aluminum oxide compared with lubricant, embodiment 10-12 changes aluminum oxide Property after lubricant as high polymer material, preferred by being carried out to modifying agent, the tearing strength of polymeric material improves, power Learn performance enhancement.Compared with comparative example 2-3 uses silane coupler, embodiment 13-15 is entered using amino acid to silane coupler Row is modified, and the species of amino acid and silane coupler is carried out preferably, and amino-acid modified rear coupling agent can be by inorganic component, height Polymeric base material, Unined RM antiseptics preferably combine, and improve dispersiveness and cohesive, therefore improve for resisting The tearing strength of the high polymer material of bacterium toothbrush.The present invention antibacterial toothbrush high polymer material it is solid firmly, be not easy by Damage.

Measure of merit example 3

The direct injection molding of high polymer material for antibacterial toothbrush prepared by embodiment 9-15, comparative example 2-3.Note Barrel temperature is leading portion during modeling：180-190 DEG C, 190-200 DEG C of stage casing, 200-210 DEG C of back segment, mold temperature be 25 DEG C, nozzle 200 DEG C of temperature, under conditions of injection pressure is 60MPa, 4cm × 6cm × 0.1cm experiment sample is made on 350T injection machines Piece.Then water droplet contact angle test and water absorption rate test are carried out to plaques.

Water droplet contact angle is tested：Measured using JCZ000C types contact angle/interfacial tension of upper marine morning equipment Co., Ltd Instrument is tested, 0-180 ° of Contact-angle measurement scope, during experiment, plaques is entirely placed on sample stage, by 1pL water droplets in sample Product surface, catches image immediately, makees tangent line and reads the contact angle number of degrees, each sample is tested 5 times and averaged.Water absorption rate test：Survey The weight W of plaques is weighed before examination₀, then sample is placed in 25 DEG C of deionized water and soaked 120 hours, table is dried in taking-up Face moisture, weigh be designated as W immediately₁, calculate water absorption rate, water absorption rate=(W₁-W₀)/W₀, 3 parallel laboratory tests are done, as a result take three to put down The average value of row experiment.Test result is shown in Table 4.

Table 4：Water droplet contact angle is surveyed and water absorption rate test result table

Compared with Example 9, embodiment 10-15 water droplet contact angle increase, water absorption rate decline, wetting of the water droplet to surface Ability is low, beneficial to the sewage corrosion resistance for improving antibacterial toothbrush high polymer material surface.The water drop contact of embodiment 15 More than 90 °, hydrophobic properties of the surface greatly improve at angle.The antibacterial toothbrush high polymer material of the present invention has good hydrophobicity Can, it is not easy to soak using rear surface, the recovery surface-dry state used time is short, can effectively avoid the moisture-induced bacterium of brush surface Growing concern.

Toothbrush application：

The mould external member that toothbrush product designs according to ordinary toothbrush produces.The formula for being first according to embodiment 5 is molded by PP Toothbrush handle.Toothbrush handle is put into encapsulation die to be formulated POE materials coating and injection moulding in PP toothbrush handles according to embodiment 6. It is molded by another mold according to the formula of embodiment 7 after TPU head toothbrushes and is directly embedded in shape in cladding POE PP toothbrush handles Into antibacterial toothbrush.The antibacterial toothbrush product (by above-mentioned formula but does not add antiseptic and manufactured tooth with ordinary toothbrush product Brush) contrast be placed on toilet (Shenzhen 4-5 months) inner 1 month after, on ordinary toothbrush have been found that there is black mould spot to go out It is existing.And it is used to not find any black mould spot then on the antibacterial toothbrush of the production of the high polymer material of antibacterial toothbrush at this.

Preferred embodiment of the invention described in detail above.It should be appreciated that one of ordinary skill in the art without Creative work can is needed to make many modifications and variations according to the design of the present invention.Therefore, all technologies in the art Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical scheme, all should be in the protection domain being defined in the patent claims.

Claims

1. a kind of high polymer material for antibacterial toothbrush, it is characterised in that be prepared by the raw material of following weight parts：Base Plinth material 95-99 parts, lubricant 0.5-2 parts, coupling agent 0.2-0.6 parts, Unined RM antiseptic 4.75-9.9 parts.

A kind of 2. high polymer material for antibacterial toothbrush according to claim 1, it is characterised in that the basic material Expect for polypropylene plastics resin, POE elastomer, TPUE, polybutylene terephthalate One or more of compositions in ester.

3. the high polymer material according to claim 1 for antibacterial toothbrush, it is characterised in that the Unined RM Antiseptic is prepared by the raw material of following weight parts：10-15 parts phenols, 1-3 parts isoquercitrin, 2-4 parts N, N- dihydroxy second Base glycine, 3-5 parts glycitin, the 5-8 part 4- benzoyls -3- methyl isophthalic acids-pyrazolin-5-one of phenyl -2,0.3-10 parts point Powder, 0.56-22 parts acrylic acid and 10-15 part 2,4,5,6- tetrachloro phthalonitriles.

4. the high polymer material according to claim 3 for antibacterial toothbrush, it is characterised in that the phenols is isopropyl One or more combination thing in ylmethyl phenol, triclosan, antiphen, clorofene, chloreresol；The dispersant is A11 types Dispersant.

5. a kind of high polymer material for antibacterial toothbrush according to claim 3, it is characterised in that described The preparation method of UninedRM antiseptics is：

(1) each raw material is weighed by weight, by phenols, isoquercitrin, N, N- dihydroxyethylglycins, glycitin, 4- benzene Formoxyl -3- methyl isophthalic acids-the pyrazolin-5-one of phenyl -2, dispersant and 2,4,5,6- tetrachloro phthalonitriles are well mixed, in temperature Spend for 90-95 DEG C, pressure is that 48-60 hours are stirred under 500-550mm Hgs, obtains mixture；

(2) add acrylic acid in the mixture obtained to step (1), be well mixed after temperature be 90-95 DEG C, pressure 500- 48-72 hours are stirred under 550mm Hgs, natural cooling, obtain UninedRM antiseptics.

6. the high polymer material according to claim 1 for antibacterial toothbrush, it is characterised in that the lubricant is poly- Ethylene waxes or aluminum oxide.

7. the high polymer material according to claim 1 for antibacterial toothbrush, it is characterised in that the lubricant is to change The aluminum oxide of property, the preparation method of the aluminum oxide of the modification are as follows：Following raw materials are parts by weight, and 5-8 part aluminum oxide is added Enter to 8-15 parts mass fraction be 70% ethanol water in, add 0.08-0.12 part modifying agent, temperature be 40-65 DEG C, Mixture is obtained with 800-1000 revs/min of rotating speed stirring 12-24 hours, mixture is crossed into 300-500 mesh sieves, filter residue is existed 45-65 DEG C of vacuum drying 5-10 hour, obtain modified aluminum oxide；The modifying agent is the miscellaneous alkane of nitrogen silicon three of chloromethyl, M- chlorobenzenes Epoxide chlorine silicon is peaceful, one kind in hetero nitrogen silicon tricyclic ethylene glycol.

8. the high polymer material according to claim 1 for antibacterial toothbrush, it is characterised in that the coupling agent is silicon Alkane coupling agent.

9. the high polymer material according to claim 1 for antibacterial toothbrush, it is characterised in that the coupling agent is ammonia The modified silane coupler of base acid, the preparation method of the amino-acid modified silane coupler are as follows：Following raw materials are attached most importance to Part is measured, 8-16 parts amino acid, 30-60 parts silane coupler are well mixed and be added in 300-500 part tetrahydrofurans, in ice bath Under the conditions of with 50-150 revs/min of rotating speed stirring 2-4 hours after, add 0.2-1 parts N, N- dicyclohexylcarbodiimide, continue To cross 300 mesh sieves after 100-300 revs/min of rotating speed stirring 24-48 hours under condition of ice bath, retain filtrate, filtrate passes through Tetrahydrofuran is distilled off, that is, obtains amino-acid modified silane coupler；The amino acid is L-phenylalanine, the bright ammonia of L- One kind in acid, L-Aspartic acid, the silane coupler are 3- chloropropyls dimethoxymethylsilane, vinyl diethoxy One kind in methyl-monosilane, (3- glycidoxypropyl groups) methyldimethylsilane.

A kind of 10. preparation method of the high polymer material as claimed in claim 1 for antibacterial toothbrush, it is characterised in that Basic material, lubricant, coupling agent, Unined RM antiseptics are weighed by weight, and basic material, lubricant, coupling agent are thrown Enter in mixer, 10-30min is stirred with 100-300 revs/min of rotating speed with mixer at 25-30 DEG C, is then fed into twin-screw In extruder main feeding hopper, while Unined RM antiseptics are added from side spout, screw speed be 50-150 turn/ Minute, 120-260 DEG C of temperature range in 70-120 DEG C of dry 30-180 minute, be made and be used for after melting extrusion, cooling, granulation The antibacterial matrices of the high polymer material of toothbrush.