CN101586264A - The method of manufacturing antibacterial acrylon by adopting blending addition modifying method - Google Patents
The method of manufacturing antibacterial acrylon by adopting blending addition modifying method Download PDFInfo
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- CN101586264A CN101586264A CNA2008100378768A CN200810037876A CN101586264A CN 101586264 A CN101586264 A CN 101586264A CN A2008100378768 A CNA2008100378768 A CN A2008100378768A CN 200810037876 A CN200810037876 A CN 200810037876A CN 101586264 A CN101586264 A CN 101586264A
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Abstract
A kind of method of manufacturing antibacterial acrylon by adopting blending addition modifying method, adopting sodium thiocyanate water solution is the wet spinning process of solvent.Spinning solution adds antibacterial additives and mixes, and makes fiber product through spinning and last handling process.Antibacterial additives is a kind of solution, and component comprises antiseptic, solubilizer, emulsifying agent and solvent.Antiseptic is A, or the mixture of A and B, A be 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, B takes from 4-chloro-3,5-xylenol or 2,4-two chloro-3, a kind of in the 5-xylenols, the weight ratio of A and B is 1: 0～0.3; Solubilizer is polyox-yethylene-polyoxypropylene block copolymer, molecular weight 7500～9500, wherein polyoxyethylene content 80～85wt%; Emulsifying agent is taken among Tween-20, Tween-40, Tween-60 or the Tween-80 a kind of, or two or more mixtures; Solvent is a polyethylene glycol-400.With spinning solution always is benchmark admittedly, and the antiseptic addition is 0.5～2.2wt%.The invention solves antiseptic and this technical problem of spinning solution compatibility difference.
Description
Technical field
The present invention relates to a kind of manufacture method of antibacterial acrylic fibre, particularly employing is the method for the wet spinning technology and the manufacturing antibacterial acrylon by adopting blending addition modifying method of solvent with the sodium thiocyanate water solution.
Background technology
In recent years, people also more and more pay attention to the health care of fabric when pursuing the chemical ﹠ blended fabric comfortableness, and the antibiotic fabric that wherein has sterilization or bacteria resistance function is just favored very much, as antibacterial underwear, antimicrobial socks etc.Antibiotic fabric is formed by the functional antibacterial fibre manufacturing with anti-microbial property usually, acrylic fibers have good warmth retention property and poisture-penetrability, and be easy to and wool and cotton blending, the fabric that suitable manufacturing underwear, socks etc. wear next to the skin, thereby antibacterial acrylic fibre is very desirable functional antibacterial fibre, and its research and development are also paid close attention to very much.
At present, make antibacterial acrylic fibre mainly by physical modification and two kinds of approach of chemical modification.Chemical modification makes antiseptic link with chemical bond and polymer molecule, has washable, antifriction, and the advantage that antibiotic property is lasting is introduced as Chinese patent application 200610023798.7.But chemical modification needs polymerization technique is carried out bigger change, implements comparatively complicated on existing acrylic fiber production process device.Physical modification mainly comprises methods such as blend interpolation, back arrangement or coating, though back arrangement or coating do not relate to the change of acrylic spinning manufacturing technique essence, because antiseptic generally exists only in the surface of fiber, antibiotic property is not lasting, and is not washable, wear-resisting.Comparatively speaking, the method for blending addition modifying is comparatively desirable, and it is blend interpolation antiseptic in spinning solution normally, makes antiseptic be uniformly distributed in fibrous inside behind the spinning technique.Though antiseptic does not have linking of chemical bond with polymer molecule, antiseptic still can be retained in the fiber for a long time, and antibiotic property is also very lasting.
In the prior art, the adopted antiseptic that is used to make antibacterial acrylic fibre has the inorganic matter that is insoluble to acrylic spinning stoste.Being presented in the particle diameter that adds 10～35wt% in the acrylic fibers fibre-forming polymer as Japan Patent JP8060434 is 0.1～2.0 micron ZnO, SiO
2And B
2O
3Particle makes antibacterial acrylic fibre, obviously, adds a large amount of solid particle like this in the fibre-forming polymer and will worsen the spinning technique condition, shortens the life cycle of filament spinning component and filter, and can cause the decline of fibrous physical property index.
Known by prior art, the organic matter of diphenyl ether derivative one class also is a kind of desirable antiseptic, as 2,4, and 4 '-three chloro-2 '-dihydroxy diphenyl ether, when better with the composite Use Limitation fruit of the derivative of phenol.Their nontoxic or low toxicities, and wide spectrum, efficient.As Japan Patent JP58169511 introduce to adopt as 2,4,4 '-three chloro-2 '-diphenyl ether derivative of dihydroxy diphenyl ether is an antiseptic, is the solvent medium of spinning solution with the organic solvent, makes antibacterial acrylic fibre by wet spinning technology.Because this antiseptic has the fine solubility energy in spinning solution, the spinning technique condition is not produced harmful effect substantially, and antiseptic is present between polymer molecule with molecular conformation equably in the fiber that finally makes, so it is washable, wear-resisting, antibiotic property is lasting, and the fibrous physical property index can not descend yet.But regrettably, above-mentioned organic matter antiseptic then can form crystalline precipitate in inorganic aqueous solvent (as sodium thiocyanate water solution).And we know, are that the wet spinning technology of solvent is still one of main acrylic fiber production process route at present with the sodium thiocyanate water solution, and therefore, above-mentioned organic matter antiseptic is used for this technology, and to make antibacterial acrylic fibre be that the present technique field is desired.
Summary of the invention
The invention provides a kind of method of manufacturing antibacterial acrylon by adopting blending addition modifying method, it is the wet spinning technology of solvent that this method adopts with the sodium thiocyanate water solution, and it is antiseptic that antibacterial additives adopts the organic matter of diphenyl ether derivative one class.The invention solves antiseptic and this technical problem of spinning solution compatibility difference.
Below be the concrete technical scheme of the present invention:
A kind of method of manufacturing antibacterial acrylon by adopting blending addition modifying method, it is the wet spinning technology of solvent that this method adopts with the sodium thiocyanate water solution, comprises adding antibacterial additives in the spinning solution and mixing, and makes fiber product through spinning and last handling process.Antibacterial additives is a kind of solution, and its component comprises antiseptic, solubilizer, emulsifying agent and solvent, wherein:
Antiseptic is A, or the mixture of A and B, A be 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, B takes from 4-chloro-3,5-xylenol or 2,4-two chloro-3, a kind of in the 5-xylenols, the weight ratio of A and B is 1: 0～0.3; Solubilizer is polyox-yethylene-polyoxypropylene block copolymer, and molecular weight is 7500～9500, and wherein polyoxyethylene content is 80～85wt%; Emulsifying agent is taken among Tween-20, Tween-40, Tween-60 or the Tween-80 a kind of, or two or more mixtures; Solvent is a polyethylene glycol-400.
The total amount of solubilizer and emulsifying agent and the weight ratio of antiseptic are 1～3: 1; The weight ratio of solubilizer and emulsifying agent is 10: 0.5～4, and the content of antiseptic is 5～20wt% in the antibacterial additives.
Always to be benchmark admittedly in the spinning solution, the addition of antiseptic is 0.5～2.2wt%.
In the above-mentioned antibacterial additives: the weight ratio of antiseptic A and B is preferably 1: 0.1～and 0.2; Emulsifying agent is preferably Tween-60; The total amount of solubilizer and emulsifying agent and the weight ratio of antiseptic are preferably 1～2: 1; The weight ratio of solubilizer and emulsifying agent is preferably 10: 1～and 3; The content of antiseptic is preferably 8～15wt%.
Total solid content generally is controlled to be 8～20% in the above-mentioned spinning solution, and the solvent of preparation spinning solution is that concentration is the sodium thiocyanate water solution of 35～58wt%.And last handling process generally comprises cold drawing-off, washing, hot drawing-off, oils, compacting by drying, curl and HEAT SETTING etc.These all with common be that the acrylic fibre wet spinning technique of solvent is identical with the sodium thiocyanate water solution.
Essence of the present invention is that antiseptic is mixed with stable solution, and this solution has very good compatibility with the acrylic spinning stoste that with the sodium thiocyanate water solution is solvent.One of its key is to have selected a kind of suitable solvent for use, and antiseptic just has very high solubility under the normal temperature in polyethylene glycol-400, can form transparent, stable solution.In addition, polyethylene glycol-400 also has extraordinary compatibility with water or sodium thiocyanate water solution.However, after the solution that simple polyethylene glycol-400 and above-mentioned antiseptic form and the aqueous solution of water or sodium sulfocyanate, antiseptic still can form crystalline thing and separate out from system.The inventor found through experiments, (molecular weight is 7500～9500 to have added an amount of polyox-yethylene-polyoxypropylene block copolymer in above-mentioned solution, wherein polyoxyethylene content is 80～85wt%, the Lutrol F-68 that produces as BASF AG) and an amount of specific emulsifying agent, form a kind of multi-component solution then, the compatibility of this multi-component solution and water or sodium thiocyanate water solution is greatly improved, can form optically transparent, stable " accurate solution ", this is another key point of the present invention.
Learn by test, this multicomponent solution has very good compatibility with the acrylic spinning stoste that with the sodium thiocyanate water solution is solvent, when the addition of multicomponent solution reaches the antiseptic content that satisfies in the antibacterial acrylic fibre fiber and is 2.0wt% (this moment, the antibiotic property of fiber was enough to satisfy various instructions for uses), spinnability is not affected yet.The result of the test of long period spinning has also shown under the pressure reduction period of change of parts such as nozzle component, filter and the situation that antiseptic does not add identical.
The solvent that it is emphasized that above-mentioned multicomponent solution employing in addition is nontoxic, non-stimulated to human body, is commonly used for solvent in pharmacy industry, makes the medicine as classes such as oral liquid, eye drops; Solubilizer and emulsifying agent also are the component that often adopts in the preparation medium.Therefore their security need not doubted.Secondly, from the test result of the anti-microbial property of the antibacterial acrylic fibre that makes, the adding of above-mentioned substance does not cause any negative influence.
This shows that compared with prior art, good effect of the present invention is very remarkable, it has solved the organic matter antiseptic of diphenyl ether derivative one class effectively and has been this technical problem of acrylic spinning stoste compatibility difference of solvent with the sodium thiocyanate water solution.Provide a kind of desirable sodium sulfocyanate wet spinning technology to make the method for antibacterial acrylic fibre, simple liquid mixing device is only acquired by general acrylic fibers manufacturing firm, can realize the manufacturing of the antibacterial acrylic fibre of function admirable on existing common acrylic fiber production process device.
The invention will be further described below by embodiment.Because key of the present invention is the improvement of antibacterial additives, the preparation of other parts such as stoste, spinning and aftertreatment technology are that the wet spinning acrylic fiber spinning technique of solvent is basic identical with traditional sodium thiocyanate water solution all, so embodiment will pay attention to enumerating of antibacterial additives test data.
The specific embodiment
One, the preparation of antibacterial additives
[embodiment 1～10]
Under 70 ℃, solubilizer and emulsifying agent are evenly mixed with solvent polyethylene glycol-400 in required ratio, under stirring, the antiseptic of aequum is added wherein gradually then, continue to impose stirring, be as clear as crystal to system, cooling, it is standby to make antibacterial additives.
[comparative example 1～2]
Except that not using solubilizer and emulsifying agent, all the other are with embodiment 1～10.
The composition of each embodiment or comparative example antibacterial additives see Table 1 and table 2 listed.
Table 1.
| Antiseptic (B) | Antiseptic proportioning (weight ratio, A: B) | Antiseptic content (wt%) | |
| Embodiment 1 | 4-chloro-3, the 5-xylenol | 1∶0.2 | 5 |
| Embodiment 2 | 4-chloro-3, the 5-xylenol | 1∶0.1 | 8 |
| Embodiment 3 | - | 1∶0 | 19 |
| Embodiment 4 | 4-chloro-3, the 5-xylenol | 1∶0.1 | 13 |
| Embodiment 5 | 4-chloro-3, the 5-xylenol | 1∶0.1 | 10 |
| Embodiment 6 | 2,4-two chloro-3,5-xylenols | 1∶0.1 | 12 |
| Embodiment 7 | 2,4-two chloro-3,5-xylenols | 1∶0.1 | 20 |
| Embodiment 8 | 2,4-two chloro-3,5-xylenols | 1∶0.1 | 15 |
| Embodiment 9 | - | 1∶0 | 11 |
| Embodiment 10 | 2,4-two chloro-3,5-xylenols | 1∶0.3 | 8 |
| Comparative example 1 | 4-chloro-3, the 5-xylenol | 1∶0.1 | 15 |
| Comparative example 2 | 2,4-two chloro-3,5-xylenols | 1∶0.1 | 15 |
Table 2.
| Emulsifying agent | Solubilizer: emulsifying agent (weight ratio) | (solubilizer+emulsifying agent): antiseptic (weight ratio) | |
| Embodiment 1 | Tween-40 | 10∶1 | 3∶1 |
| Embodiment 2 | Tween-60 | 10∶0.5 | 3∶1 |
| Embodiment 3 | Tween-60 | 10∶3 | 1∶1 |
| Embodiment 4 | Tween-60 | 10∶2 | 1.5∶1 |
| Embodiment 5 | Tween-20 | 10∶3 | 2∶1 |
| Embodiment 6 | Tween-80 | 10∶4 | 2∶1 |
| Embodiment 7 | Tween-60 | 10∶3 | 2∶1 |
| Embodiment 8 | Tween-40、Tween-60 | 10∶4 | 2∶1 |
| Embodiment 9 | Tween-60 | 10∶3 | 3∶1 |
| Embodiment 10 | Tween-40 | 10∶1 | 3∶1 |
| Comparative example 1 | - | - | - |
| Comparative example 2 | - | - | - |
Annotate:
Among the embodiment or comparative example that above-mentioned table 1 and table 2 are listed, the A in the antiseptic be 2.4.4 '-three chloro-2 '-dihydroxy diphenyl ether; Solubilizer is that (polyox-yethylene-polyoxypropylene block copolymer, molecular weight are 7500～9500 to Lutrol F-68, and wherein polyoxyethylene content is 80～85wt%).
Two, antibacterial additives and spinning solution compatibility test
For ease of representing the invention effect, employing concentration is the compatibility that the sodium thiocyanate water solution of 52wt% is tested antibacterial additives and acrylic spinning stoste, because the compatibility of antibacterial additives and spinning solution depends primarily on spin solvent, from theory analysis and experimental result, compatibility can not change because of the adding of polymer basically.
The antibacterial additives that embodiment 1～10 and comparative example 1～2 are made joins respectively in the 52wt% sodium thiocyanate water solution that temperature is 25 ℃, 40 ℃ and 60 ℃ and carries out compatibility test.Wherein the concentration of sodium thiocyanate water solution is prepared acrylic spinning stoste desired concn basically identical with reality, and 40 ℃, 60 ℃ the spinning solution temperature with one-step method, two-step method acrylic fibre wet spinning technique reality is close respectively.
Result of the test sees Table 3.
Table 3.
Annotate:
The antibacterial additives addition is the weight ratio of antibacterial additives and sodium thiocyanate water solution, and the test situation of embodiment 1 is similar to that total solid content is 12wt% in spinning solution, and antiseptic content is the addition of 1.0wt% in the fiber that expectation makes; Compatibility leaves standstill the system status of observing after 10 hours for insulation.
Three, the preparation of antibacterial acrylic fibre
[embodiment 11～18]
Adding with sodium thiocyanate water solution (concentration be 51.3wt%) by online injection device antibacterial additives is in the acrylic spinning stoste of spin solvent (total solid content of stoste is 12wt%), spinning solution mixes antibacterial additives and stoste by a static mixer.Carry out spinning and back processing (back manufacturing procedure comprises cold drawing-off, washing, hot drawing-off, oils, compacting by drying, curling and HEAT SETTING etc.) by general wet spinning technology condition, make the antibacterial acrylic fibre that fiber number is 1.67dtex.ANOMALOUS VARIATIONS does not take place in the pressure of nozzle component and filter in the whole spinning process, and spinning process is smooth.
Antiseptic addition and antibacterial tests the results are shown in Table 4 in embodiment 11～18 spinning solutions.The antibacterial value (antibacterial value greater than 2.0 be qualified) of anti-microbial property I for pressing JIS L-1902:2002 standard detection staphylococcus aureus and pneumobacillus in the table 4; Anti-microbial property II is for pressing AATCC 100-2004 standard detection staphylococcus aureus and colibacillary antibiotic rate (%).
Test implementation example 11～18 makes the fibrous physical property index of antibacterial acrylic fibre, and the result is primes (GB/T16602-1996).
Table 4.
Claims (8)
1, a kind of method of manufacturing antibacterial acrylon by adopting blending addition modifying method, it is the wet spinning technology of solvent that this method adopts with the sodium thiocyanate water solution, comprise in the spinning solution and to add antibacterial additives and mix, make fiber product through spinning and last handling process, it is characterized in that antibacterial additives is a kind of solution, its component comprises antiseptic, solubilizer, emulsifying agent and solvent, wherein:
Antiseptic is A, or the mixture of A and B, A be 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, B takes from 4-chloro-3,5-xylenol or 2,4-two chloro-3, a kind of in the 5-xylenols, the weight ratio of A and B is 1: 0～0.3; Solubilizer is polyox-yethylene-polyoxypropylene block copolymer, and molecular weight is 7500～9500, and wherein polyoxyethylene content is 80～85wt%; Emulsifying agent is taken among Tween-20, Tween-40, Tween-60 or the Tween-80 a kind of, or two or more mixtures; Solvent is a polyethylene glycol-400,
The total amount of solubilizer and emulsifying agent and the weight ratio of antiseptic are 1～3: 1; The weight ratio of solubilizer and emulsifying agent is 10: 0.5～4, and the content of antiseptic is 5～20wt% in the antibacterial additives,
Always to be benchmark admittedly in the spinning solution, the addition of antiseptic is 0.5～2.2wt%.
2, the method for manufacturing antibacterial acrylon by adopting blending addition modifying method according to claim 1 is characterized in that antiseptic A in the described antibacterial additives and the weight ratio of B are 1: 0.1～0.2.
3, the method for manufacturing antibacterial acrylon by adopting blending addition modifying method according to claim 1 is characterized in that the emulsifying agent in the described antibacterial additives is Tween-60.
4, the method for manufacturing antibacterial acrylon by adopting blending addition modifying method according to claim 1 is characterized in that the solubilizer in the described antibacterial additives and the total amount of emulsifying agent and the weight ratio of antiseptic are 1～2: 1.
5, the method for manufacturing antibacterial acrylon by adopting blending addition modifying method according to claim 1 is characterized in that the solubilizer in the described antibacterial additives and the weight ratio of emulsifying agent are 10: 1～3.
6, the method for manufacturing antibacterial acrylon by adopting blending addition modifying method according to claim 1, the content that it is characterized in that the antiseptic in the described antibacterial additives is 8～15wt%.
7, the method for manufacturing antibacterial acrylon by adopting blending addition modifying method according to claim 1 is characterized in that total solid content is 8～20% in the described spinning solution, and the solvent of spinning solution is that concentration is the sodium thiocyanate water solution of 35～58wt%.
8, the method for manufacturing antibacterial acrylon by adopting blending addition modifying method according to claim 1 is characterized in that described last handling process comprises cold drawing-off, washing, hot drawing-off, oils, compacting by drying, curls and HEAT SETTING.
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Open date: 20091125 |