A kind of antibiotic-mould proof textile fabric and preparation method thereof
Technical field
The present invention relates to a kind of textile and preparation method thereof, particularly relates to antibiotic-mould proof textile fabric and its preparation
Method.
Background technology
Textile can absorb the effluents such as the sweat of human secretory, sebum, under the suitable environment of temperature and humidity, live away from home
Microorganism on the textile can amount reproduction, decompose human secretion, produce the material that ammonia etc. carries peculiar smell, or on fabric
Bacterial plaque is generated, so that in dress or application process, uncomfortable or harmful effect is produced to human body, textile is produced and goes mouldy, be crisp
Change even rotten.With the development and the improvement of people's living standards of society, the new market demand is generated, consumer wishes to spin
Fabric has antibacterial functions, to meet the comfortable living needs of civilization.In textile, natural fiber is arranged than synthetic fibers moisture absorption
Sweat performance is good and comfortable and easy to wear, and the personal clothing overwhelming majority such as the underwear of people, socks, towel, sheet uses natural fiber material
Material, so natural fiber material turns into the main product of antibiotic fabric.Antibiotic fabric refer to do not change fabric sense organ itself or
On the premise of physical and chemical character (such as intensity, water imbibition, feel, aberration), antibacterial is carried out to fabric with various antiseptics and added
Work, fibrous material is resisted microorganism decomposition in itself and go bad, can also make the microorganism devitalization being attached on fabric
Or not excessive multiplication, the quality of textile and the quality of life of consumer are improved, antibiotic fabric is also entered household consumption
Conduct arranges.
Antibacterial product in the market, substantially produced using three kinds of methods:First, antiseptic is first added into spinning
Anti-bacterial fibre is made in material, various antibacterial fabrics are then made.The method durable antibacterial effect, washability is good, but technology
Content is high, and difficulty is big, and it is wide to be related to field, requires high to antiseptic;It is commonly used to production synthesis fiber class product.Second, in fabric
Antiseptic (being commonly referred to as antibacterial finishing agent) is added during finishing process in printing and dye-ing, various antibacterial fabrics are then made.The method adds
Work processing is relatively simple, and washability and durable antibacterial effect are poor.Made third, first antiseptic is added in spinning material
Into anti-bacterial fibre, then antibacterial finishing agent is added during fabric printing final finishing, various antibacterial fabrics are then made, it is this
Method only uses in the specialities required with high anti-microbial property, limits use range.
Natural fiber (including cotton, fiber crops, hair, silk etc.) material is due to the effect for being difficult to reach antibacterial deodourizing by fibre modification
Fruit, up to the present, the antibacterial deodourizing technique of natural fibre products is still based on final finishing.Conventional antiseptic mainly whether there is
Machine, organic, the natural and major class of polymer antibacterial agent four.Inorganic antiseptic is mostly heavy metal ion antiseptic, wherein again with silver from
Based on son and its compound.Inorganic antiseptic belongs to dissolution type antiseptic, and its Antibacterial Mechanism is ion sustained-release antibacterial mechanism, that is, is existed
During use, antibacterial activity ion slowly discharges, by metal ion activity destroy bacterial cell membrane or with bacterium zymoprotein
The groups such as sulfydryl combine, the activity of destructive enzyme, so as to play antibacterial action.Antiseptic made of these heavy metal components, makes
Into the anxiety of the heavy metal pollution of textile.The heavy metal contained on antibacterial fabric, majority belong to free state, although its dissolution
Property it is not high, but prolonged application may do harm to huamn body.Due to it can be discharged from fiber surface and and skin contact,
Human body is penetrated into by skin pore to accumulate in the liver in human body, kidney, the heart, brain and bone, when the heavy metal product in involved organs
When tiring out certain degree, irreversible damage will be caused to healthy body.So the harmful heavy metal such as Hg, Ag, Cu from
Son has stronger damaging effect to human body.Also some inorganic antiseptics, though there is good anti-microbial property, because can not be with fiber
Firm bonding state is formed, it is not water-fastness gradually to be eliminated.
The predominantly compound such as quaternary ammonium salt, alcohols, halogen amine, biguanides of organic antibacterial agent, has quick, and sterilization can be strong
The characteristics of, wherein again based on quaternary ammonium salt.Quaternary ammonium salt chemism is relatively low, substantially exists with free state during application, toxicity compared with
Greatly, excitant is also stronger.It is dissolution type to be applied to as antiseptic on textile, and heat resistance is poor, easy to migrate, washable
It is de-, and be easily progressively enriched with human body surface, long-term use is also easy to produce lesion, produces resistance to (anti-) property of medicine of microorganism.Patent CN
1048846A discloses a kind of quaternary ammonium salt antiseptic WS-8810.The antiseptic has epoxy isoreactivity group, can with fiber
The active hydrogen groups such as hydroxyl, amino react, and its preparation process is complicated, and substantial amounts of formaldehyde, benzyl are added in preparation process
Chlorine, benzyl amine etc. have the raw material of high toxic side effect, if purification process is incomplete, can bring many toxic side effects.And arrange
Technique is also relatively cumbersome, it is necessary in high temperature progress, produces certain adverse effect to the performance of fiber in itself unavoidably.In addition, WS-
8810 be yellow to brown color thick liquid, easily textile is changed colour, and influences the color and luster of textile in itself.
Natural antibacterial agent comes from natural extract, and such as patent CN 1704521A disclose chitosan, its main antibacterial
Mechanism is considered as similar with organic quaternary ammonium salt, but effect is not so good as organic antibacterial agent, and product is still immature.High-molecular anti-bacteria
Agent is people carries out MOLECULE DESIGN according to the Antibacterial Mechanism of organic antibacterial agent and natural polymer antiseptic, by organic antibacterial agent and
The characteristics of natural polymer antiseptic, combines synthesis, macromolecule, the band pyridine of the main pyridine type main chain for including synthesis
The polyolefine material of side base and modified PS- polystyrene hydantoin (POLY1), are currently in the research starting stage.
Although bio-enzyme immobilization technology and the (letter of 3- (trimethyoxysilane) propyl-dimethyls octadecyl ammonium chloride
Claim:DC-5700) natural textile is arranged and reported, but bio-enzyme immobilization technology employs H2O2Or NaIO4
The oxidizer treatment textile stronger etc. oxidisability, then fixed on the textile by lysozyme, method damage fiber, from
And influence the physical property (such as ultimate strength) of textile in itself.There is substantial amounts of solvent methanol in DC5700 treatment fluids, handles
During also produce methanol, these carry out potential safety hazard to people's health care belt.
Patent CN 101760963A disclose a kind of antibiotic-mould proof textile fabric, are had on antibiotic-mould proof textile fabric
Machine silicon glycine betaine.The antibiotic-mould proof textile fabric preparation method is including step:1) textile is placed in antibiotic finishing solution and impregnated
On the textile brush or spray antimicrobial dressing liquid;2) textile of step (1) processing is dried or dried;3) by step
(2) shaped after gained sample clean, re-dry obtains finished product.Although the antibiotic-mould proof textile fabric anti-microbial property of above-mentioned preparation is good,
But its Durability of antimicrobial effect need further to improve, especially anti-microbial property has declined after repeatedly washing.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency of prior art, there is provided a kind of antibiotic-mould proof textile fabric and its system
Preparation Method, used by the collaboration of dodecyldimethylammonium hydroxide inner salt and the dihydroxy polydiphenylsiloxane of ZnO Modified, and
Ultrasonic immersing at a certain temperature obtains the textile material that a kind of Durability of antimicrobial effect can be excellent, while the textile material maintains
Excellent mechanical property.
Another object of the present invention is to provide a kind of preparation method of antibiotic-mould proof textile fabric.
In order to realize foregoing invention purpose, technical scheme is as follows:
In a first aspect, the invention provides a kind of antibiotic-mould proof textile fabric, have 12 on the antibiotic-mould proof textile fabric
The mixture of alkyl dimethyl betaine and the dihydroxy polydiphenylsiloxane of ZnO Modified.
Wherein, the mol ratio of dodecyldimethylammonium hydroxide inner salt and the dihydroxy polydiphenylsiloxane of ZnO Modified
For (3~7):1, such as 3:1、4:1、5:1、6:1 or 7:1 etc..
In the present invention, the dihydroxy polydiphenylsiloxane of the dodecyldimethylammonium hydroxide inner salt and ZnO Modified
Mol ratio be 5:1.
Second aspect, the invention provides the preparation method of above-mentioned antibiotic-mould proof textile fabric, comprise the following steps:
1) textile is placed in the poly- diphenyl silicon of the dihydroxy containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified
30~60min is ultrasonically treated in the mixed solution of oxygen alkane at 60~80 DEG C;
2) textile of step (1) processing is dried or dried;
3) will be shaped after sample clean obtained by step (2), re-dry obtains finished product.
Wherein, the temperature of supersound process can be 60 DEG C, 63 DEG C, 65 DEG C, 67 DEG C, 70 DEG C, 73 DEG C, 75 DEG C, 77 DEG C or 80 DEG C
Deng;The time of supersound process can be 30min, 33min, 35min, 37min, 40min, 43min, 45min, 47min, 50min,
53min, 55min, 57min or 60min etc..
In the present invention, textile is in the dihydroxy containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified in step (1)
The temperature being ultrasonically treated in the mixed solution of polydiphenylsiloxane is 70 DEG C.
Preferably, textile gathers in the dihydroxy containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified in step (1)
The time being ultrasonically treated in the mixed solution of diphenyl siloxane is 50min.In the present invention, the weaving after step (2) processing
Product can also be again placed in the mixed of the dihydroxy polydiphenylsiloxane containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified
Close and be ultrasonically treated 30~60min in solution at 60~80 DEG C, then dry the finished product of cleaning sizing.
In the present invention, the dihydroxy polydiphenylsiloxane of the dodecyldimethylammonium hydroxide inner salt and ZnO Modified
It is dissolved in organic solvent, the volume ratio of organic solvent and dodecyldimethylammonium hydroxide inner salt is (6~10):1, such as 6:1、7:
1、8:1、9:1 or 10:1 etc..
In the present invention, described organic solvent is ethyl acetate, butyl acetate, chloroform, dichloromethane, tetrahydrofuran, third
Any one in ketone, butanone, ethanol, normal propyl alcohol, n-butanol, dimethylformamide, dimethyl acetamide or dimethyl sulfoxide (DMSO) or
At least two combination, the combination is typical but non-limiting examples have:The combination of ethyl acetate, butyl acetate and chloroform, two
The combination of chloromethanes, tetrahydrofuran, acetone and butanone, the combination of acetone, butanone, ethanol and normal propyl alcohol, n-butanol, dimethyl methyl
Combination of acid amides, dimethyl acetamide and dimethyl sulfoxide (DMSO) etc., preferably ethanol.
In the present invention, drying is to do the textile after dipping under the conditions of less than 120 DEG C in described step (2)
It is dry.
The present invention possesses advantages below compared with prior art:
The association that the present invention passes through dodecyldimethylammonium hydroxide inner salt and the dihydroxy polydiphenylsiloxane of ZnO Modified
With using, ultrasonic immersing at a certain temperature obtains the textile material that a kind of Durability of antimicrobial effect can be excellent, and it is after 50 washings
Antibacterial activity remains to keep more than 97%, and maintains good mechanical property.
Embodiment
In order that technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining
The present invention, it is not intended to limit the present invention.
Antibiotic-mould proof textile fabric provided by the invention, has dodecyl dimethyl beet on the antibiotic-mould proof textile fabric
The mixture of alkali and the dihydroxy polydiphenylsiloxane of ZnO Modified.Wherein, dodecyldimethylammonium hydroxide inner salt and nanometer
The mol ratio for the dihydroxy polydiphenylsiloxane that ZnO is modified is (3~7):1.
The preparation method of antibiotic-mould proof textile fabric of the present invention, comprises the following steps:
1) textile is placed in the poly- diphenyl silicon of the dihydroxy containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified
30~60min is ultrasonically treated in the mixed solution of oxygen alkane at 60~80 DEG C;2) textile by step (1) processing dries or dried
It is dry;
3) will be shaped after sample clean obtained by step (2), re-dry obtains finished product.
Further, the above-mentioned textile after step (2) processing can be also again placed in containing dodecyl dimethyl beet
In the mixed solution of alkali and the dihydroxy polydiphenylsiloxane of ZnO Modified at 60~80 DEG C be ultrasonically treated 30~
60min, then dry the finished product of cleaning sizing.
Above-mentioned dipping is to immerse textile in antibiotic finishing solution, and the dosage of antibiotic finishing solution can according to actual conditions
It can lack more, but minimum amount limit is to soak textile.
The preferred natural fabric of textile, antibacterial and mouldproof effect, flexibility, moisture retention are more.The preferred acetic acid of organic solvent
Ethyl ester, butyl acetate, chloroform, dichloromethane, tetrahydrofuran, acetone, butanone, ethanol, normal propyl alcohol, n-butanol, dimethyl formyl
Any one in amine, dimethyl acetamide or dimethyl sulfoxide (DMSO) or at least two combination, preferably ethanol.
The dress of antibacterial fabric should not be beaten using the micro-ecological environment for destroying human body skin mucous membrane as cost once balancing
It is broken, it is possible to cause skin infection or other diseases, by the inherently safe of the serious threat mankind and economic sustainable development.Can
Safety risks can be brought.If dress prepares bad, constantly release antibacterials antibiotic fabrics, human body pore is destroyed
And the balance of the normal flora of skin, skin will be made to lose the intrinsic barrier action for resisting external microorganism infringement, so as to drop
Low immunity of organisms;The prolonged application of low dosage antibacterials can induce microbial variation, and increase produces the probability of drug resistance.Institute
Using the desired characteristics of antibacterial finishing agent as:(1) there is the function of excellent suppression, sterilization, sterilization and deodorization, there is broad-spectrum antiseptic
Effect.(2) antibacterial effect resistance to persistence is strong, resistance to rinsing and Exposure to Sunlight.(3) side effect is not produced to human body, it is nontoxic, do not pollute ring
Border.(4) style and features of textile in itself are not influenceed, do not damage fiber, the effect of not influenceing other textile auxiliaries.(5) antibacterial
The application method of agent is easy, cost is low, has compatibility with other finishing agents.
Therefore, from the view of security, the antibacterial fabric present invention of the present invention by dodecyldimethylammonium hydroxide inner salt and
The collaboration of the dihydroxy polydiphenylsiloxane of ZnO Modified is used, and ultrasonic immersing at a certain temperature obtains a kind of antibacterial and held
The textile material of long excellent performance, its antibacterial activity after 50 washings remains to keep more than 97%, and maintains good
Mechanical property, product safety is reliable.
The present invention can obtain extensively in fields such as the arrangement of clothes anti-bacteria wet keeping, medical and health use non-woven cloth antimicrobial treatments
Application.
Embodiment 1
(1) pending textile is impregnated in into the dihydroxy containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified to gather
Mixed solution (wherein, dodecyldimethylammonium hydroxide inner salt and the poly- diphenyl of the dihydroxy of ZnO Modified of diphenyl siloxane
The mol ratio of siloxanes is 5:1, organic solvent is the volume ratio of ethyl acetate, organic solvent and dodecyldimethylammonium hydroxide inner salt
For 8:1) 50min is ultrasonically treated at 70 DEG C;
(2) by the textile of step (1) processing in 120 DEG C of drying;
(3) after step (2) gained sample clean, sizing, drying, the mould proof moisturizing textile of durable antibiotic is produced.
The performance such as its anti-microbial property and mechanical property is as shown in appendix 1.
Embodiment 2
(1) pending textile is impregnated in into the dihydroxy containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified to gather
Mixed solution (wherein, dodecyldimethylammonium hydroxide inner salt and the poly- diphenyl of the dihydroxy of ZnO Modified of diphenyl siloxane
The mol ratio of siloxanes is 3:1, organic solvent is the volume ratio of butyl acetate, organic solvent and dodecyldimethylammonium hydroxide inner salt
For 10:1) 30min is ultrasonically treated at 80 DEG C;
(2) by the textile naturally dry at room temperature of step (1) processing;
(3) sample obtained by step (2) is impregnated in again and above-mentioned contains dodecyldimethylammonium hydroxide inner salt and ZnO Modified
Dihydroxy polydiphenylsiloxane mixed solution in be ultrasonically treated 50min at 70 DEG C;
(4) after sample clean, sizing obtained by step (3) and drying, the mould proof moisturizing textile of durable antibiotic is produced.
The performance such as its anti-microbial property and mechanical property is as shown in appendix 1.
Embodiment 3
(1) pending textile is impregnated in into the dihydroxy containing dodecyldimethylammonium hydroxide inner salt and ZnO Modified to gather
Mixed solution (wherein, dodecyldimethylammonium hydroxide inner salt and the poly- diphenyl of the dihydroxy of ZnO Modified of diphenyl siloxane
The mol ratio of siloxanes is 7:1, organic solvent is the volume ratio of ethyl acetate, organic solvent and dodecyldimethylammonium hydroxide inner salt
For 6:1) 60min is ultrasonically treated at 60 DEG C;
(2) by the textile of step (1) processing in 100 DEG C of drying;
(3) sample obtained by step (2) is impregnated in again and above-mentioned contains dodecyldimethylammonium hydroxide inner salt and ZnO Modified
Dihydroxy polydiphenylsiloxane mixed solution in be ultrasonically treated 60min at 60 DEG C;
(4) after step (3) gained sample clean, sizing, drying, the mould proof moisturizing textile of durable antibiotic is produced.
The performance such as its anti-microbial property and mechanical property such as subordinate list 1.
Embodiment 4
Above-mentioned containing dodecyldimethylammonium hydroxide inner salt and received except being impregnated in sample obtained by step (2) again in step (3)
It is ultrasonically treated in the mixed solution for the dihydroxy polydiphenylsiloxane that rice ZnO is modified at 80 DEG C outside 30min, other steps and original
Expect that dosage is same as Example 2.
The performance such as its anti-microbial property and mechanical property such as subordinate list 1.
Comparative example 1:
Except pending textile is impregnated in dodecyldimethylammonium hydroxide inner salt solution, other steps are and embodiment
It is identical in 1.
Obtained antibacterial and mouldproof moisturizing textile, the performance such as its anti-microbial property and mechanical property such as subordinate list 1.
Comparative example 2:
Except in the solution for the dihydroxy polydiphenylsiloxane that pending textile is impregnated in ZnO Modified, its
His step is in the same manner as in Example 1.
Obtained antibacterial and mouldproof moisturizing textile, the performance such as its anti-microbial property and mechanical property such as subordinate list 1.
Comparative example 3:
In addition to without being ultrasonically treated, other steps are in the same manner as in Example 1.
Comparative example 4:
Embodiment 1 in patent CN 101760963A.
Obtained antibacterial and mouldproof moisturizing textile, the performance such as its anti-microbial property and mechanical property such as subordinate list 1.
Table 1:Antibacterial and mouldproof moisturizing properties of textile tests table in embodiment 1-4 and comparative example 1-4
Integrated embodiment 1-4 and comparative example 1-4 result can be seen that the present invention and passes through dodecyldimethylammonium hydroxide inner salt
Collaboration with the dihydroxy polydiphenylsiloxane of ZnO Modified is used, and ultrasonic immersing at a certain temperature obtains a kind of antibacterial
The excellent textile material of enduring quality, its antibacterial activity after 50 washings remains to keep more than 97%, and maintains good
Good mechanical property.
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.