CN1325462A - Incorporation of organic anti-microbials into fibres during a fibre spinning - Google Patents
Incorporation of organic anti-microbials into fibres during a fibre spinning Download PDFInfo
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- CN1325462A CN1325462A CN99812791A CN99812791A CN1325462A CN 1325462 A CN1325462 A CN 1325462A CN 99812791 A CN99812791 A CN 99812791A CN 99812791 A CN99812791 A CN 99812791A CN 1325462 A CN1325462 A CN 1325462A
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- acid
- antimicrobial
- phenol
- formaldehyde
- condensation product
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0058—Biocides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/22—Cellulose xanthate
- C08L1/24—Viscose
Abstract
The present invention relates to a process for finishing regenerated cellulose fibres with an anti-microbial and/or antifungal agent or a mixture thereof wherein in the first step, a formulation comprising an anti-microbial agent and one or more surface active agents are added to the soluble form of the fibres prior to regeneration and in a second step this mixture is extruded from a spinneret to form the regenerated fibre. The fibres treated according to the process of the present invention show good anti-microbial and antifungal activity.
Description
The present invention relates in fiber, mix the method for antimicrobial, antifungal agent or its mixture and the fiber that obtains by this method.
Now for the regenerated celulose fibre that can demonstrate antimicrobial and/or anti-fungal property, comprise that as artificial silk and by this fiber the demand of the textiles that blend fibre is made constantly increases, its reason is in order to suppress the growth of bacterium and mould, and these bacteriums and mould can damage the healthy of consumer and make fabric produce stench.
The antibacterial fabric processing of carrying out with the fabric surface treatments form is known, but this fabric its antiseptic in use is subsequently easily washed off.
In order to reach the anti-repeatedly durability of this antibacterial activity of washing, a kind of preferably method of mixing is that the antimicrobial acivity composition is joined in the fiber.Say that technically this unique feasible method of mixing is that antimicrobial is joined in the cellulose of dissolved state, extrude from spinnerets then and form soft long filament, and then generate cellulose.All kinds of artificial silks all are to adopt wet spinning to make, wet spinning be meant from the spun long filament of spinnerets directly be passed into for solidify or the chemical bath of the usefulness of regenerating.
Yet, find that in practice will mix antimicrobial, especially organic antimicrobial is inconvenient, because comprised the processing conditions of severe corrosive in the production of rayon fiber.
The antimicrobial of solid granular should not be incorporated in the cellulose of dissolved state, because this can cause the obstruction of spinneret orifice.In order to address this problem, mill technology so that make the particle diameter of antimicrobial be reduced to enough little with regard to requiring to adopt.But this technology of milling is expensive often, and for some antimicrobial, is very difficult, because the fusing point of these compounds is lower.
Another kind of reasonable method is that antimicrobial is dissolved in a kind of solvent compatible with cellulose dissolved state.But its difficulty be when the cellulose of dissolved state when spinnerets is extruded, it directly is passed in the chemical bath to regenerated cellulose generation chemical reaction.If antimicrobial is dissolved in a kind of organic solvent, then this antimicrobial can still be stayed in the organic facies after the regeneration.If this antimicrobial is dissolved in the water-soluble solvent, then this antimicrobial can still be stayed in the solution, thereby can ooze out from fiber in regenerative process.The method of therefore mixing antimicrobial in fiber often can not be satisfactory.
It has surprisingly been found that, can provide by following method and to have the fiber that improves antimicrobial and/or antifungal activity, in the method antimicrobial, antifungal agent or its mixture and one or more surfactants are joined in the cellulose of dissolved state, extrude the formation fiber from spinnerets then, make this regeneration become cellulose at last.
The present invention relates to a kind of method with antimicrobial, antifungal agent or its mixture process cellulose fibre, wherein in the first step, the preparation that will comprise antimicrobial, antifungal agent or its mixture and one or more surfactants before regeneration joins in the cellulose of dissolved state, in second step, this mixture is extruded to form regenerated fiber from spinnerets.
Antimicrobial is selected from one group that is made up of following:
(a) halo-neighbour-hydroxydiphenyl compounds;
(b) phenol derivatives;
(c) benzyl alcohol;
(d) triocil (chlorohexidine) and derivative thereof;
(e) C
12-C
14Alkyl betaine and C
8-C
18Fatty acid acyl aminoalkyl betaine;
(f) amphoteric surfactant;
(g) three halogen carbanilides;
(h) quaternary compound and many quaternary compounds; And
(i) thiazolium compounds,
Preferably, antimicrobial is selected from the compound shown in the following formula
Wherein
X be oxygen, sulphur or-CH
2-,
Y is a chlorine or bromine,
Z is SO
2H, NO
2Or C
1-C
4Alkyl,
R is 0～3,
O is 0～3,
P is 0 or 1,
M be 0 or 1 and
N is 0 or 1;
And have 1 among r or the o at least and be not equal to 0.
Preferably, in the method, the antimicrobial (a) of use formula (1), wherein
X be oxygen, sulphur or-CH
2-,
Y is a chlorine or bromine,
M is 0,
N is 0 or 1,
O is 1 or 2,
R is 1 or 2, and
P is 0.
As antimicrobial (a), valuable especially is the compound shown in the following formula
Wherein
X is-O-or-CH
2-;
M is 1～3; With
N is 1 or 2 and the compound of following formula most preferably:
Most preferred antimicrobial is the compound shown in the following formula
Or
Formula (3) expression antimicrobial 2,4,4 '-three chloro-2-hydroxyl-2-diphenyl ether, or claim Triclosan (Triclosan).Formula (4) expression antimicrobial 4,4 '-two chloro-2-dihydroxy diphenyl ethers, or claim two tagathens (Diclosan).
Preferred phenol derivatives (b) is equivalent to following formula:
Wherein
R
1Be hydrogen, hydroxyl, C
1-C
4Alkyl, chlorine, nitro, phenyl or benzyl.
R
2Be hydrogen, hydroxyl, C
1-C
6Alkyl or halogen,
R
3Be hydrogen, C
1-C
6Alkyl, hydroxyl, chlorine, nitro or be the sulfo group of alkali metal salts or ammonium salt form,
R
4Be hydrogen or methyl, and
R
5Be hydrogen or nitro.
Such compound be typical chlorophenol (adjacent-,-, right-chlorophenol), 2,4-chlorophenesic acid, p-nitrophenol, picric acid, xylenols, to chloro-meta-xylene phenol, cresols (adjacent-,-, p-Cresol), to chloro-m-cresol, catechol (pyrocatechin), resorcinol, orcin, 4-n-hexyl-1,3-benzenediol, pyrogallol, phloroglucin, carvacrol, thymol, to chlorothymol, o-phenyl phenol, 2-methane, to chloro-2-methane and 4-phenolsulfonic acid.
Typical antimicrobial (c) is equivalent to following formula
Wherein
R
1, R
2, R
3, R
4And R
5Independently of one another, respectively be hydrogen or chlorine.
The illustrative example of formula (6) compound is a benzyl alcohol, 2, and 4-, 3,5-or 2, the pure and mild trichlorine benzyl alcohol of 6-dichloro benzyl.
Antimicrobial (d) is two hot chlorine pyridines and salt thereof, for example 1,1 '-hexa-methylene-two-(5-(rubigan)-biguanides) and organic and inorganic acid salt thereof, and the triocil derivative, as their diacetin, digluconate or dihydrochloride compound.
Antimicrobial (e) is C typically
8-C
18Ke blocks amido propyl betaine.
That be fit to as the amphoteric surfactant of antimicrobial (f) is C
12Alkyl amino carboxylic acid and C
1-C
3The alkane carboxylic acid is as p dialkylaminobenzoic acid ester or alkyl aminopropionic acid ester.
The typical three halogen carbanilides that can be used as antimicrobial (g) are compounds of following formula
Wherein
Hal is a chlorine or bromine,
N and m are 1 or 2, and
N and m sum equal 3.
The compound that comprises following formula corresponding to quaternary compound and many quaternary compounds of antimicrobial (h)
Wherein
R
6, R
7, R
8And R
9Independently of one another, respectively be C
1-C
18Alkyl, C
1-C
18Alkoxyl or phenyl-low alkyl group, and
Hal is a chlorine or bromine.
In these salt, the compound of following formula is particularly preferred,
Wherein
N is 7～17 integer.
Further exemplary compound is a cetyl trimethyl ethyl ammonium bromide.
In the method for the antimicrobial of the positively charged that other is important as those that are called quaternary ammonium compound also can be included in.Except the fiber that the such agent treated of this usefulness can be provided, also having an advantage is that this reagent has good compatibility to cellulose matrix.The example of this reagent comprises the compound of following formula
This compound is also referred to as Aegis DC5700, or the phosphate derivative of the quaternary compound of following formula:
The epoxide derivate of following formula:
Or a kind of table chloride derivatives of following formula, be called Degussa Quab 342:
Valuable especially as antimicrobial (i) is methyl chloride isotahazoline.
Can provide the advantage of combination of the antimicrobial of antibiotic and antifungal activity to be that they can provide the processing fiber with further function such as functions such as antibiotic, antimycotic, antidusting tick and deodoriging properties.
Demonstrate anti-fungal property and be applicable to that the compound of this method comprises:
-contain the compound of naphthalene ether, preferred 2-naphthyl-N-methyl-N-(3-tolyl) thionocarbamate:
Benzimidizole derivatives, for example those compounds that are called Protectol BCM shown in the following formula:
Benzoate derivatives, preferred Ergol:
What it should be noted that is, other many compounds that demonstrate anti-fungal property are also applicable to this method, and this is known to those skilled in the art.The example that provides above is not intended to be used for limiting the scope of the invention.
This method formulations employed can be compatible with the cellulosic aqueous solution, and help being incorporated in this fiber.
The antimicrobial or the antifungal agent that are used for the inventive method are water-soluble or just water-soluble slightly.Therefore these compounds use with discrete form., they be milled with suitable surfactant for this reason, make particle diameter reach about 1～2mm or littler, can adopt quartz ball grinding machine or homogenizer easily.Be made into stable formulation by adding the antimicrobial that suitable dispersant or emulsifying agent will so make then.
As an important feature of the present invention, have been found that antimicrobial, antifungal agent or its mixture can be dissolved in the surfactant with 1～60% concentration.By selecting suitable surfactant or surfactant system, and use or do not use extra dispersant, when above-mentioned preparation joins in the cellulose of dissolved state, just can form uniform mixture.
Surfactant solution dilution by with antimicrobial and/or antifungal agent forms a kind of dispersion, then it is pumped in the cellulose solution, immediately extrudes.The concentration of antimicrobial and/or antifungal agent is every liter of solution 10g～100g, preferred every liter of solution 40g～60g.
Perhaps, the surfactant concentrated solution of antimicrobial and/or antifungal agent directly is pumped in the cellulose solution, extrudes immediately then.This method requires accurate metering and mixes very uniformly, because be incorporated into antimicrobial in the fiber and/or the amount of antifungal agent is very little.
The surfactant that is applicable to the inventive method is:
The acid esters of-alkylene oxide adduct or its salt, be typically, the acid esters of the polynary adduct of 4～40mol oxirane and 1mol phenol or its salt, or 6～30mol oxirane and 1mol4-nonyl phenol, 1mol two nonylbenzene phenol, or preferably do not have that the styrene that replaces or replacement is arranged adds on the 1mol phenol and acid esters or its salt of the polynary adduct of Phosphation of the compound of preparation by 1～3mol with 1mol
-poly styrene sulfonate,
-aliphatic acid taurine ester,
-alkylation diphenyl ether list-or disulfonate,
The sulfonate of-polycarboxylate,
The fatty amine, aliphatic acid or the fatty alcohol that respectively contain 8-22 carbon atom in-1～60mol oxirane and/or expoxy propane and the alkyl chain, with the alkyl phenol that contains 4～16 carbon atoms in the alkyl chain, or with the polynary adduct that contains three of 3～6 carbon atoms～hexa-atomic alkanol, this polynary adduct changes into acid esters with organic dicarboxylic acid or with inorganic multivariate acid
-lignosulphonates, and most preferably,
-formaldehyde condensation products, condensation product as lignosulphonates and/or phenol and formaldehyde, the condensation product of formaldehyde and aromatic sulfonic acid, be typically the condensation product of xylyl ether sulfonate and formaldehyde, benzene sulfonic acid and/or naphthols-or the condensation product of naphthylamine sulfonic acid and formaldehyde, the condensation product of phenolsulfonic acid and/or sulfonation dihydroxydiphenylsulisomer and various phenol or cresols and formaldehyde and/or urea, and the condensation product of diphenyl ether disulfonic acid derivatives and formaldehyde.
Preferred surfactants is general formula C
9H
19C
6H
5O (CH
2CH
2O)
10Nonylplenyl ether shown in the H.
Have been found that and advantageously in preparation, be used in combination two or more as top listed surfactant.
During second step, mixture enters chemical bath by spinnerets, as containing 5%～15% sulfuric acid usually, and the coagulating bath of preferred 7%～12% sulfuric acid concentrated solution, cellulose is regenerated in this coagulating bath.Antimicrobial and/or antifungal agent precipitate rapidly in cellulose fibre when fiber contacts with coagulating bath, form very little particle.These particles are difficult to remove from fiber, and little as to be enough to avoid spinnerets to stop up.
Preparation of the present invention can be used to antimicrobial and/or antifungal agent are incorporated in the synthetic fiber of being produced by wet spinning technology and blend fibre thereof.This fiber comprises artificial silk, cellulose ethanoate, cellulosic triacetate, poly-ammonia ethene and polyacrylonitrile or its blend fibre.
The expection concentration of antimicrobial and/or antifungal agent is 0.1%～3% in the fiber, preferred 0.5%～1%.
Another aspect of the present invention provides the composition that is used for treatment process.Said composition comprises and is selected from following antimicrobial or its mixture:
(a) halo-neighbour-hydroxydiphenyl compounds;
(b) phenol derivatives;
(c) benzyl alcohol;
(d) triocil (chlorohexidine) and derivative thereof;
(e) C
12-C
14Alkyl betaine and C
8-C
18Fatty acid acyl aminoalkyl betaine;
(f) amphoteric surfactant;
(g) three halogen carbanilides;
(h) quaternary compound and many quaternary compounds; And
(i) thiazolium compounds and one or more are selected from following surfactant:
The acid esters of-alkylene oxide adduct or its salt, be typically, the acid esters of the polynary adduct of 4～40mol oxirane and 1mol phenol or its salt, or 6～30mol oxirane and 1mol4-nonyl phenol, 1mol two nonylbenzene phenol, or preferably do not have that the styrene that replaces or replacement is arranged adds on the 1mol phenol and acid esters or its salt of the polynary adduct of Phosphation of the compound of preparation by 1～3mol with 1mol
-poly styrene sulfonate,
-aliphatic acid taurine ester,
-alkylation diphenyl ether list-or disulfonate,
The sulfonate of-polycarboxylate,
The fatty amine, aliphatic acid or the fatty alcohol that respectively contain 8-22 carbon atom in-1～60mol oxirane and/or expoxy propane and the alkyl chain, with the alkyl phenol that contains 4～16 carbon atoms in the alkyl chain, or with the polynary adduct that contains three of 3～6 carbon atoms～hexa-atomic alkanol, this polynary adduct changes into acid esters with organic dicarboxylic acid or with inorganic multivariate acid
-lignosulphonates, and most preferably,
-formaldehyde condensation products, condensation product as lignosulphonates and/or phenol and formaldehyde, the condensation product of formaldehyde and aromatic sulfonic acid, be typically the condensation product of xylyl ether sulfonate and formaldehyde, benzene sulfonic acid and/or naphthols-or the condensation product of naphthylamine sulfonic acid and formaldehyde, the condensation product of phenolsulfonic acid and/or sulfonation dihydroxydiphenylsulisomer and various phenol or cresols and formaldehyde and/or urea, and the condensation product of diphenyl ether disulfonic acid derivatives and formaldehyde.
The compound that preferred compositions comprises by 40g formula (3) is dissolved in 60g general formula C
9H
19C
6H
5O (CH
2CH
2O)
10The solution of forming in the nonylplenyl ether shown in the H.
Said composition also can contain antifungal agent.The concentration of antimicrobial or anti-microbial/fungal agent mixture is 1～60%.
Another kind of composition comprises and is selected from following antifungal agent:
-naphthyl ether derivative,
-benzimidizole derivatives,
-benzoate derivatives, and be selected from following surfactant:
The acid esters of-alkylene oxide adduct or its salt, be typically, the acid esters of the polynary adduct of 4～40mol oxirane and 1mol phenol or its salt, or 6～30mol oxirane and 1mol4-nonyl phenol, 1mol two nonylbenzene phenol, or preferably do not have that the styrene that replaces or replacement is arranged adds on the 1mol phenol and acid esters or its salt of the polynary adduct of Phosphation of the compound of preparation by 1～3mol with 1mol
-poly styrene sulfonate,
-aliphatic acid taurine ester,
-alkylation diphenyl ether list-or disulfonate,
The sulfonate of-polycarboxylate,
The fatty amine, aliphatic acid or the fatty alcohol that respectively contain 8-22 carbon atom in-1～60mol oxirane and/or expoxy propane and the alkyl chain, with the alkyl phenol that contains 4～16 carbon atoms in the alkyl chain, or with the polynary adduct that contains three of 3～6 carbon atoms～hexa-atomic alkanol, this polynary adduct changes into acid esters with organic dicarboxylic acid or with inorganic multivariate acid
-lignosulphonates, and most preferably,
-formaldehyde condensation products, condensation product as lignosulphonates and/or phenol and formaldehyde, the condensation product of formaldehyde and aromatic sulfonic acid, be typically the condensation product of xylyl ether sulfonate and formaldehyde, benzene sulfonic acid and/or naphthols-or the condensation product of naphthylamine sulfonic acid and formaldehyde, the condensation product of phenolsulfonic acid and/or sulfonation dihydroxydiphenylsulisomer and various phenol or cresols and formaldehyde and/or urea, and the condensation product of diphenyl ether disulfonic acid derivatives and formaldehyde.
These compositions can dilute, and are every liter of 10g～100g so that make the concentration of antimicrobial wherein and/or antifungal agent, the dispersion liquid of preferred every liter of 40g～60g.
Put it briefly, preparation of the present invention and this preparation is used for fibre manufacturing technique can makes and have the fiber that improves antimicrobial and/or antifungal activity, and can not produce the spinnerets blockage problem, and antimicrobial acivity and/or the difficult removal of antifungal activity, because anti-microbial/fungal agent is evenly dispersed in the fiber.
The following example further specifies the present invention.
Embodiment 1
Contain the preparation of the preparation of antimicrobial
The 40g Triclosan, promptly the compound of formula (3) is dissolved in 60g general formula C
9H
19C
6H
5O (CH
2CH
2O)
10In the nonylplenyl ether shown in the H.Gained preparation (preparation A) is a kind of clear solution.
Embodiment 2
The preparation of dilution preparation
100g preparation A is joined in an amount of water (deionized water), be made into the 800ml preparation.Gained preparation (preparation B) is a kind of stable dispersion, and wherein the concentration of Triclosan is the 50g/ liter.
Embodiment 3
Contain the preparation of the rayon fiber of antimicrobial
The cellulose that is its dissolved state with the conventional method preparation.The steps include: to handle the cellulose of starching with caustic soda, oxidant and sulfonating agent, then with its solubilization/pulverizings with the formation aqueous solution, then filter and outgas.The cellulose of Zhi Bei dissolving just can be used for spinning and make fiber like this.With a membrane pump preparation B is injected in the Trunk Line, wherein Rong Xie artificial silk is being transported to spinnerets for extruding usefulness.The mixture of the artificial silk of preparation B and dissolving further mixes to improve uniformity in pipeline, extrudes the formation fiber from spinnerets then.Regulate pump speed and make that the content of Triclosan is 0.5～1% in the formed fiber.
Allow the solidification liquid of fiber by forming by 10% sulfuric acid of formation like this, and then the stretch bath by forming by 1% sulfuric acid, make it to solidify and stretch, then carry out desulfonation and react, wash, oil and drying.
Embodiment 4
The content of Triclosan in the rayon fiber
Extract with the 3.5g rayon fiber of 150ml methyl alcohol to embodiment 4 preparations in Soxhlet apparatus, its condition is as follows:
Temperature extremes: 300 ℃
290 ℃ of extraction temperature
Boiling time: 4 hours
Solvent reduction A:5 * 15ml
The extraction time: 6 hours
Solvent reduction interval: 4 minutes
Solvent reduction phase: 3 seconds
Under following condition, extract is carried out the anti-phase efficient liquid phase chromatographic analysis then:
Instrument: HP 1100 or other comparable system
Chromatographic column: Nucleosil 3C 18,70mm * 4.6mm ID, 40 ℃
Detector: 280 nm UV
Syringe: 2.0 μ l
Flow: 0.20ml/ minute
Solvent: 50% solvent orange 2 A (acetonitrile): 50% solvent B (water), 20 minutes
The time 100% solvent orange 2 A.
Result: (table 1)
| Sample | Triclosan content is analyzed for the first time | Triclosan content is analyzed for the second time |
| Mixed antimicrobial rayon short fibre's dimension of preparation A and B | ????0.71％ | ????0.82％ |
This result shows that claimed preparation A and the B of use the present invention can make the content of staying the antimicrobial in the fiber significantly increase.
Embodiment 5
The anti-microbial effect of the rayon fiber of handling with Triclosan
Purpose
With agar gel diffusion test measure antimicrobial contain the product of antimicrobial or the antibacterial or restraining epiphyte of the product handled with antimicrobial active.
Principle
The material of handling (being generally disc) is applied on the agar plate of inoculating.Can be diffused in the agar and bacteria growing inhibiting at the nurturing period active material.The product of diffusivity difference should can suppress the bacterial growth below the disk at least.
Described agar gel diffusion test is based on AATCC 90-1974 method.
Other method based on diffusion/inhibition principle has:
-SNV 195 ' 920: measure the method (1976) of the antibacterial effect of textiles and other material by agar gel diffusion test,
-SNV 195 ' 921: the method (1976) of measuring the anti-microbial effect of textiles and other material by agar gel diffusion test.
Test procedure
0.05g fiber is applied to the upper strata of solidifying agar of containing bacterium.In order to prepare top-layer agar,, get this dilution of 3.5ml then and join in the 500ml agar from having cultivated culture preparation 1: 100 (staphylococcus aureus) and 1: 1000 (Escherichia coli and proteus vulgaris) dilution at a night.
The bacterium of test: staphylococcus aureus ATCC 9144
Escherichia coli NCTC 8196
Common deformation bacillus ATCC 6896
Nutrient media:
The casein soy sauce eats peptone agar (2 layers of agar: bottom 15ml, no bacterium, upper strata 5ml has bacterium)
Cultivate: 37 ℃ 18-24 hour.
Result's (table 2)
| Staphylococcus aureus ATCC 9144 | Escherichia coli NCTC 8196 | Proteus vulgaris NCTC 8196 | ||||
| ???ZI | ???VR | ????ZI | ??VR | ???ZI | ??VR | |
| Mixed antimicrobial rayon short fibre's dimension of preparation A and B | ?20/20 | ??4/4 | ??15/15 | ??4/4 | ??13/13 | ??4/4 |
Each test is carried out 2 times, and 2 times the result all lists in the table.
Code name in the table: the ZI=inhibition zone, mm,
The VR=disk is the Vinson grade of growth down,
0=growth prosperous and powerful (non-activity),
The medium growth of 2=,
4=do not grow (active good).
See also people such as L.J.Vinson about the Vinson grade: J.Pharm Sci. (pharmaceutical science magazine) 50,827-830,1961.
Indicated as top microbiological test, the rayon fiber that contains the antimicrobial Triclosan can suppress microorganism also can provide fiber inhibition zone on every side in the growth (being measured by the Vinson grade) of fiber surface, the a small amount of Triclosan that in this inhibition zone, from fiber, diffuses out owing to existence, so microbial growth is suppressed.
Embodiment 6
The preparation of antifungal preparation
Antimycotic material with structural formula (15):
Prepare a kind of preparation that contains proportional following anion surfactant, non-ionic dispersing agent, a small amount of organic solvent and water:
Formulation C 1:
Compound (15): 10%
Anion surfactant: 30%
Dispersant: 10%
Solvent: 10%
Water: 40%
Compound (15) also is used for preparing a kind of preparation that contains the compound of proportional following anion surfactant, non-ionic dispersing agent, a spot of organic solvent, water and formula (3):
Preparation D1:
Compound (15): 10%
Compound (3): 10%
Anion surfactant: 30%
Dispersant: 10%
Solvent: 10%
Water: 30%
Embodiment 7
The preparation of dilution preparation
100g formulation C 1 joins in an amount of water (deionized water) and is made into the 800ml preparation.Resulting preparation (formulation C 2) is a kind of stable dispersion, and the concentration of the antimycotic material of its Chinese style (15) is the 50g/ liter.
Embodiment 8
Contain the preparation of the rayon fiber of antimicrobial
The cellulose that is its dissolved state with the conventional method preparation.The steps include: to handle the cellulose of starching with caustic soda, oxidant and sulfonating agent, then with its solubilization/pulverizings with the formation aqueous solution, then filter and outgas.The cellulose of Zhi Bei dissolving just can be used for spinning and make fiber like this.With a membrane pump formulation C 2 is injected in the Trunk Line, wherein Rong Xie artificial silk is being transported to spinnerets for extruding usefulness.The mixture of the artificial silk of formulation C 2 and dissolving further mixes to improve uniformity in pipeline, extrudes the formation fiber from spinnerets then.Regulate pump speed and make that the content of material (15) is 0.5～1% in the formed fiber.
Allow the solidification liquid of fiber by forming by 10% sulfuric acid of formation like this, and then the stretch bath by forming by 1% sulfuric acid, make it to solidify and stretch, then carry out desulfonation and react, wash, oil and drying.
Embodiment 9
The anti-microbial effect of the rayon fiber of handling with material (15)
Purpose:
With agar gel diffusion test measure antimicrobial contain the product of antimicrobial or the antibacterial or restraining epiphyte of the product handled with antimicrobial active.
Principle
The material of handling (being generally disc) is applied on the agar plate of inoculating.Can be diffused in the agar and bacteria growing inhibiting at the nurturing period active material.The product of diffusivity difference should can suppress the bacterial growth below the disk at least.
Described agar gel diffusion test is based on AATCC 90-1974 method.
Other method based on diffusion/inhibition principle has:
-SNV 195 ' 920: measure the method (1976) of the antibacterial effect of textiles and other material by agar gel diffusion test,
-SNV 195 ' 921: the method (1976) of measuring the anti-mycotic efficiency of textiles and other material by agar gel diffusion test.
Test procedure
0.05g fiber is applied to the upper strata of solidifying agar of containing bacterium.In order to prepare top-layer agar,, get this dilution of 3.5ml then and join in the 500ml agar from having cultivated 1: 100 (staphylococcus aureus) dilution of culture preparation at a night.Under the situation of trichophyton mentagrophytes and aspergillus niger (Aspergnis Niger), 4ml fungal spore suspension is mixed with 500ml fusion agar at 47 ℃.The purpose of this preparation is to make that the ultimate density of bacterium reaches about 10 in the agar
4Cfu/ml.
The bacterium of test: staphylococcus aureus ATCC 9144
Trichophyton mentagrophytes ATCC 9553
Aspergillus niger (Aspergnis niger) ATCC 6275
Nutrient media:
The casein soy sauce eats peptone agar (2 layers of agar: bottom 15ml, no bacterium, upper strata 5ml has bacterium)
Cultivate: 37 ℃ 18～24 hours, for test antibacterial activity usefulness, 28 ℃ 4 days, supply
The test antifungal activity is used.
Result's (table 3)
Sample: rayon short fibre's dimension of having mixed formulation C 2
| Bacterium | Inhibition zone (mm) | The Vinson grade |
| Staphylococcus aureus ATCC 9144 | ????0/0 | ????0/0 |
| Trichophyton mentagrophytes ATCC 9553 | ????5/5 | ????4/4 |
| Aspergillus niger (Aspergillus niger) ATCC 6275 | ????1/1 | ????4/4 |
Each test is carried out 2 times, and 2 times the result all lists in the table.
Code name in the table: the VR=disk is the Vinson grade of growth down,
0=growth prosperous and powerful (non-activity),
The medium growth of 2=,
4=do not grow (active good).
See also people such as L.J.Vinson about the Vinson grade: J.Pharm Sci. (pharmaceutical science magazine) 50,827-830,1961.
The result shows that the rayon fiber of handling with antimycotic substance C 1 demonstrates the good antimicrobial acivity to fungi, but bacterium is not then had antibiotic activity.
Embodiment 10
The preparation of dilution preparation
100g formulation C 1 joins in an amount of water (deionized water) and is made into the 800ml preparation.Resulting preparation (formulation C 2) is a kind of stable dispersion, and wherein the concentration of compound (15) and compound (3) is the 50g/ liter.
Embodiment 11
Contain the preparation of the rayon fiber of antimicrobial
The cellulose that is its dissolved state with the conventional method preparation.The steps include: to handle the cellulose of starching with caustic soda, oxidant and sulfonating agent, then with its solubilization/pulverizings with the formation aqueous solution, then filter and outgas.The cellulose of Zhi Bei dissolving just can be used for spinning and make fiber like this.With a membrane pump preparation D2 is injected in the Trunk Line, wherein Rong Xie artificial silk is being transported to spinnerets for extruding usefulness.The mixture of the artificial silk of preparation D2 and dissolving further mixes to improve uniformity in pipeline, extrudes the formation fiber from spinnerets then.Regulate pump speed and make that the content of material D2 and Triclosan is 0.5～1% in the formed fiber.
Allow the solidification liquid of fiber by forming by 10% sulfuric acid of formation like this, and then the stretch bath by forming by 1% sulfuric acid, make it to solidify and stretch, then carry out desulfonation and react, wash, oil and drying.
Embodiment 12
The anti-microbial effect of the rayon fiber of handling with compound (15) and compound (3)
Purpose
With agar gel diffusion test measure antimicrobial contain the product of antimicrobial or the antibacterial or restraining epiphyte of the product handled with antimicrobial active.
Principle
The material of handling (being generally disc) is applied on the agar plate of inoculating.Can be diffused in the agar and bacteria growing inhibiting at the nurturing period active material.The product of diffusivity difference should can suppress the bacterial growth below the disk at least.
Described agar gel diffusion test is based on AATCC 90-1974 method.
Other method based on diffusion/inhibition principle has:
-SNV 195 ' 920: measure the method (1976) of the antibacterial effect of textiles and other material by agar gel diffusion test,
-SNV 195 ' 921: the method (1976) of measuring the anti-mycotic efficiency of textiles and other material by agar gel diffusion test.
Test procedure
0.05g fiber is applied to the upper strata of solidifying agar of containing bacterium.In order to prepare top-layer agar,, get this dilution of 3.5ml then and join in the 500ml agar from having cultivated 1: 100 (staphylococcus aureus) dilution of culture preparation at a night.Under the situation of trichophyton mentagrophytes and aspergillus niger (Aspergnis Niger), 4ml fungal spore suspension is mixed with 500ml fusion agar at 47 ℃.The purpose of this preparation is to make that the ultimate density of bacterium reaches about 10 in the agar
4Cfu/ml.
The bacterium of test: staphylococcus aureus ATCC 9144
Trichophyton mentagrophytes ATCC 9553
Aspergillus niger (Aspergnis niger) ATCC 6275
Nutrient media:
The casein soy sauce eats peptone agar (2 layers of agar: bottom 15ml, no bacterium, upper strata 5ml has bacterium)
Cultivate: 37 ℃ 18～24 hours, for test antibacterial activity usefulness, 4 days, anti-for test
Fungi activity is used.
Result's (table 4)
Sample: rayon short fibre's dimension of having mixed preparation D2
| Bacterium | Inhibition zone (mm) | The Vinson grade |
| Staphylococcus aureus ATCC 9144 | ????20/20 | ????4/4 |
| Trichophyton mentagrophytes ATCC 9553 | ????7/7 | ????4/4 |
| Aspergillus niger (Aspergillus niger) ATCC 6275 | ????1/1 | ????4/4 |
Each test is carried out 2 times, and 2 times the result all lists in the table.
Code name in the table: the VR=disk is the Vinson grade of growth down,
0=growth prosperous and powerful (non-activity),
The medium growth of 2=,
4=do not grow (active good).
See also people such as L.J.Vinson about the Vinson grade: J.Pharm Sci. (pharmaceutical science magazine) 50,827-830,1961.
The result shows that the rayon fiber of handling with compound (15) and compound (3) all demonstrates antimicrobial acivity to fungi and bacterium.
Claims (18)
1. method with antimicrobial, antifungal agent or its mixture process regenerated cellulose wherein in the first step, will comprise before regeneration and be selected from following antimicrobial:
(a) halo-neighbour-hydroxydiphenyl compounds;
(b) phenol derivatives;
(c) benzyl alcohol;
(d) triocil (chlorohexidine) and derivative thereof;
(e) C
12-C
14Alkyl betaine and C
8-C
18Fatty acid acyl aminoalkyl betaine;
(f) amphoteric surfactant;
(g) three halogen carbanilides;
(h) quaternary compound and many quaternary compounds; And
(i) thiazolium compounds, and/or be selected from following antifungal agent:
-naphthyl ether derivative;
-benzimidizole derivatives;
-benzoate derivatives; Join in the cellulose of dissolved state with the preparation of one or more surfactants, this mixture is expressed into the chemical bath to form regenerated fiber from spinnerets in second step.
2. according to the process of claim 1 wherein that this antimicrobial is the compound shown in the following formula:
Wherein
X be oxygen, sulphur or-CH
2-,
Y is a chlorine or bromine,
Z is SO
2H, NO
2Or C
1-C
4Alkyl,
R is 0～3,
O is 0～3,
P is 0 or 1,
M be 0 or 1 and
N is 0 or 1;
And have 1 among r or the o at least and be not equal to 0.
3. according to the process of claim 1 wherein that this antimicrobial is the compound shown in the following formula:
4. according to the process of claim 1 wherein that this antimicrobial is the compound shown in the following formula:
5. according to the process of claim 1 wherein that this antifungal agent is the compound shown in the following formula:
6. according to any one method in the claim 1～5, wherein this surfactant is selected from:
The acid esters of-alkylene oxide adduct or its salt, be typically, the acid esters of the polynary adduct of 4～40mol oxirane and 1mol phenol or its salt, or 6～30mol oxirane and 1mol4-nonyl phenol, 1mol two nonylbenzene phenol, or preferably do not have that the styrene that replaces or replacement is arranged adds on the 1mol phenol and acid esters or its salt of the polynary adduct of Phosphation of the compound of preparation by 1～3mol with 1mol
-poly styrene sulfonate,
-aliphatic acid taurine ester,
-alkylation diphenyl ether list-or disulfonate,
The sulfonate of-polycarboxylate,
The fatty amine, aliphatic acid or the fatty alcohol that respectively contain 8-22 carbon atom in-1～60mol oxirane and/or expoxy propane and the alkyl chain, with the alkyl phenol that contains 4～16 carbon atoms in the alkyl chain, or with the polynary adduct that contains three of 3～6 carbon atoms～hexa-atomic alkanol, this polynary adduct changes into acid esters with organic dicarboxylic acid or with inorganic multivariate acid
-lignosulphonates, and most preferably,
-formaldehyde condensation products, condensation product as lignosulphonates and/or phenol and formaldehyde, the condensation product of formaldehyde and aromatic sulfonic acid, be typically the condensation product of xylyl ether sulfonate and formaldehyde, benzene sulfonic acid and/or naphthols-or the condensation product of naphthylamine sulfonic acid and formaldehyde, the condensation product of phenolsulfonic acid and/or sulfonation dihydroxydiphenylsulisomer and various phenol or cresols and formaldehyde and/or urea, and the condensation product of diphenyl ether disulfonic acid derivatives and formaldehyde.
7. according to any one method in the claim 1～6, the preparation that wherein contains antimicrobial and one or more surfactants is a kind of solution or aqueous dispersions.
8. according to any one method in the claim 1～6, the preparation that wherein contains antifungal agent and one or more surfactants is a kind of solution or aqueous dispersions.
9. according to any one method in the claim 1～6, wherein the concentrated solution of antimicrobial in surfactant directly is pumped in the cellulose solution, extrudes immediately then.
10. according to any one method in the claim 1～6, wherein the concentrated solution of antifungal agent in surfactant directly is pumped in the cellulose solution, extrudes immediately then.
11. according to any one method in the claim 1～10, wherein this surfactant is general formula C
9H
19C
6H
5O (CH
2CH
2O)
10Nonylplenyl ether shown in the H.
12. according to any one method in the claim 1～11, wherein this solution contains two or more surfactants.
13. according to any one method in the claim 1～12, wherein this solution or aqueous dispersions contain the antimicrobial that concentration is said preparation gross weight 1～60%.
14. according to any one method in the claim 1～13, wherein in second step, this mixture enters in the chemical bath that contains 5%～15% concentrated sulfuric acid by spinnerets.
15. the fiber that makes by any one desired method in the claim 1～14.
16. a composition wherein comprises and is selected from following antimicrobial:
(a) halo-neighbour-hydroxydiphenyl compounds;
(b) phenol derivatives;
(c) benzyl alcohol;
(d) triocil (chlorohexidine) and derivative thereof;
(e) C
12-C
14Alkyl betaine and C
8-C
18Fatty acid acyl aminoalkyl betaine;
(f) amphoteric surfactant;
(g) three halogen carbanilides;
(h) quaternary compound and many quaternary compounds; And
(i) thiazolium compounds, and/or be selected from following antifungal agent:
-naphthyl ether derivative;
-benzimidizole derivatives;
-benzoate derivatives; Be selected from following surfactant with one or more:
The acid esters of-alkylene oxide adduct or its salt, be typically, the acid esters of the polynary adduct of 4～40mol oxirane and 1mol phenol or its salt, or 6～30mol oxirane and 1mol4-nonyl phenol, 1mol two nonylbenzene phenol, or preferably do not have that the styrene that replaces or replacement is arranged adds on the 1mol phenol and acid esters or its salt of the polynary adduct of Phosphation of the compound of preparation by 1～3mol with 1mol
-poly styrene sulfonate,
-aliphatic acid taurine ester,
-alkylation diphenyl ether list-or disulfonate,
The sulfonate of-polycarboxylate,
The fatty amine, aliphatic acid or the fatty alcohol that respectively contain 8-22 carbon atom in-1～60mol oxirane and/or expoxy propane and the alkyl chain, with the alkyl phenol that contains 4～16 carbon atoms in the alkyl chain, or with the polynary adduct that contains three of 3～6 carbon atoms～hexa-atomic alkanol, this polynary adduct changes into acid esters with organic dicarboxylic acid or with inorganic multivariate acid
-lignosulphonates, and most preferably,
-formaldehyde condensation products, condensation product as lignosulphonates and/or phenol and formaldehyde, the condensation product of formaldehyde and aromatic sulfonic acid, be typically the condensation product of xylyl ether sulfonate and formaldehyde, benzene sulfonic acid and/or naphthols-or the condensation product of naphthylamine sulfonic acid and formaldehyde, the condensation product of phenolsulfonic acid and/or sulfonation dihydroxydiphenylsulisomer and various phenol or cresols and formaldehyde and/or urea, and the condensation product of diphenyl ether disulfonic acid derivatives and formaldehyde.
17. according to the composition of claim 16, said composition comprises two or more surfactants as claim 16 definition.
18. according to any one composition in the claim 16～17, said composition is diluted, and makes that the concentration of antimicrobial and/or antifungal agent is that 10g～100g/ rises solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98811085.4 | 1998-10-29 | ||
| EP98811085 | 1998-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1325462A true CN1325462A (en) | 2001-12-05 |
Family
ID=8236417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99812791A Pending CN1325462A (en) | 1998-10-29 | 1999-10-18 | Incorporation of organic anti-microbials into fibres during a fibre spinning |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1141453A1 (en) |
| KR (1) | KR20010087382A (en) |
| CN (1) | CN1325462A (en) |
| AU (1) | AU6473499A (en) |
| TR (1) | TR200101052T2 (en) |
| WO (1) | WO2000026447A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351475C (en) * | 2002-06-07 | 2007-11-28 | 密克罗伴产品公司 | Antimicrobial wallboard |
| CN100419137C (en) * | 2003-11-14 | 2008-09-17 | 宜宾丝丽雅股份有限公司 | Antibiotic cellulose viscose and process for making same |
| CN102933753A (en) * | 2010-04-08 | 2013-02-13 | 利斯特股份公司 | Process for producing a product |
| CN102933753B (en) * | 2010-04-08 | 2016-12-14 | 利斯特股份公司 | For the method manufacturing product |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0937812A2 (en) | 1998-02-20 | 1999-08-25 | Ciba SC Holding AG | Process for the treatment of nonwovens with antimicrobial agents |
| DE10200717A1 (en) | 2002-01-10 | 2003-07-31 | Knoell Hans Forschung Ev | Use of polysaccharide derivatives as anti-infective substances |
| JP2010532433A (en) * | 2007-07-03 | 2010-10-07 | アディティア ビルラ サイエンス アンド テクノロジー カンパニー リミテッド | Viscose fiber having modified properties and method for producing the same |
| CN101952322B (en) * | 2008-02-08 | 2013-06-26 | 利斯特股份公司 | Method and device for the production of molded bodies |
| DE102010037530A1 (en) * | 2010-06-11 | 2011-12-15 | List Holding Ag | Process for the preparation of a product |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1036593A (en) * | 1962-03-31 | 1966-07-20 | Fisons Pest Control Ltd | Fungicidal compositions |
| US3506720A (en) * | 1963-02-22 | 1970-04-14 | Geigy Chem Corp | Halogenated hydroxy-diphenyl ethers |
| US3296000A (en) * | 1966-04-06 | 1967-01-03 | Fmc Corp | Shaped regenerated cellulose products having bacteriostatic properties |
| CH501364A (en) * | 1967-04-11 | 1971-01-15 | Du Pont | 2-Benzimidazolecarbamic acid alkyl esters - fungicidal compsns. |
| CH494533A (en) * | 1969-04-25 | 1970-08-15 | Agripat Sa | Polychlorobenzimidazole bactericides for - protecting cellulosic non-textiles |
| JPS6048908A (en) * | 1983-08-26 | 1985-03-16 | Sanyo Chem Ind Ltd | Antimicrobial processing agent |
| JP2750785B2 (en) * | 1991-03-12 | 1998-05-13 | 東邦レーヨン株式会社 | Manufacturing method of antibacterial cellulose fiber |
| DE4242389C2 (en) * | 1992-12-08 | 1995-09-21 | Schuelke & Mayr Gmbh | Aqueous dispersion with fungicidal and algistatic action |
| EP0908553A3 (en) * | 1997-10-13 | 2001-03-07 | Ciba SC Holding AG | Process for the treatment of textile materials with an antimicrobial agent |
| EP0937812A2 (en) * | 1998-02-20 | 1999-08-25 | Ciba SC Holding AG | Process for the treatment of nonwovens with antimicrobial agents |
-
1999
- 1999-10-18 TR TR2001/01052T patent/TR200101052T2/en unknown
- 1999-10-18 KR KR1020017005295A patent/KR20010087382A/en not_active Application Discontinuation
- 1999-10-18 AU AU64734/99A patent/AU6473499A/en not_active Abandoned
- 1999-10-18 EP EP99952595A patent/EP1141453A1/en not_active Withdrawn
- 1999-10-18 CN CN99812791A patent/CN1325462A/en active Pending
- 1999-10-18 WO PCT/EP1999/007875 patent/WO2000026447A1/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351475C (en) * | 2002-06-07 | 2007-11-28 | 密克罗伴产品公司 | Antimicrobial wallboard |
| CN100419137C (en) * | 2003-11-14 | 2008-09-17 | 宜宾丝丽雅股份有限公司 | Antibiotic cellulose viscose and process for making same |
| CN102933753A (en) * | 2010-04-08 | 2013-02-13 | 利斯特股份公司 | Process for producing a product |
| CN102933753B (en) * | 2010-04-08 | 2016-12-14 | 利斯特股份公司 | For the method manufacturing product |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1141453A1 (en) | 2001-10-10 |
| KR20010087382A (en) | 2001-09-15 |
| TR200101052T2 (en) | 2001-08-21 |
| WO2000026447A1 (en) | 2000-05-11 |
| AU6473499A (en) | 2000-05-22 |
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