EP1873300A1 - Antimicrobial textile - Google Patents
Antimicrobial textile Download PDFInfo
- Publication number
- EP1873300A1 EP1873300A1 EP20060116455 EP06116455A EP1873300A1 EP 1873300 A1 EP1873300 A1 EP 1873300A1 EP 20060116455 EP20060116455 EP 20060116455 EP 06116455 A EP06116455 A EP 06116455A EP 1873300 A1 EP1873300 A1 EP 1873300A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- microparticles
- textile
- active ingredient
- biocidal active
- melamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004753 textile Substances 0.000 title claims abstract description 94
- 230000000845 anti-microbial effect Effects 0.000 title description 9
- 230000003115 biocidal effect Effects 0.000 claims abstract description 78
- 239000011859 microparticle Substances 0.000 claims abstract description 67
- 239000003139 biocide Substances 0.000 claims abstract description 42
- 239000013543 active substance Substances 0.000 claims abstract description 34
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- 239000011347 resin Substances 0.000 claims abstract description 31
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- 239000004480 active ingredient Substances 0.000 claims description 49
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 38
- 229920000877 Melamine resin Polymers 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
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- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 239000007859 condensation product Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960003887 dichlorophen Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical class O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229940124561 microbicide Drugs 0.000 description 1
- 239000002855 microbicide agent Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 229940070805 p-chloro-m-cresol Drugs 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
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- 230000002085 persistent effect Effects 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
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- 235000021317 phosphate Nutrition 0.000 description 1
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- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
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- 229920002689 polyvinyl acetate Polymers 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- FAUOSXUSCVJWAY-UHFFFAOYSA-N tetrakis(hydroxymethyl)phosphanium Chemical class OC[P+](CO)(CO)CO FAUOSXUSCVJWAY-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/12—Processes in which the treating agent is incorporated in microcapsules
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2041—Two or more non-extruded coatings or impregnations
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2525—Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]
Definitions
- the invention relates to a textile antimicrobially finished with at least one biocidal active substance.
- the biocidal agent is enclosed in an aminoplast-based resin.
- the enclosed biocidal active ingredient is useful as a textile auxiliaries for finishing textiles such as tent fabrics, awnings, covers, shower curtains, nonwovens, filters, carpets and the like.
- Most textiles contain microbiologically degradable material. They are either completely or partially made of microbiologically degradable fibers, for example cotton, hemp, flax, linen, viscose, tencel, acetate, silk, wool.
- Textiles of synthetic fibers e.g. Polyester, polyacrylonitrile, polyamide, polypropylene, nomex, aramid become microbiologically vulnerable when treated with finishing agents such as e.g. Sizing, spun oils, lubricants, plasticizers, water repellents, antistatics, and / or binders, or to receive microbiologically degradable material during use, e.g. organic substances from the environment or soap residues.
- finishing agents such as e.g. Sizing, spun oils, lubricants, plasticizers, water repellents, antistatics, and / or binders
- microbiologically degradable material e.g. organic substances from the environment or soap residues.
- the textiles In the textile industry, high demands are placed on the biocides used for finishing textiles. For example, after finishing, the textiles usually have to be dried at temperatures of from 100 to 130 ° C. and, in order to additionally achieve sufficient hydrophobicity, then be treated at temperatures up to 180 ° C.
- the high evaporation rate of the biocides often leads to high drug losses.
- synthetic fibers such as polyester, polyamide, polypropylene or polyacrylonitrile fibers, drug losses of over 95% are observed after equipping.
- the active substance remaining on the textile after finishing is washed out in practice during washing of the textile, for example during irrigation. This is another notable loss of active ingredient. Furthermore, the influence of light can also lead to a decomposition of the biocidal active substances remaining after the finishing.
- biocides which have a low evaporation rate and / or remain largely by irrigation on the textile.
- satisfactory biocides are less suitable for finishing textiles because of their toxic effects.
- These include chlorothalonil and in particular the carbendazim classified as carcinogenic.
- skin irritations are to be called as disadvantageous.
- skin contact also occurs with textiles that generally do not come in contact with the human body during intended use.
- the invention is therefore based on the object of providing an antimicrobially finished textile which largely avoids the disadvantages listed above and, in particular, minimizes the escape of the biocidal active substance during finishing.
- the aim is to reduce the environmental impact and the cost of the equipment of the textile to combat harmful microorganisms and reduce the evaporation rate of the biocidal active ingredient from the finished textile.
- the antimicrobial effect of the microbicide used for the equipment should be guaranteed for as long as possible.
- biocidal active substance which contains 2-n-octyl-4-isothiazolin-3-one (OIT) as biocidal active substance and furthermore optionally one or more other biocides in which the biocidal active ingredient is enclosed in microparticles of an aminoplast resin, preferably of a melamine-formaldehyde resin.
- OIT 2-n-octyl-4-isothiazolin-3-one
- biocidal active substance refers to the substance or mixture of substances which has the biocidal effect of the invention
- the biocidal active ingredient in each case contains OIT, in addition to optionally further active ingredient, as defined in more detail below becomes.
- the microparticles contain OIT as biocidal active ingredient and additionally one or more other biocides.
- the ratio of OIT to the other biocide (s) can, in principle, vary and be varied within wide limits, for example in the range from 100: 1 to 1: 100, preferably 50: 1 to 1:50.
- the OIT is usually present in amounts of from 10 to 95% by weight, in particular from 20 to 80% by weight, and the other biocides in amounts of from 5 to 90% by weight, in particular from 20 to 80 wt .-%, in each case based on the total amount of contained biocidal active ingredient.
- the biocidal active ingredient included in the microparticles consists predominantly of OIT.
- OIT entrapped biocidal active ingredient as the main component OIT, preferably in an amount of equal to or greater than 50 wt .-% OIT, more preferably in an amount of equal to or greater than 70 wt .-%, in particular in an amount equal to or greater 90 wt .-%, in particular in an amount of equal to or greater than 95 wt .-% OIT, based on the total mass of biocidal active ingredient.
- at least one other biocide may be present.
- the biocidal active ingredient enclosed in the microparticles consists essentially of OIT, ie, in addition to OIT one or more other biocides may still be present, but these are present in an amount in which no contribution of the respective OIT different biocides to the overall effect of the resulting mixture is present.
- the biocidal active ingredient may consist of OIT as the only biocidal active ingredient, ie an active ingredient content of 100% OIT. In such a case, it is only possible that one or more other ingredients are present without a biocidal effect.
- textile fibers for textile use such as threads, yarns, threads, fabrics, knits, woven / knitted fabric, nonwovens, and the like.
- textile finished goods such as clothing.
- textile textile units or subunits of textiles such as tent fabrics, awnings, umbrellas and sunshades, covers, shower curtains, nonwovens, filters, carpets and the like to understand.
- aminoplast resins are polycondensation products of carbonyl compounds, in particular of formaldehyde and compounds containing NH groups, for example urea (urea resins), melamine (melamine resins), urethanes (urethane resins), cyanogens and Dicyanamide (cyano or dicyanamide), aromatic amines (aniline resins) and sulfonamides (sulfonamide resins), see Römpp, Chemie Lexikon, Thieme Verlag Stuttgart, 9th, extended edition, 1995, volume A-Cl, page 159 , The said section of the reference is incorporated by reference into the present application.
- Preferred materials of the microparticles are melamine, urea and dicyandiamide-formaldehyde resins, particularly preferred materials are melamine-formaldehyde resins.
- urea resins mentioned above are hardenable condensation products of ureas and aldehydes belonging to the aminoplasts, in particular these include formaldehyde.
- formaldehyde For their preparation, urea or substituted ureas are reacted with formaldehyde in molar excess under mostly alkaline conditions. The result is hydroxymethyl group-containing oligomers, which are cured with crosslinking.
- formaldehyde it is also possible to use other aldehydes, for example acetaldehyde or glyoxal.
- Condensates based on modified ureas are also starting materials which can be used in the preparation of the microparticle material in the context of the invention.
- melamine resins is to be understood as meaning aminoplast resins in which melamine has been polycondensed under suitable conditions with carbonyl compounds such as aldehydes and ketones, for example formaldehyde, acetaldehyde or glyoxal. For their preparation, melamine is generally reacted with the carbonyl compound in molar excess.
- carbonyl compounds such as aldehydes and ketones, for example formaldehyde, acetaldehyde or glyoxal.
- melamine is generally reacted with the carbonyl compound in molar excess.
- polycondensation products of melamine with formaldehyde (melamine-formaldehyde resins) or with urea or phenol-modified melamine-formaldehyde resins (melamine-urea-formaldehyde resins, melamine-phenol-formaldehyde resins).
- microparticles containing the biocidal active ingredient may also be formed from two or more of the aforementioned aminoplast resins.
- particular care must be taken that there is no destruction or inhibition of the biocidal active substance during production.
- biocidal active substance Due to the inclusion of the biocidal active substance in the microparticles, this surprising manner is not or only to a very small extent volatilized or released in the production of the textile during drying and condensation, despite the high temperatures used, while at the same time remaining biocidally active; and he rather remains on the textile, so that it can be used in correspondingly low concentrations.
- the biocidal active ingredient is released only slowed down (retarding). It has been shown in an advantageous manner that the biocidal active ingredient enclosed in the microparticles is not washed out to a great extent during the irrigation or washing of the textiles equipped therewith, as would have been usual to be expected.
- smaller amounts of active ingredient can be used for the equipment, and on the other hand, it is possible to achieve considerably longer effective times
- microparticles refers to any type of particle comprising a wall structure and at least one cavity formed by the wall structure.
- the wall structure in this case contains one or more aminoplast resins, preferably one.
- the cavities formed by the wall structure may be closed or open and contain the biocidal active ingredient and optionally other various excipients. Closed cavities may, for example, be in the form of capsule structures or cell structures, open cavities in the form of pores, channels and the like.
- the term microparticles may likewise mean a matrix of an aminoplast resin, wherein the biocidal active ingredient is enclosed in the matrix or enveloped by it.
- microparticles may refer to so-called microcapsules, in the interior of which the biocidal active ingredient is encapsulated encapsulated.
- the microparticles have a spherical shape.
- This shape has the advantage of high volume, low surface area, whereby impinging water has a low wetting area.
- sprinkling the textiles finished with the microparticles releases only a small portion of the biocidal active substance.
- the long-term effect of the antimicrobial finish of textiles is significantly improved. This results in a durable protection of the textiles against microbial attack.
- the average diameter of microparticles useful for finishing textiles is usually in the range of about 0.5 to about 100 microns, the preferred average diameter is in the range of about 1 to about 10 microns.
- the size of the microparticles can be determined, for example, under a microscope using a micrometer scale.
- the textiles are finished in such a way that the antimicrobially finished textile generally has an amount of biocidal active substance, based on the total weight of the textile, of 0.0001% by weight to 0.5% by weight, preferably of 0.01% by weight. to 0.2% by weight, more preferably from 0.05% to 0.15% by weight.
- biocidal active substance is lost only to a small extent during the processing of the textiles and can thus be used in much smaller quantities.
- biocidal agent in the microparticles not only has the advantage of sustained release of the biocidal agent, but the shielding of the biocidal agent through the particle wall has the consequence that this thereby increased stability to UV radiation, elevated temperatures, heavy metal ions and pH Values.
- Biocides are used in many areas and are used to fight bacteria, fungi or algae. It has long been known to use compounds of the class of 3-isothiazolin-3-ones (which are also referred to as 3-isothiazolones) in such compositions in particular. In this class of substances are very effective biocides with sometimes different profile of action. Often, combinations of different 3-isothiazolin-3-ones, or of one or more 3-isothaziolin-3-ones with other known biocidal agents used (see, inter alia others. WO 99/08530 A . EP 0457435 A . EP 0542721 A and WO 02/17716 A ). In view of the ever-increasing demands on such biocidal compositions, for example with regard to health and environmental protection aspects, the antimicrobial finishing of textiles requires a further development of the known products.
- a melamine-formaldehyde resin enclosed biocidal agents for application in coating compositions, in particular in facade plasters are from WO 2004/000953 the applicant known.
- this application gives no indication that OIT trapped in an aminoplast resin, preferably in a melamine-formaldehyde resin, is excellent for finishing textiles.
- the fact that the high temperatures required in the finishing step on the one hand cause only a slight escape of the biocidal active substance from the microparticles is surprising, and the particles release the biocidal active substance to a desired extent after the equipment has been provided after retarding.
- the antimicrobial textile is characterized in that less than about 70%, preferably less than about 50%, more preferably less than 10% of the biocidal active ingredient escape during drying or thermal aftertreatment. This not only reduces the loss of biocidal active substance, but also the entry into the exhaust air / environment. Despite the inclusion of the biocidal agent in the microparticles, the biocidal activity of the biocidic agent is maintained.
- microparticles according to the invention then have a good effect according to the invention when they contain from 5 to 99.99% by weight of the aminoplast resin and from 0.01 to 95% by weight of the biocidal active substance, preferably from 15 to 60% by weight of the aminoplast Resin and 85 to 40% by weight of the biocidic agent based on the total weight of the aminoplast resin and the biocidic agent.
- the known 2-n-octyl-4-isothiazolin-3-one has antimicrobial properties which are desirable for the finishing of textiles.
- OIT 2-n-octyl-4-isothiazolin-3-one
- BIT 1,2-benzoisothiazolin-3-one
- the very good has bactericidal properties, due to its high water solubility and high volatility at higher temperatures also only partially suitable for textile applications.
- the use of the microparticles according to the invention is particularly suitable for the finishing of textiles which are used in the outdoor area, because OIT is a biocide with fungicidal and algicidal action, because of the broad spectrum of activity of OIT. It contains no halogen or heavy metal compounds, is not persistent or accumulable, is not classified as a CMR substance and has a favorable human and ecotoxicological profile. It is therefore generally suitable for the finishing of textiles in terms of its properties. Thus, its use from both the ecological and economic point of view also advantageous because of its advantageous spectrum of action.
- one or more other biocides can additionally be used, which can be selected depending on the field of application. Specific examples of such additional biocides are given below:
- benzyl alcohol 2,4-dichlorobenzyl; 2-phenoxyethanol; 2-phenoxyethanolhemiformal, phenylethyl alcohol; 5-bromo-5-nitro-1,3-dioxane; bronopol; Formaldehyde and formaldehyde depot substances; dimethyloldimethylhydantoin; glyoxal; glutaraldehyde; sorbic acid; benzoic acid; salicylic acid; p-hydroxybenzoic acid esters; chloroacetamide; N-methylolchloroacetamide; Phenols such as p-chloro-m-cresol and o-phenylphenol; N-methylol; N, N'-dimethylolurea;benzylformal;4,4-dimethyl-1,3-oxazolidine;1,3,5-hexahydrotriazine; Quaternary ammonium compounds such as N-alkyl-N, N-dimethylbenzy
- formaldehyde releasing agent examples include N-formals such as tetramethylolacetylenediurea; N, N'-dimethylolurea; N-methylol; dimethyloldimethylhydantoin; N-methylolchloroacetamide; Reaction products of allantoin; Glycol formals, such as ethylene glycol formal; Butyldiglykolformal; Benzylformal.
- biocidal agents are OIT alone or OIT in combination with one or more biocides from the group BIT, N-butyl-BIT, N-methyl-BIT, IPBC, tebuconazole, DCOIT terbutryn, cyfluthrin, isoproturon triclosan and zinc pyrithione.
- OIT as the sole biocidic agent is preferred.
- biocidal active substances OIT and BIT are preferred.
- this further biocide may be contained together with the OIT as a mixture in the microparticles.
- microparticles containing only OIT are mixed with microparticles containing only the further biocide, and this mixture of microparticles is applied to the textile.
- microparticles containing the biocidal active substance may additionally contain other customary additives which are customary for the textile application and which are known to the person skilled in the art. These are e.g. Thickeners, defoamers, substances for adjusting the pH, fragrances, dispersing aids and coloring or discoloration-preventing substances, complexing agents and stabilizers such as UV stabilizers.
- the microparticles used for finishing textiles preferably do not comprise any harmful solvents.
- the preferred solvent used in the preparation is water.
- solvents are used in the preparation of the microparticles, these may be polar or nonpolar or mixtures containing polar and non-polar solvents.
- polar liquid solvent aliphatic alcohols having 1 to 4 carbon atoms, for.
- ethanol and isopropanol a glycol, for.
- a glycol for.
- the polar liquid solvent is especially water.
- aromatics, preferably xylene and toluene can serve as nonpolar liquid solvents. These may also be used alone or as a mixture of 2 or more such solvents.
- the microparticles are anchored on the textiles by means of a finish (for example polymer dispersions, amino resins, melamine-formaldehyde resins, paraffin emulsions, fluorocarbon emulsions, silicone emulsions).
- the finish is an impregnating liquid, which is applied to textile threads or textiles by spraying, dipping or coating. The finishing of the textiles with the microparticles can thus be carried out in one operation with the application of the finish.
- the attachment of reactive groups on the surface or a reactive anchoring of the microparticles with the textile fibers is not necessary here.
- microparticles can be physically bound to the fibers of the textiles by means of a polymer.
- the polymer coating is usually a coating of polymers such as polyacrylates, polyvinyl acetate, polyesters, polyvinyl alcohols, polyurethanes, and mixtures thereof.
- the polymer is preferably used as a dispersion during application.
- a chemical anchoring of the microparticles according to the invention with the surface of the textiles is carried out.
- the surface of the microparticles has reactive groups, such as amino, hydroxyl and methylol groups (CH 2 -OH), it is possible to formulate these with the aid of a suitable reactive binder, for example an isocyanate, in particular a protected or blocked one Isocyanates permanently anchored to the textile surface.
- a suitable reactive binder for example an isocyanate, in particular a protected or blocked one Isocyanates permanently anchored to the textile surface.
- the invention further relates to the use of the active ingredient 2-n-octyl-4-isothiazolin-3-one and optionally one or more other biocides containing microparticles based on an aminoplast resin for the protection of textiles against microorganism infestation.
- the term textile may also be a filter or fleece, preferably an air filter equipped with the microparticles in which the biocidal active substance is enclosed.
- the filter material is in this case equipped with the microparticles according to the invention to prevent the growth of fungi, algae and bacteria in the filter at least largely.
- the thus equipped filters are suitable for use in air conditioning systems, as well as in exhaust air and supply air systems.
- such equipped filters are suitable for use in ventilation systems or air conditioners in slaughterhouses, since the equipment of the filter material with the microparticles according to the invention makes it possible to wash out the filter without this thereby losing its antimicrobial activity.
- biocidal active ingredient is a mixture of OIT and BIT.
- OIT effectively prevents the infestation of the filter by algae and fungi and BIT the attack by bacteria.
- the biocidal active ingredient is preferably enclosed in finely dispersed, liquid or solid phase, more preferably in the preparation of the microparticles the biocidal active substance is introduced in an aqueous medium.
- the preparation of the preferably used melamine-formaldehyde microparticles comprises the use of melamine-formaldehyde precondensates which are water-soluble and from which melamine-formaldehyde-resin microparticles are prepared from the aqueous phase.
- the manufacturing process has several advantages, such as, in addition to inexpensive compared to other possible polymerization process starting materials and the environmentally friendly use of water as a preferred solvent.
- partial substitution of the solvent used in the process with water can be made by water-miscible organic solvents.
- microparticles according to the invention preference is given to starting from an aqueous suspension of the biocidal active substance or active substance mixture using water as solvent.
- the microparticles according to the invention are preferably prepared with stirring in an acidic medium.
- acidic medium serve inorganic and / or organic acids such as hydrochloric acid, phosphoric acid and citric acid.
- the microparticles can be prepared in conventional apparatus for condensation polymerizations. These include stirred tanks, stirred tank cascades, autoclaves, tube reactors and kneaders.
- the reaction is carried out, for example, in stirred tanks equipped with an armature, blade, impeller, dissolver or multistage pulse counterstirrer.
- apparatuses that allow the direct isolation of the product following the polymerization such as. B. paddle dryer.
- the resulting suspensions can be dried directly in evaporators, such as belt dryers, paddle dryers, spray dryers or fluid bed dryers. But you can also cut off by filtration or centrifugation, the majority of the water.
- melamine-formaldehyde resins As starting material for the preferably used melamine-formaldehyde resins, on the one hand, etherified melamine-formaldehyde condensates obtainable, preferably with low solubility free formaldehyde such as Quecodur DM 70 (available from THOR GmbH) used. Furthermore, the melamine-formaldehyde resin may also be prepared by polycondensation of melamine and formaldehyde in the presence of the biocidic agent by techniques known to those skilled in the art, such as by reaction between melamine and formaldehyde at a molar ratio of 1 to 6 parts of formaldehyde to one part of melamine.
- the reaction is preferably carried out in aqueous solution.
- concentration of the prepolymer in the aqueous solution can be varied over a wide range.
- the prepolymer is supplied or formed such that the prepolymer concentration is from about 1 to about 70 weight percent, preferably from about 5 to about 50 weight percent.
- the microparticles according to the invention may contain further substances which are generally known and customary depending on the intended use. These include on the one hand corresponding binders and film formers, such as polyacrylates, polystyrene or silicone resins, on the other hand, known auxiliaries, such as pigments; Fillers such as calcium carbonate, talc, kaolins, silicates, fumed silica and / or zeolites; Solvents; Thickeners such as polysaccharides and / or cellulose ethers; defoamers; plasticizers; Dispersants such as phosphates and / or acrylates; Emulsifiers such as fatty alcohol ethoxylates, EO / PO block polymers and / or sulfonates; Stabilizers such as UV stabilizers, dyes or discoloration-preventing substances.
- binders and film formers such as polyacrylates, polystyrene or silicone resins
- auxiliaries such as pigments
- the polycondensation of the aminoplast resin may be conducted anywhere within the range of about 20 to about 95 ° C, preferably between about 50 and 80 ° C.
- the reaction will generally be completed within a few hours, although the reaction at high temperature may be completed within a few minutes.
- microparticles Once the microparticles are formed, they can be stored as dispersions and used or filtered as dried particles. In any form, the particles are useful and effective in the controlled release of the biocidic agent.
- the preparation examples illustrate the preparation of microparticles in which the biocidal active ingredient is included.
- microparticles of melamine-formaldehyde were prepared in which the biocidal active ingredient 2-n-octyl-4-isothiazolin-3-one was included.
- Used substances Quantities [g] water 430.00 polyacrylate (Coatex BR 3, Dimed company) 1.50 Gum arabic 0.60 silicone defoamers (Aspumit AP, Thor GmbH) 0.30 OIT 60,00 Hydrochloric acid 1% 46.10 Melamine-formaldehyde resin (Quecodur DM 70, Thor GmbH) 85,00 623.50
- the water was initially charged with the melamine resin. In it were stirred in polyacrylate, gum arabic, silicone defoamer and 2-n-octyl-4-isothiazolin-3-one. The resulting mixture was heated to 90 ° C and added dropwise over 1 h hydrochloric acid to a pH of 4. Subsequently, the mixture was stirred for 2 h at the same temperature.
- the contained mixture contained the desired microparticles in which the biocidal active ingredient is included.
- Table 1 Results of the example and the comparative example for loss of active ingredient in the drying of textiles.
- Material of the textile pattern theoretically determined value [ppm] trapped OIT [ppm] dispersed OIT [ppm] polyester 1400 1205 18 polyacrylonitrile 2400 2032 44 cotton 2500 2085 761
- Example 1 The polyester samples prepared according to Example 1 and Comparative Example were examined for their fungi-inhibiting properties according to DIN 53931. The results are shown in Table 3.
- Table 3 Results of the Example and Comparative Example of the Fungal Inhibiting Effect of the Encapsulated OIT. material enclosed OIT [surface vegetation] Dispersed OIT [surface vegetation] Aspergillus niger, Orig. (0) 4.5 Aspergillus niger, 24h, wt. (0) 5.5 Chaetomium globosum, Orig. (0) 4.4 Chaetomium globosum, 24h, wt. (0) 4.5 Penicillium funiculosum, Orig. (0) 3.4 Penicillium funiculosum, 24h, wt.
- the trapped OIT textile samples show excellent antifungal properties. These antifungal properties are still present even after the washing of the textiles.
Abstract
Description
Die Erfindung betrifft ein mit zumindest einem bioziden Wirkstoff antimikrobiell ausgerüstetes Textil. Der biozide Wirkstoff ist in einem Harz auf Basis eines Aminoplasten eingeschlossen. Der eingeschlossene biozide Wirkstoff eignet sich als Textilhilfsmittel zur Ausrüstung von Textilien, wie zum Beispiel Zeltstoffen, Markisen, Persenninge, Duschvorhängen, Vliesen, Filtern, Teppichen und dergleichen.The invention relates to a textile antimicrobially finished with at least one biocidal active substance. The biocidal agent is enclosed in an aminoplast-based resin. The enclosed biocidal active ingredient is useful as a textile auxiliaries for finishing textiles such as tent fabrics, awnings, covers, shower curtains, nonwovens, filters, carpets and the like.
Die meisten Textilien enthalten mikrobiologisch abbaubares Material. Sie sind entweder vollständig oder teilweise aus mikrobiologisch abbaubaren Fasern hergestellt, beispielsweise aus Baumwolle, Hanf, Flachs, Leinen, Viskose, Tencel, Acetat, Seide, Wolle. Textilien aus synthetischen Fasern wie z.B. Polyester, Polyacrylnitril, Polyamid, Polypropylen, Nomex, Aramid werden mikrobiologisch angreifbar, wenn sie mit Ausrüstungsmitteln, wie z.B. Schlichten, Spulölen, Schmälzen, Weichmachern, Hydrophobierungsmitteln, Antistatika, und/oder Bindern, versehen werden oder während des Gebrauchs mikrobiologisch abbaubares Material aufnehmen, wie z.B. organische Substanzen aus der Umwelt oder Seifenrückstände. Durch den Befall der Textilien durch Pilze, Algen oder Bakterien können nicht nur die Optik sondern auch die Gebrauchseigenschaften der Textilien negativ verändert werden. Darüber hinaus können durch die Freisetzung von Stoffwechselprodukten unangenehme Geruchsbelästigungen oder eine Gesundheitsgefährdung verursacht werden.Most textiles contain microbiologically degradable material. They are either completely or partially made of microbiologically degradable fibers, for example cotton, hemp, flax, linen, viscose, tencel, acetate, silk, wool. Textiles of synthetic fibers, e.g. Polyester, polyacrylonitrile, polyamide, polypropylene, nomex, aramid become microbiologically vulnerable when treated with finishing agents such as e.g. Sizing, spun oils, lubricants, plasticizers, water repellents, antistatics, and / or binders, or to receive microbiologically degradable material during use, e.g. organic substances from the environment or soap residues. The infestation of textiles by fungi, algae or bacteria can not only negatively affect the appearance but also the functional properties of the textiles. In addition, unpleasant odor nuisance or a health hazard can be caused by the release of metabolic products.
Es ist daher erforderlich, Textilien mit Konservierungsmitteln, insbesondere mit Bioziden wie Bakteriziden, Fungiziden und/oder Algiziden auszurüsten, um einen Befall durch Mikroorganismen, z. B. durch Pilze, wie Schimmelpilze, sowie durch Bakterien, Cyanobakterien, Hefen und Algen zu verhindern oder zumindest zu minimieren.It is therefore necessary to equip textiles with preservatives, especially with biocides such as bactericides, fungicides and / or algicides, to prevent infestation by microorganisms, eg. As by fungi, such as mold, as well as by bacteria, cyanobacteria, yeasts and algae to prevent or at least minimize.
Bei der Ausrüstung des Textils mit Bioziden treten jedoch Schwierigkeiten auf, die sowohl den Ausrüstungsvorgang als solchen als auch durch die Ausrüstung entstehende Phänomene betreffen.However, when equipping the textile with biocides, difficulties arise concerning both the finishing process as such and equipment-related phenomena.
In der Textilindustrie werden hohe Ansprüche an die zur Ausrüstung von Textilen verwendeten Biozide gestellt. Die Textilien müssen beispielsweise nach dem Ausrüsten üblicherweise bei Temperaturen von 100 bis 130°C getrocknet und, um zusätzlich eine ausreichende Hydrophobie zu erreichen, anschließend bei Temperaturen bis 180°C behandelt werden. Dabei führt die hohe Abdampfrate der Biozide häufig zu hohen Wirkstoffverlusten. Insbesondere auf der Oberfläche synthetischer Fasern, wie zum Beispiel Polyester-, Polyamid- , Polypropylen oder Polyacrylnitrilfasern, sind Wirkstoffverluste von über 95 % nach dem Ausrüsten zu beobachten.In the textile industry, high demands are placed on the biocides used for finishing textiles. For example, after finishing, the textiles usually have to be dried at temperatures of from 100 to 130 ° C. and, in order to additionally achieve sufficient hydrophobicity, then be treated at temperatures up to 180 ° C. The high evaporation rate of the biocides often leads to high drug losses. In particular, on the surface of synthetic fibers, such as polyester, polyamide, polypropylene or polyacrylonitrile fibers, drug losses of over 95% are observed after equipping.
Der nach dem Ausrüsten auf dem Textil verbliebene Wirkstoff wird bedingt durch die große Oberfläche der Textilien und die geringe Schichtdicke der Ausrüstung im praktischen Gebrauch bei Wässerung des Textils, etwa bei der Beregnung, ausgewaschen. Hierdurch ist ein weiterer beachtlicher Wirkstoffverlust zu verzeichnen. Weiterhin kann auch der Einfluss von Licht zu einer Zersetzung der nach dem Ausrüsten verbliebenen bioziden Wirkstoffe führen.Due to the large surface area of the textiles and the small layer thickness of the equipment, the active substance remaining on the textile after finishing is washed out in practice during washing of the textile, for example during irrigation. This is another notable loss of active ingredient. Furthermore, the influence of light can also lead to a decomposition of the biocidal active substances remaining after the finishing.
Nach erfolgter Ausrüstung sind durch die Wechselwirkung bestimmter Schwermetallionen, wie zum Beispiel Eisen mit bestimmten Bioziden, wie zum Beispiel Zinkpyrithion, Verfärbungen der Textilien zu beobachten.After equipment has been used, the interaction of certain heavy metal ions, such as iron with certain biocides, such as zinc pyrithione, causes discoloration of the textiles.
Es existieren wirksame Biozide, die eine geringe Abdampfrate aufweisen und/oder auch durch Bewässerung zum großen Teil auf dem Textil verbleiben. Generell sind jedoch in dieser Hinsicht an sich zufrieden stellende Biozide aufgrund toxischer Effekte weniger für die Ausrüstung von Textilien geeignet. Zu nennen sind hier Chlorothalonil und insbesondere das als cancerogen eingestufte Carbendazim. Auch Hautirritationen sind als nachteilig zu nennen. Bei der Konfektion (z.B. Zuschneiden, Nähen etc.) der antimikrobiell ausgerüsteten Textilien tritt ein Hautkontakt auch bei Textilien auf, die generell während des vorgesehenen Gebrauchs nicht mit dem menschlichen Körper in Berührung kommen.There are effective biocides, which have a low evaporation rate and / or remain largely by irrigation on the textile. In general, however, in this respect satisfactory biocides are less suitable for finishing textiles because of their toxic effects. These include chlorothalonil and in particular the carbendazim classified as carcinogenic. Also skin irritations are to be called as disadvantageous. In the manufacture (e.g., trimming, sewing, etc.) of the antimicrobial textiles, skin contact also occurs with textiles that generally do not come in contact with the human body during intended use.
Bedingt durch das oben beschriebene Verflüchtigen der Wirkstoffe ist es häufig erforderlich, teilweise teure Wirkstoffe mit hohen minimalen Hemmkonzentrationswerten (MHK-Werten) in hoher Konzentration einzusetzen, um trotz der Wirkstoffverluste bei der Trocknung, Beregnung oder Bewässerung die gewünschte, den praktischen Anforderungen genügende antimikrobielle Wirkung zu erzielen, was erhebliche Kosten zur Folge hat. Weiterhin belasten die hohen Einsatzkonzentrationen und die hohen Verluste an biozidem Wirkstoff während Herstellung und Gebrauch dieser Produkte die Umwelt.Due to the above-described volatilization of the active ingredients, it is often necessary to use partially expensive active ingredients with high minimum inhibitory concentration values (MIC values) in high concentration in order, in spite of the losses of active ingredient during the drying, Irrigation or irrigation to achieve the desired, practical requirements sufficient antimicrobial effect, resulting in significant costs. Furthermore, the high use concentrations and the high losses of biocidal active ingredient during production and use of these products pollute the environment.
Zu erwähnen ist schließlich der negative Effekt vieler Biozide auf die wasserabweisende Wirkung der Imprägnierung oder Beschichtung. Die hierdurch bedingte schnellere Benetzung mit Wasser führt zu einer beschleunigten Freisetzung der Wirkstoffe. Im Allgemeinen fällt die Wirkstoffkonzentration nach nur wenigen Beregnungszyklen unter die minimale Hemmkonzentration (MHK) der Biozide. Eine Langzeitwirkung ist daher nicht mehr gegeben.Finally, the negative effect of many biocides on the water-repellent effect of the impregnation or coating should be mentioned. The resulting faster wetting with water leads to an accelerated release of the active ingredients. In general, the drug concentration falls below the minimum inhibitory concentration (MIC) of the biocides after only a few irrigation cycles. A long-term effect is therefore no longer present.
Der Erfindung liegt daher die Aufgabe zugrunde, ein antimikrobiell ausgerüstetes Textil zur Verfügung zu stellen, welches die vorstehend aufgeführten Nachteile weitgehend vermeidet und insbesondere das Entweichen des bioziden Wirkstoffes während des Ausrüstens minimiert. So sollen die Umweltbelastung und die Kosten der Ausrüstung des Textils zur Bekämpfung schädlicher Mikroorganismen gesenkt und die Abdampfrate des bioziden Wirkstoffes aus dem ausgerüsteten Textil vermindert werden. Die antimikrobielle Wirkung des zur Ausrüstung verwendeten Mikrobizids soll über einen möglichst langen Zeitraum gewährleistet bleiben.The invention is therefore based on the object of providing an antimicrobially finished textile which largely avoids the disadvantages listed above and, in particular, minimizes the escape of the biocidal active substance during finishing. The aim is to reduce the environmental impact and the cost of the equipment of the textile to combat harmful microorganisms and reduce the evaporation rate of the biocidal active ingredient from the finished textile. The antimicrobial effect of the microbicide used for the equipment should be guaranteed for as long as possible.
Diese Aufgabe wird gelöst, indem ein Textil, welches mit einem bioziden Wirkstoff ausgerüstet ist, bereitgestellt wird, welches als bioziden Wirkstoff 2-n-Octyl-4-isothiazolin-3-on (OIT) sowie darüber hinaus gegebenenfalls ein oder mehrere andere Biozide enthält, wobei der biozide Wirkstoff in Mikropartikeln aus einem Aminoplast-Harz, vorzugsweise aus einem Melamin-Formaldehyd-Harz, eingeschlossen ist.This object is achieved by providing a textile which is provided with a biocidal active substance, which contains 2-n-octyl-4-isothiazolin-3-one (OIT) as biocidal active substance and furthermore optionally one or more other biocides in which the biocidal active ingredient is enclosed in microparticles of an aminoplast resin, preferably of a melamine-formaldehyde resin.
Der Begriff "biozider Wirkstoff' bezeichnet im Zusammenhang mit der vorliegenden Erfindung die Substanz oder das Substanzgemisch, das den der Erfindung zugrunde liegenden bioziden Effekt aufweist. In dem bioziden Wirkstoff ist in jedem Fall OIT enthalten, neben gegebenenfalls weiterem Wirkstoff, wie dies nachstehend genauer definiert wird.In the context of the present invention, the term "biocidal active substance" refers to the substance or mixture of substances which has the biocidal effect of the invention The biocidal active ingredient in each case contains OIT, in addition to optionally further active ingredient, as defined in more detail below becomes.
In einer Ausführungsform der vorliegenden Erfindung enthalten die Mikropartikel als bioziden Wirkstoff OIT sowie zusätzlich ein oder mehrere andere Biozide. Dabei kann das Verhältnis von OIT zu dem oder den anderen Bioziden grundsätzlich in weiten Grenzen schwanken und variiert werden, beispielsweise im Bereich von 100:1 bis 1:100, vorzugsweise 50:1 bis 1:50. Gemäß dieser Ausführungsform der Erfindung liegt das OIT üblicherweise in Mengen von 10 bis 95 Gew.-%, insbesondere von 20 bis 80 Gew.-%, und das oder die anderen Biozide in Mengen 5 bis 90 Gew.-%, insbesondere von 20 bis 80 Gew.-%, jeweils bezogen auf die gesamte Menge an enthaltenem biozidem Wirkstoff vor.In one embodiment of the present invention, the microparticles contain OIT as biocidal active ingredient and additionally one or more other biocides. In principle, the ratio of OIT to the other biocide (s) can, in principle, vary and be varied within wide limits, for example in the range from 100: 1 to 1: 100, preferably 50: 1 to 1:50. According to this embodiment of the invention, the OIT is usually present in amounts of from 10 to 95% by weight, in particular from 20 to 80% by weight, and the other biocides in amounts of from 5 to 90% by weight, in particular from 20 to 80 wt .-%, in each case based on the total amount of contained biocidal active ingredient.
In einer weiteren Ausführungsform besteht der in die Mikropartikel eingeschlossene biozide Wirkstoff überwiegend aus OIT. Dies bedeutet, dass der eingeschlossene biozide Wirkstoff als Hauptbestandteil OIT, vorzugsweise in einer Menge von gleich oder größer 50 Gew.-% OIT, mehr bevorzugt in einer Menge von gleich oder größer 70 Gew.-%, insbesondere in einer Menge von gleich oder größer 90 Gew.-%, insbesondere in einer Menge von gleich oder größer 95 Gew.-% OIT, bezogen auf die Gesamtmasse an biozidem Wirkstoff, enthält. Daneben kann mindestens ein weiteres Biozid vorhanden sein.In another embodiment, the biocidal active ingredient included in the microparticles consists predominantly of OIT. This means that the entrapped biocidal active ingredient as the main component OIT, preferably in an amount of equal to or greater than 50 wt .-% OIT, more preferably in an amount of equal to or greater than 70 wt .-%, in particular in an amount equal to or greater 90 wt .-%, in particular in an amount of equal to or greater than 95 wt .-% OIT, based on the total mass of biocidal active ingredient. In addition, at least one other biocide may be present.
In einer weiteren Ausführungsform der Erfindung besteht der in die Mikropartikel eingeschlossene biozide Wirkstoff im Wesentlichen aus OIT, d.h., dass neben OIT wohl noch ein oder auch mehrere andere Biozide enthalten sein können, diese aber in einer solchen Menge vorliegen, in der kein Beitrag des jeweiligen von OIT verschiedenen Biozids zum Gesamteffekt der entstehenden Mischung vorliegt. Wenn also die biozide Wirkung eines bioziden Wirkstoffs (Biozid-Gemisch), das neben OIT als wesentlichen Bestandteil noch ein oder mehrere weitere Biozide in untergeordneter bzw. geringfügiger Konzentration aufweist, nicht verändert ist gegenüber dem Einsatz von OIT alleine als einzigem Biozid, wird dieses im Zusammenhang mit der vorliegenden Erfindung als "im Wesentlichen bestehend" bezeichnet.In a further embodiment of the invention, the biocidal active ingredient enclosed in the microparticles consists essentially of OIT, ie, in addition to OIT one or more other biocides may still be present, but these are present in an amount in which no contribution of the respective OIT different biocides to the overall effect of the resulting mixture is present. Thus, if the biocidal activity of a biocidal active substance (biocide mixture), which apart from OIT has one or more further biocides in minor or minor concentration, is not changed compared to the use of OIT alone as sole biocide, this is In connection with the present invention referred to as "substantially consisting".
In einer weiteren Ausführungsform kann der biozide Wirkstoff aus OIT als einzigem bioziden Wirkstoff bestehen, also einem Wirkstoffgehalt von 100% OIT. In einem solchen Fall ist es lediglich möglich, dass ein oder mehrere weitere Bestandteile ohne eine biozide Wirkung vorhanden sind.In another embodiment, the biocidal active ingredient may consist of OIT as the only biocidal active ingredient, ie an active ingredient content of 100% OIT. In such a case, it is only possible that one or more other ingredients are present without a biocidal effect.
Im Sinne der Erfindung betrifft der Begriff Textil Fasern für den textilen Einsatz, textile Halb- und Fertigfabrikate, wie Fäden, Garne, Zwirne, Gewebe, Gestricke, Web/Maschenware, Vliese, und dgl. sowie textile Fertigwaren wie beispielsweise Kleidung. Vorzugsweise sind unter dem Begriff Textil textile Einheiten oder Untereinheiten von Textilien, wie zum Beispiel Zeltstoffe, Markisen, Sonnen- und Regenschirme, Persenninge, Duschvorhänge, Vliese, Filter, Teppiche und dergleichen zu verstehen.For the purposes of the invention, the term textile fibers for textile use, textile semi-finished and finished, such as threads, yarns, threads, fabrics, knits, woven / knitted fabric, nonwovens, and the like. As well as textile finished goods such as clothing. Preferably, the term textile textile units or subunits of textiles, such as tent fabrics, awnings, umbrellas and sunshades, covers, shower curtains, nonwovens, filters, carpets and the like to understand.
Unter dem Begriff Aminoplast-Harze sind im Sinne der Erfindung Polykondensationsprodukte aus Carbonyl-Verbindungen, insbesondere aus Formaldehyd und NH-Gruppen enthaltenden Verbindungen, wie zum Beispiel Harnstoff (Harnstoffharze), Melamin (Melamin-Harze), Urethane (Urethanharze), Cyan- und Dicyanamid (Cyan- beziehungsweise Dicyanamidharze), aromatischen Aminen (Anilin-Harze) und Sulfonamiden (Sulfonamid-Harze) zu verstehen, siehe hierzu
Die vorstehend genannten Harnstoffharze sind zu den Aminoplasten gehörende härtbare Kondensationsprodukte aus Harnstoffen und Aldehyden, insbesondere umfassen diese Formaldehyd. Zu ihrer Herstellung werden Harnstoff oder substituierte Harnstoffe mit Formaldehyd in molarem Überschuss unter meist alkalischen Bedingungen umgesetzt. Es entstehen Hydroxymethyl-Gruppen-haltige Oligomere, die unter Vernetzung gehärtet werden. Anstelle von Formaldehyd können auch andere Aldehyde beispielsweise Acetaldehyd oder Glyoxal eingesetzt werden. Auch Kondensate auf der Basis modifizierter Harnstoffe sind im Rahmen der Erfindung bei der Herstellung des Mikropartikelmaterials verwendbare Ausgangsstoffe.The urea resins mentioned above are hardenable condensation products of ureas and aldehydes belonging to the aminoplasts, in particular these include formaldehyde. For their preparation, urea or substituted ureas are reacted with formaldehyde in molar excess under mostly alkaline conditions. The result is hydroxymethyl group-containing oligomers, which are cured with crosslinking. Instead of formaldehyde, it is also possible to use other aldehydes, for example acetaldehyde or glyoxal. Condensates based on modified ureas are also starting materials which can be used in the preparation of the microparticle material in the context of the invention.
Unter dem Begriff Melamin-Harze sind Aminoplast-Harze zu verstehen, bei denen Melamin unter geeigneten Bedingungen mit Carbonylverbindungen wie Aldehyden und Ketonen, zum Beispiel Formaldehyd, Acetaldehyd oder Glyoxal, polykondensiert worden ist. Zu ihrer Herstellung wird im allgemeinen Melamin mit der Carbonylverbindung in molarem Überschuß umgesetzt. Von besonderem Interesse sind in diesem Zusammenhang die Polykondensationsprodukte von Melamin mit Formaldehyd (Melamin-Formaldehyd-Harze) oder auch mit Harnstoff beziehungsweise Phenol modifizierte Melamin-Formaldehyd-Harze (Melamin-Harnstoff-Formaldehyd-Harze, Melamin-Phenol-Formaldehyd-Harze).The term melamine resins is to be understood as meaning aminoplast resins in which melamine has been polycondensed under suitable conditions with carbonyl compounds such as aldehydes and ketones, for example formaldehyde, acetaldehyde or glyoxal. For their preparation, melamine is generally reacted with the carbonyl compound in molar excess. Of particular interest in this context are the polycondensation products of melamine with formaldehyde (melamine-formaldehyde resins) or with urea or phenol-modified melamine-formaldehyde resins (melamine-urea-formaldehyde resins, melamine-phenol-formaldehyde resins).
Die Mikropartikel, die den bioziden Wirkstoff eingeschlossen enthalten, können auch aus zwei oder mehreren der vorgenannten Aminoplast-Harze gebildet werden. Bei der Auswahl des Mikropartikelmaterials ist insbesondere darauf zu achten, dass es bei der Herstellung nicht zu einer Zerstörung beziehungsweise Inhibierung des bioziden Wirkstoffes kommt.The microparticles containing the biocidal active ingredient may also be formed from two or more of the aforementioned aminoplast resins. When selecting the microparticle material, particular care must be taken that there is no destruction or inhibition of the biocidal active substance during production.
Durch den Einschluss des bioziden Wirkstoffes in den Mikropartikeln wird dieser überraschender Weise bei der Herstellung des Textils während der Trocknung und Kondensation trotz der hierbei zur Anwendung kommenden hohen Temperaturen nicht oder nur in sehr geringem Umfang verflüchtigt beziehungsweise freigesetzt, bleibt dabei gleichzeitig biozid wirksam; und er verbleibt vielmehr auf dem Textil, so dass er in entsprechend geringen Konzentrationen eingesetzt werden kann. Im praktischen Gebrauch wird der biozide Wirkstoff nur verlangsamt (retardierend) freigesetzt. Dabei hat sich in vorteilhafter Weise gezeigt, dass der in den Mikropartikeln eingeschlossene biozide Wirkstoff während der Beregnung beziehungsweise Wässerung der damit ausgerüsteten Textilien nicht, wie es üblicher Weise zu erwarten gewesen wäre, in hohem Maße ausgewaschen wird. Es lassen sich so erfindungsgemäß einerseits geringere Wirkstoffmengen zur Ausrüstung einsetzen, andererseits erheblich längere Wirkdauern erzielen.Due to the inclusion of the biocidal active substance in the microparticles, this surprising manner is not or only to a very small extent volatilized or released in the production of the textile during drying and condensation, despite the high temperatures used, while at the same time remaining biocidally active; and he rather remains on the textile, so that it can be used in correspondingly low concentrations. In practical use, the biocidal active ingredient is released only slowed down (retarding). It has been shown in an advantageous manner that the biocidal active ingredient enclosed in the microparticles is not washed out to a great extent during the irrigation or washing of the textiles equipped therewith, as would have been usual to be expected. On the one hand, according to the invention, on the one hand, smaller amounts of active ingredient can be used for the equipment, and on the other hand, it is possible to achieve considerably longer effective times
Gemäß der vorliegenden Erfindung betrifft der Begriff Mikropartikel jede Art von Partikeln, die eine Wandstruktur und mindestens einen durch die Wandstruktur gebildeten Hohlraum umfassen. Die Wandstruktur enthält hierbei einen oder mehrere Aminoplast-Harze, vorzugsweise einen. Die von der Wandstruktur gebildeten Hohlräume können geschlossen oder auch offen ausgebildet sein und enthalten den bioziden Wirkstoff und gegebenenfalls weitere verschiedene Hilfsstoffe. Geschlossene Hohlräume können zum Beispiel in Form von Kapselstrukturen oder Zellstrukturen vorliegen, offene Hohlräume in Form von Poren, Kanälen und dergleichen. Im Sinne der Erfindung kann der Begriff Mikropartikel ebenfalls eine Matrix aus einem Aminoplast-Harz bedeuten, wobei der biozide Wirkstoff in der Matrix eingeschlossen, beziehungsweise von dieser umhüllt ist. Auch kann der Begriff Mikropartikel so genannte Mikrokapseln betreffen, in deren Innern der biozide Wirkstoff verkapselt eingeschlossen ist.According to the present invention, the term microparticles refers to any type of particle comprising a wall structure and at least one cavity formed by the wall structure. The wall structure in this case contains one or more aminoplast resins, preferably one. The cavities formed by the wall structure may be closed or open and contain the biocidal active ingredient and optionally other various excipients. Closed cavities may, for example, be in the form of capsule structures or cell structures, open cavities in the form of pores, channels and the like. For the purposes of the invention, the term microparticles may likewise mean a matrix of an aminoplast resin, wherein the biocidal active ingredient is enclosed in the matrix or enveloped by it. Also, the term microparticles may refer to so-called microcapsules, in the interior of which the biocidal active ingredient is encapsulated encapsulated.
Vorzugsweise haben die Mikropartikel eine sphärische Form. Diese Form weist den Vorteil eines hohen Volumens bei geringer Oberfläche auf, wodurch auftreffendes Wasser eine geringe Benetzungsfläche hat. Hierdurch wird durch Beregnung der mit den Mikropartikeln ausgerüsteten Textilien lediglich ein geringer Teils des bioziden Wirkstoffs freigesetzt. So wird verhindert, dass ein Großteil des bioziden Wirkstoffes bereits nach wenigen Regengüssen aus den Textilien, wie Zeltstoffen, Markisen, Persenningen, Duschvorhängen, und dergleichen ausgewaschen wird. Der Langzeiteffekt der antimikrobiellen Ausrüstung der Textilien wird erheblich verbessert. Es ergibt sich ein dauerhafter Schutz der Textilien gegen mikrobiellen Befall.Preferably, the microparticles have a spherical shape. This shape has the advantage of high volume, low surface area, whereby impinging water has a low wetting area. As a result, sprinkling the textiles finished with the microparticles releases only a small portion of the biocidal active substance. This prevents a large proportion of the biocidal active substance from being washed out of the textiles, such as tent fabrics, awnings, tarpaulins, shower curtains, and the like, after a few downpours. The long-term effect of the antimicrobial finish of textiles is significantly improved. This results in a durable protection of the textiles against microbial attack.
Der mittlere Durchmesser der zur Ausrüstung von Textilien verwendbaren Mikropartikel liegt üblicher Weise im Bereich von etwa 0,5 bis etwa 100 µm, der bevorzugte mittlere Durchmesser im Bereich von etwa 1 bis etwa 10 µm. Die Größe der Mikropartikel lässt sich beispielsweise unter dem Mikroskop unter Verwendung einer Mikrometerskala bestimmen.
Die Textile werden derart ausgerüstet, dass das antimikrobiell ausgerüstete Textil im allgemeinen eine Menge an biozidem Wirkstoff bezogen auf das Gesamtgewicht des Textils von 0,0001 Gew.-% bis 0,5 Gew.-%, bevorzugt von 0,01 Gew.-% bis 0,2 Gew.-%, besonders bevorzugt von 0,05 Gew.-% bis 0,15 Gew.-%, umfasst.The average diameter of microparticles useful for finishing textiles is usually in the range of about 0.5 to about 100 microns, the preferred average diameter is in the range of about 1 to about 10 microns. The size of the microparticles can be determined, for example, under a microscope using a micrometer scale.
The textiles are finished in such a way that the antimicrobially finished textile generally has an amount of biocidal active substance, based on the total weight of the textile, of 0.0001% by weight to 0.5% by weight, preferably of 0.01% by weight. to 0.2% by weight, more preferably from 0.05% to 0.15% by weight.
Da sich immer nur eine geringe Konzentration des bioziden Wirkstoffes auf der Oberfläche der Mikropartikel und damit auf der Oberfläche der Textile befindet, werden die Produkteigenschaften des Textils, wie zum Beispiel deren Hydrophobie oder Oleophobie nicht negativ beeinträchtigt.Since there is always only a small concentration of the biocidal active ingredient on the surface of the microparticles and thus on the surface of the textile, the product properties of the textile, such as their hydrophobicity or oleophobicity are not adversely affected.
Weiterhin kann durch die langsame Freisetzung des bioziden Wirkstoffes bereits mit geringeren Einsatzkonzentrationen ein Langzeiteffekt erreicht werden. Dieses birgt sowohl ökologische als auch ökonomische Vorteile, da der biozide Wirkstoff während der Verarbeitung der Textilien nur zu einem geringen Teil verloren geht und hierdurch in wesentlich geringeren Mengen eingesetzt werden kann.Furthermore, a long-term effect can be achieved even with lower use concentrations due to the slow release of the biocidal active substance. This has both ecological and economic advantages, since the biocidal active ingredient is lost only to a small extent during the processing of the textiles and can thus be used in much smaller quantities.
Der Einschluss des bioziden Wirkstoffes in die Mikropartikel hat nicht nur den Vorteil der retardierten Freisetzung des bioziden Wirkstoffes, vielmehr hat die Abschirmung des bioziden Wirkstoffes durch die Partikelwand zur Folge, dass dieser hierdurch eine erhöhte Stabilität gegenüber UV-Strahlung, erhöhten Temperaturen, Schwermetallionen und pH-Werten aufweist. So ist beispielsweise die Wirkdauer des bioziden Wirkstoffes, bedingt durch eine geringere Zersetzungsrate, erheblich verlängert.The inclusion of the biocidal agent in the microparticles not only has the advantage of sustained release of the biocidal agent, but the shielding of the biocidal agent through the particle wall has the consequence that this thereby increased stability to UV radiation, elevated temperatures, heavy metal ions and pH Values. For example, the duration of action of the biocidal active ingredient, due to a lower rate of decomposition, is considerably prolonged.
Biozide kommen in vielen Bereichen zum Einsatz und werden zur Bekämpfung von Bakterien, Pilzen oder Algen verwendet. Es ist seit langem bekannt, in solchen Zusammensetzungen insbesondere Verbindungen aus der Stoffklasse der 3-Isothiazolin-3-one (die auch als 3-Isothiazolone bezeichnet werden) zu verwenden. In dieser Stoffklasse finden sich sehr wirksame Biozide mit teilweise unterschiedlichem Wirkprofil. Oft werden Kombinationen aus verschiedenen 3-Isothiazolin-3-onen, oder auch aus einem oder mehreren 3-Isothaziolin-3-onen mit anderen bekannten bioziden Wirkstoffen benutzt (siehe hierzu unter anderem.
In einem Melamin-Formaldehyd-Harz eingeschlossene biozide Wirkstoffe zur Applikation in Beschichtungsmassen, insbesondere in Fassadenputzen, sind aus der
Durch den Einschluss des bioziden Wirkstoffes in die Mikropartikel auf Basis des Aminoplast-Harzes wird dessen Freisetzung beim Trocknen oder der thermischen Nachbehandlung während der textilen Ausrüstung, wie erwähnt, weitgehend verhindert. So ist das antimikrobiell ausgerüstete Textil dadurch gekennzeichnet, dass während des Trocknens oder der thermischen Nachbehandlung weniger als etwa 70 %, bevorzugt weniger als etwa 50 %, besonders bevorzugt weniger als 10 % des bioziden Wirkstoffes entweichen. Dadurch reduziert sich nicht nur der Verlust an biozidem Wirkstoff, sondern gleichzeitig der Eintrag in die Abluft/Umwelt. Trotz des Einschlusses des bioziden Wirkstoffes in die Mikropartikel bleibt die biozide Aktivität des bioziden Wirkstoffes erhalten.As a result of the inclusion of the biocidal active substance in the microparticles based on the aminoplast resin, its release during drying or thermal aftertreatment during the textile finish, as mentioned, is largely prevented. Thus, the antimicrobial textile is characterized in that less than about 70%, preferably less than about 50%, more preferably less than 10% of the biocidal active ingredient escape during drying or thermal aftertreatment. This not only reduces the loss of biocidal active substance, but also the entry into the exhaust air / environment. Despite the inclusion of the biocidal agent in the microparticles, the biocidal activity of the biocidic agent is maintained.
Die erfindungsgemäßen Mikropartikel weisen dann einen guten erfindungsgemäßen Effekt auf, wenn diese 5 bis 99,99 Gew.-% des Aminoplast-Harzes und 0,01 bis 95 Gew.-% des bioziden Wirkstoffes, bevorzugt 15 bis 60 Gew.-% des Aminoplast-Harzes und 85 bis 40 Gew.-% des bioziden Wirkstoffes bezogen auf das Gesamtgewicht des Aminoplast-Harzes und des bioziden Wirkstoffes umfassen.The microparticles according to the invention then have a good effect according to the invention when they contain from 5 to 99.99% by weight of the aminoplast resin and from 0.01 to 95% by weight of the biocidal active substance, preferably from 15 to 60% by weight of the aminoplast Resin and 85 to 40% by weight of the biocidic agent based on the total weight of the aminoplast resin and the biocidic agent.
Das bekannte 2-n-Octyl-4-isothiazolin-3-on (OIT) weist antimikrobielle Eigenschaften auf, die an sich für die Ausrüstung von Textilien erwünscht sind. Zu nennen sind hier die fungizide und algizide Wirkung, die sich zu einem für die textile Anwendung vorteilhaften Wirkstoffprofil ergänzen. Das 1,2-Benzoisothiazolin-3-on (BIT), das ausgesprochen gute bakterizide Eigenschaften aufweist, ist aufgrund seiner hohen Wasserlöslichkeit und hohen Flüchtigkeit bei höheren Temperaturen ebenfalls nur bedingt für textile Anwendungen geeignet.The known 2-n-octyl-4-isothiazolin-3-one (OIT) has antimicrobial properties which are desirable for the finishing of textiles. To mention here are the fungicidal and algicidal effect, which complement each other to an advantageous for textile application drug profile. The 1,2-benzoisothiazolin-3-one (BIT), the very good has bactericidal properties, due to its high water solubility and high volatility at higher temperatures also only partially suitable for textile applications.
Die Verwendung der erfindungsgemäßen Mikropartikel ist aufgrund des breiten Wirkspektrums von OIT besonders geeignet für die Ausrüstung von Textilien, die im Outdoor-Bereich eingesetzt werden, da es sich bei OIT um ein Biozid mit fungizider und algizider Wirkung handelt. Es enthält weder Halogen- noch Schwermetallverbindungen, ist nicht persistent oder akkumulierbar, ist nicht als CMR-Stoff klassifiziert und verfügt über ein günstiges Human- und Ökotoxizitätsprofil. Es ist somit generell von seinen Eigenschaften her bestens für die Ausrüstung von Textilen geeignet. So ist dessen Verwendung sowohl vom ökologischen und wirtschaftlichen Gesichtspunkt aus auch aufgrund seines vorteilhaften Wirkungsspektrum von Vorteil.The use of the microparticles according to the invention is particularly suitable for the finishing of textiles which are used in the outdoor area, because OIT is a biocide with fungicidal and algicidal action, because of the broad spectrum of activity of OIT. It contains no halogen or heavy metal compounds, is not persistent or accumulable, is not classified as a CMR substance and has a favorable human and ecotoxicological profile. It is therefore generally suitable for the finishing of textiles in terms of its properties. Thus, its use from both the ecological and economic point of view also advantageous because of its advantageous spectrum of action.
Zum Einschluss in die Mikropartikel können neben OIT zusätzlich noch ein oder mehrere andere Biozide mitverwendet werden, die in Abhängigkeit des Anwendungsgebietes ausgewählt werden können. Spezielle Beispiele für solche zusätzlichen Bioziden sind nachfolgend angegeben:For inclusion in the microparticles, in addition to OIT, one or more other biocides can additionally be used, which can be selected depending on the field of application. Specific examples of such additional biocides are given below:
Benzylalkohol; 2,4-Dichlorbenzylalkohol; 2-Phenoxyethanol; 2-Phenoxyethanolhemiformal, Phenylethylalkohol; 5-Brom-5-nitro-1,3-dioxan; Bronopol; Formaldehyd und Formaldehyd-Depotstoffe; Dimethyloldimethylhydantoin; Glyoxal; Glutardialdehyd; Sorbinsäure; Benzoesäure; Salicylsäure; p-Hydroxybenzoesäureester; Chloracetamid; N-Methylolchloracetamid; Phenole, wie p-Chlor-m-kresol und o-Phenylphenol; N-Methylolharnstoff; N,N'-Dimethylolharnstoff; Benzylformal; 4,4-Dimethyl-1,3-oxazolidin; 1,3,5-Hexahydrotriazinderivate; Quartäre Ammoniumverbindungen, wie N-Alkyl-N,N-dimethyl-benzylammoniumchlorid und Di-n-decyldimethylammoniumchlorid; Cetylpyridiniumchlorid; Diguanidin; Polybiguanid; Chlorhexidin; 1,2-Dibrom-2,4-dicyanobutan; 3,5-Dichlor-4-hydroxybenzaldehyd; Ethylenglykolhemiformal; Tetra-(hydroxymethyl)-phosphoniumsalze; Dichlorophen; 2,2-Dibrom-3-nitrilopropionsäureamid; 3-Iod-2-propinyl-N-butylcarbamat; Methyl-N-benzimidazol-2-ylcarbamat; 2,2'-Dithio-dibenzoesäure-di-N-methylamid; 2-Thiocyanomethylthiobenzthiazol; C-Formale wie 2-Hydroxymethyl-2-nitro-1,3-propandiol und 2-Brom-2-nitropropan-1,3-diol; Methylenbisthiocyanat; Umsetzungsprodukte von Allantoin; 2-Methyl-isothiazolin-3-on; N-Alkyl-1,2-benzisothiazolin-3-one mit 1 bis 8 C-Atomen im Alkylrest; N-Methyl-1,2-benzisothiazolin-3-on; N-Butyl-1,2-benzisothiazolin-3-on; 4,5-Dichlor-2-n-Octylisothiazolin-3-on; 4,5-Trimethylen-2-methylisothiazolin-3-on; 1,2-Benzisothiazolin-3-on (BIT); Zinkpyrithion; Chlorothalonin; Propioconazol; Tebuconazol; TCMTB; IPBC, Terbutryn, Cyfluthrin, Isoproturon Triclosan.benzyl alcohol; 2,4-dichlorobenzyl; 2-phenoxyethanol; 2-phenoxyethanolhemiformal, phenylethyl alcohol; 5-bromo-5-nitro-1,3-dioxane; bronopol; Formaldehyde and formaldehyde depot substances; dimethyloldimethylhydantoin; glyoxal; glutaraldehyde; sorbic acid; benzoic acid; salicylic acid; p-hydroxybenzoic acid esters; chloroacetamide; N-methylolchloroacetamide; Phenols such as p-chloro-m-cresol and o-phenylphenol; N-methylol; N, N'-dimethylolurea;benzylformal;4,4-dimethyl-1,3-oxazolidine;1,3,5-hexahydrotriazine; Quaternary ammonium compounds such as N-alkyl-N, N-dimethylbenzylammonium chloride and di-n-decyldimethylammonium chloride; cetylpyridinium chloride; diguanidine; polybiguanide; chlorhexidine; 1,2-dibromo-2,4-dicyanobutane; 3,5-dichloro-4-hydroxybenzaldehyde; Ethylenglykolhemiformal; Tetra (hydroxymethyl) phosphonium salts; dichlorophen; 2,2-nitrilopropionsäureamid-dibromo-3; 3-iodo-2-propynyl-N-butylcarbamate; Methyl-N-benzimidazol-2-ylcarbamate; 2,2'-dithio-dibenzoic-di-N-methyl;2-thiocyanomethylthiobenzothiazole; C-formals such as 2-hydroxymethyl-2-nitro-1,3-propanediol and 2-bromo-2-nitropropane-1,3-diol; methylene bis; Reaction products of allantoin; 2-methyl-isothiazolin-3-one; N-alkyl-1,2-benzisothiazolin-3-ones with 1 to 8 C atoms in the alkyl radical; N-methyl-1,2-benzisothiazolin-3-one; N-butyl-1,2-benzisothiazolin-3-one; 4,5-dichloro-2-n-octylisothiazolin-3-one; 4,5-trimethylene-2-methylisothiazolin-3-one; 1,2-benzisothiazolin-3-one (BIT); zinc pyrithione; Chlorothalonin; Propioconazol; tebuconazole; TCMTB; IPBC, terbutryn, cyfluthrin, isoproturon triclosan.
Beispiele für den Formaldehyd-Depotstoff sind N-Formale, wie Tetramethylolacetylendiharnstoff; N,N'-Dimethylolharnstoff; N-Methylolharnstoff; Dimethyloldimethylhydantoin; N-Methylolchloracetamid; Umsetzungsprodukte von Allantoin; Glykolformale, wie Ethylenglykolformal; Butyldiglykolformal; Benzylformal.Examples of the formaldehyde releasing agent are N-formals such as tetramethylolacetylenediurea; N, N'-dimethylolurea; N-methylol; dimethyloldimethylhydantoin; N-methylolchloroacetamide; Reaction products of allantoin; Glycol formals, such as ethylene glycol formal; Butyldiglykolformal; Benzylformal.
Gemäß der Erfindung sind bevorzugte biozide Wirkstoffe OIT alleine oder OIT in Kombination mit einem oder mehreren Bioziden aus der Gruppe BIT, N-Butyl-BIT, N-Methyl-BIT, IPBC, Tebuconazol, DCOIT Terbutryn, Cyfluthrin, Isoproturon Triclosan und Zinkpyrithion.According to the invention, preferred biocidal agents are OIT alone or OIT in combination with one or more biocides from the group BIT, N-butyl-BIT, N-methyl-BIT, IPBC, tebuconazole, DCOIT terbutryn, cyfluthrin, isoproturon triclosan and zinc pyrithione.
Gemäß einer Ausführungsform ist die Verwendung von OIT als alleinigem bioziden Wirkstoff bevorzugt.In one embodiment, the use of OIT as the sole biocidic agent is preferred.
In einer weiteren Ausführungsform der Erfindung ist eine Kombination der bioziden Wirkstoffe OIT und BIT bevorzugt.In a further embodiment of the invention, a combination of the biocidal active substances OIT and BIT is preferred.
Werden in den erfindungsgemäßen Mikropartikeln als biozider Wirkstoff neben OIT noch weitere Biozide mitverwendet, so kann dieses weitere Biozid zusammen mit dem OIT als Gemisch in den Mikropartikeln enthalten sein. Es ist aber auch möglich, dass man Mikropartikel, die nur OIT enthalten, mit Mikropartikeln, die nur das weitere Biozid enthalten, mit einander vermischt und diese Mischung der Mikropartikel auf das Textil aufbringt.If, in addition to OIT, other biocides are also used in the microparticles according to the invention as biocidal active ingredient, this further biocide may be contained together with the OIT as a mixture in the microparticles. However, it is also possible that microparticles containing only OIT are mixed with microparticles containing only the further biocide, and this mixture of microparticles is applied to the textile.
Die den bioziden Wirkstoff enthaltenden Mikropartikel können daneben noch andere übliche und für die textile Applikation gebräuchliche Zusatzstoffe enthalten, die dem Fachmann bekannt sind. Es sind dies z.B. Verdickungsmittel, Entschäumer, Stoffe zur Einstellung des pH-Werts, Duftstoffe, Dispergierhilfsmittel und färbende oder verfärbungsvermeidende Stoffe, Komplexierungsagenzien und Stabilisatoren wie zum Beispiel UV-Stabilisatoren.The microparticles containing the biocidal active substance may additionally contain other customary additives which are customary for the textile application and which are known to the person skilled in the art. These are e.g. Thickeners, defoamers, substances for adjusting the pH, fragrances, dispersing aids and coloring or discoloration-preventing substances, complexing agents and stabilizers such as UV stabilizers.
Gemäß der Erfindung umfassen die zur Ausrüstung von Textilien verwendeten Mikropartikel bevorzugt keine gesundheitsschädlichen Lösemittel. Das bei der Herstellung bevorzugt verwendete Lösungsmittel ist Wasser.According to the invention, the microparticles used for finishing textiles preferably do not comprise any harmful solvents. The preferred solvent used in the preparation is water.
Sollte gemäß einer besonderen Ausführungsform der Erfindung bei der Herstellung der Mikropartikel auf weitere Lösungsmittel zurückgegriffen werden, so können diese polar oder unpolar oder Gemische enthaltend polare und unpolare Lösungsmittel sein.If, according to a particular embodiment of the invention, further solvents are used in the preparation of the microparticles, these may be polar or nonpolar or mixtures containing polar and non-polar solvents.
Neben Wasser sind als weitere polare flüssige Lösungsmittel zu nennen aliphatische Alkohole mit 1 bis 4 Kohlenstoffatomen, z. B. Ethanol und Isopropanol, ein Glykol, z. B. Ethylenglykol, Diethylenglykol, 1,2-Propylenglykol, Dipropylenglykol und Tripropylenglykol, ein Glykolether, z.B. Butylglykol und Butyldiglykol, ein Glykolester, z. B. Butyldiglykolacetat oder 2,2,4-Trimethylpentandiolmonoisobutyrat, ein Polyethylenglykol, ein Polypropylenglykol, N,N-Dimethylformamid oder ein Gemisch aus 2 oder mehr solcher Lösungsmittel. Das polare flüssige Lösungsmittel ist insbesondere Wasser.
Als unpolare flüssige Lösungsmittel können z.B. Aromaten, vorzugsweise Xylol und Toluol dienen. Auch diese können alleine oder als Gemisch aus 2 oder mehr solcher Lösungsmittel eingesetzt werden.In addition to water are to be mentioned as further polar liquid solvent aliphatic alcohols having 1 to 4 carbon atoms, for. For example, ethanol and isopropanol, a glycol, for. Example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol and tripropylene glycol, a glycol ether, for example butyl glycol and butyl diglycol, a glycol ester, eg. Butyl diglycol acetate or 2,2,4-Trimethylpentandiolmonoisobutyrat, a polyethylene glycol, a polypropylene glycol, N, N-dimethylformamide or a mixture of 2 or more of such solvents. The polar liquid solvent is especially water.
For example, aromatics, preferably xylene and toluene, can serve as nonpolar liquid solvents. These may also be used alone or as a mixture of 2 or more such solvents.
Gemäß einer bevorzugten Ausführungsform der Erfindung werden die Mikropartikel mit Hilfe einer Appretur (z. B. Polymerdispersionen, Aminoharzen, Melamin-Formaldehyd-harzen, Paraffinemulsionen, Fluorcarbonemulsionen, Silikonemulsionen) auf den Textilien verankert. Die Appretur ist eine Imprägnierflüssigkeit, welche auf textile Fäden beziehungsweise Textilien durch Sprühen, Tauchen oder Beschichten aufgebracht wird. Das Ausrüsten der Textilien mit den Mikropartikeln kann somit in einem Arbeitsgang mit dem Aufbringen der Appretur erfolgen. Das Anbringen reaktiver Gruppen auf die Oberfläche beziehungsweise eine reaktive Verankerung der Mikropartikel mit den Textilfasern ist hierbei nicht notwendig.According to a preferred embodiment of the invention, the microparticles are anchored on the textiles by means of a finish (for example polymer dispersions, amino resins, melamine-formaldehyde resins, paraffin emulsions, fluorocarbon emulsions, silicone emulsions). The finish is an impregnating liquid, which is applied to textile threads or textiles by spraying, dipping or coating. The finishing of the textiles with the microparticles can thus be carried out in one operation with the application of the finish. The attachment of reactive groups on the surface or a reactive anchoring of the microparticles with the textile fibers is not necessary here.
Weiterhin können die Mikropartikel mit Hilfe eines Polymers physikalisch an die Fasern der Textilien gebunden werden. Bei dem Polymerüberzug handelt es sich üblicherweise um einen Überzug aus Polymeren wie beispielsweise aus Polyacrylaten, Polyvinylacetat, Polyestern, Polyvinylalkoholen, Polyurethanen, sowie Mischungen dieser. Das Polymer wird beim Auftragen vorzugsweise als Dispersion eingesetzt.Furthermore, the microparticles can be physically bound to the fibers of the textiles by means of a polymer. The polymer coating is usually a coating of polymers such as polyacrylates, polyvinyl acetate, polyesters, polyvinyl alcohols, polyurethanes, and mixtures thereof. The polymer is preferably used as a dispersion during application.
Gemäß einer weiteren Ausführungsform der Erfindung wird eine chemische Verankerung der erfindungsgemäßen Mikropartikel mit der Oberfläche der Textilien durchgeführt. Da die Oberfläche der Mikropartikel reaktive Gruppen, wie Amino-, Hydroxyl- und MethylolGruppen (CH2-OH) aufweist, ist es möglich diese mit Hilfe eines geeigneten reaktiven Binders, beispielsweise eines Isocyanats, insbesondere eines geschützten oder blockierten Isocyanates dauerhaft an der Textiloberfläche zu verankern. Durch die geeignete Wahl des Monomerenverhältnisses bei der Herstellung des Aminoplast-Harzes, beispielsweise des Verhältnisses von Formaldehyd zu Melamin in den Melamin-Formaldehyd-Harzen, ist es möglich, die Art und Anzahl der reaktiven Gruppen zu beeinflussen. Beispielsweise bewirkt ein Überschuss an Melamin ein vermehrtes Vorliegen von Aminogruppen.According to a further embodiment of the invention, a chemical anchoring of the microparticles according to the invention with the surface of the textiles is carried out. Since the surface of the microparticles has reactive groups, such as amino, hydroxyl and methylol groups (CH 2 -OH), it is possible to formulate these with the aid of a suitable reactive binder, for example an isocyanate, in particular a protected or blocked one Isocyanates permanently anchored to the textile surface. By appropriate choice of monomer ratio in the production of the aminoplast resin, for example, the ratio of formaldehyde to melamine in the melamine-formaldehyde resins, it is possible to influence the type and number of reactive groups. For example, an excess of melamine causes an increased presence of amino groups.
Durch die chemische Verankerung der erfindungsgemäßen Mikropartikel kann eine gute Waschpermanenz der Textilien erreicht werden.Due to the chemical anchoring of the microparticles according to the invention, a good washing permanence of the textiles can be achieved.
Die Erfindung betrifft weiterhin die Verwendung von den Wirkstoff 2-n-Octyl-4-isothiazolin-3-on und gegebenenfalls ein oder mehrere andere Biozide enthaltenden Mikropartikeln auf Basis eines Aminoplast-Harzes zum Schutz von Textilien gegen Mikroorganismenbefall.The invention further relates to the use of the active ingredient 2-n-octyl-4-isothiazolin-3-one and optionally one or more other biocides containing microparticles based on an aminoplast resin for the protection of textiles against microorganism infestation.
Gemäß einer weiteren Ausführungsform der Erfindung kann es sich im Sinne der Erfindung bei dem Begriff Textil auch um einen Filter oder Vlies, vorzugsweise um einen Luftfilter handeln, der mit den Mikropartikeln ausgerüstet ist, in dem der biozide Wirkstoff eingeschlossen ist. Das Filtermaterial ist hierbei mit den erfindungsgemäßen Mikropartikeln ausgerüstet um das Wachstum von Pilzen, Algen und Bakterien im Filter zumindest weitgehend zu verhindern. Die derart ausgerüsteten Filter eignen sich für den Einsatz in Klimaanlagen, sowie in Abluft- und Zuluftanlagen. Insbesondere sind derartig ausgerüstete Filter für den Einsatz in Lüftungsanlagen beziehungsweise Klimaanlagen in Schlachthöfen geeignet, da die Ausrüstung des Filtermaterials mit den erfindungsgemäßen Mikropartikeln es ermöglicht, den Filter auszuwaschen, ohne dass dieser dabei seine antimikrobielle Aktivität verliert. Als besonders wirkungsvoll hat es sich bei dieser Ausführungsform der Erfindung herausgestellt, wenn es sich bei dem bioziden Wirkstoff um eine Mischung aus OIT und BIT handelt. Der Vorteil dieses bioziden Wirkstoffes liegt einerseits darin, dass OIT wirksam den Befall des Filters durch Algen und Pilzen und BIT den Befall durch Bakterien verhindert.According to a further embodiment of the invention, in the context of the invention, the term textile may also be a filter or fleece, preferably an air filter equipped with the microparticles in which the biocidal active substance is enclosed. The filter material is in this case equipped with the microparticles according to the invention to prevent the growth of fungi, algae and bacteria in the filter at least largely. The thus equipped filters are suitable for use in air conditioning systems, as well as in exhaust air and supply air systems. In particular, such equipped filters are suitable for use in ventilation systems or air conditioners in slaughterhouses, since the equipment of the filter material with the microparticles according to the invention makes it possible to wash out the filter without this thereby losing its antimicrobial activity. It has been found to be particularly effective in this embodiment of the invention when the biocidal active ingredient is a mixture of OIT and BIT. The advantage of this biocidal active ingredient is on the one hand that OIT effectively prevents the infestation of the filter by algae and fungi and BIT the attack by bacteria.
In den erfindungsgemäßen Mikropartikeln ist der biozide Wirkstoff vorzugsweise in feindisperser, flüssiger oder fester Phase eingeschlossen, besonders bevorzugt wird bei der Herstellung der Mikropartikel der biozide Wirkstoff in wässrigem Medium eingebracht.In the microparticles according to the invention, the biocidal active ingredient is preferably enclosed in finely dispersed, liquid or solid phase, more preferably in the preparation of the microparticles the biocidal active substance is introduced in an aqueous medium.
Für die Herstellung dieser Mikropartikel sind zahlreiche Verfahren bekannt, siehe hierzu beispielsweise
Die Herstellung der bevorzugt verwendeten Melamin-Formaldehyd-Mikropartikel umfasst den Einsatz von Melamin-Formaldehyd-Prekondensaten, die wasserlöslich sind, und aus denen aus wässriger Phase Melamin-Formaldehyd-Harz-Mikropartikel hergestellt werden. Das Herstellungsverfahren weist verschiedene Vorteile auf, wie beispielsweise neben im Vergleich zu anderen möglichen Polymerisationsverfahren kostengünstige Ausgangsmaterialien und die umweltschonende Verwendung von Wasser als bevorzugtes Lösungsmittel. Wenn die eingeschlossenen, beziehungsweise verkapselten bioziden Wirkstoffe nicht leicht wasserlöslich sind kann als Alternative die teilweise Substitution des im Prozess eingesetzten Lösungsmittels Wasser durch mit Wasser mischbare organische Lösungsmittel vorgenommen werden.The preparation of the preferably used melamine-formaldehyde microparticles comprises the use of melamine-formaldehyde precondensates which are water-soluble and from which melamine-formaldehyde-resin microparticles are prepared from the aqueous phase. The manufacturing process has several advantages, such as, in addition to inexpensive compared to other possible polymerization process starting materials and the environmentally friendly use of water as a preferred solvent. Alternatively, if the entrapped or encapsulated biocidic agents are not readily water soluble, partial substitution of the solvent used in the process with water can be made by water-miscible organic solvents.
Bei der Herstellung der erfindungsgemäßen Mikropartikel wird bevorzugt von einer wässrigen Suspension des bioziden Wirkstoffes oder Wirkstoffgemisches unter Verwendung von Wasser als Lösungsmittel ausgegangen. Die erfindungsgemäßen Mikropartikel werden bevorzugt unter Rühren in saurem Milieu hergestellt. Zum Einstellen des sauren Milieus dienen anorganische und/oder organische Säuren wie beispielsweise Salzsäure, Phosphorsäure und Citronensäure.In the preparation of the microparticles according to the invention, preference is given to starting from an aqueous suspension of the biocidal active substance or active substance mixture using water as solvent. The microparticles according to the invention are preferably prepared with stirring in an acidic medium. To set the acidic environment serve inorganic and / or organic acids such as hydrochloric acid, phosphoric acid and citric acid.
Die Mikropartikel können in den für Kondensationspolymerisationen üblichen Apparaturen hergestellt werden. Hierzu zählen Rührkessel, Rührkesselkaskaden, Autoklaven, Rohrreaktoren und Kneter. Die Reaktion wird beispielsweise in Rührkesseln durchgeführt, die mit einem Anker-, Blatt-, Impeller-, Dissolver- oder Mehrstufenimpulsgegenstromrührer ausgestattet sind. Besonders geeignet sind Apparaturen, die im Anschluss an die Polymerisation die direkte Isolierung des Produktes gestatten, wie z. B. Schaufeltrockner. Die erhaltenen Suspensionen können direkt in Verdampfern, wie beispielsweise Bandtrocknern, Schaufeltrocknern, Sprühtrocknern oder Wirbelbetttrocknern getrocknet werden. Man kann aber auch durch Filtrieren oder Zentrifugieren die Hauptmenge des Wassers abtrennen.The microparticles can be prepared in conventional apparatus for condensation polymerizations. These include stirred tanks, stirred tank cascades, autoclaves, tube reactors and kneaders. The reaction is carried out, for example, in stirred tanks equipped with an armature, blade, impeller, dissolver or multistage pulse counterstirrer. Particularly suitable are apparatuses that allow the direct isolation of the product following the polymerization, such as. B. paddle dryer. The resulting suspensions can be dried directly in evaporators, such as belt dryers, paddle dryers, spray dryers or fluid bed dryers. But you can also cut off by filtration or centrifugation, the majority of the water.
Als Ausgangsstoff für die bevorzugt verwendeten Melamin-Formaldehyd-Harze werden einerseits erhältliche veretherte Melaminformaldehydkondensate mit vorzugsweise geringem freiem Formaldehyd, wie beispielsweise Quecodur DM 70 (erhältlich von THOR GmbH) eingesetzt. Weiterhin kann das Melamin-Formaldehyd-Harz auch durch Polykondensation von Melamin und Formaldehyd in Gegenwart des bioziden Wirkstoffes durch dem Fachmann bekannte Techniken hergestellt werden, wie durch Reaktion zwischen Melamin und Formaldehyd bei einem Molverhältnis von 1 bis 6 Teilen Formaldehyd auf einen Teil Melamin.As starting material for the preferably used melamine-formaldehyde resins, on the one hand, etherified melamine-formaldehyde condensates obtainable, preferably with low solubility free formaldehyde such as Quecodur DM 70 (available from THOR GmbH) used. Furthermore, the melamine-formaldehyde resin may also be prepared by polycondensation of melamine and formaldehyde in the presence of the biocidic agent by techniques known to those skilled in the art, such as by reaction between melamine and formaldehyde at a molar ratio of 1 to 6 parts of formaldehyde to one part of melamine.
Die Reaktion wird bevorzugt in wässriger Lösung durchgeführt. In Abhängigkeit der Wandstärke und der gewünschten Menge an biozidem Wirkstoff in den fertigen Mikropartikeln kann die Konzentration des Vorpolymers in der wässrigen Lösung über einen weiten Bereich variiert werden. Am zweckmäßigsten wird das Vorpolymer so zugeführt, beziehungsweise gebildet, dass die Vorpolymerkonzentration etwa 1 bis etwa 70 Gew.-%, bevorzugt etwa 5 bis etwa 50 Gew.-% beträgt.The reaction is preferably carried out in aqueous solution. Depending on the wall thickness and the desired amount of biocidal active substance in the finished microparticles, the concentration of the prepolymer in the aqueous solution can be varied over a wide range. Most preferably, the prepolymer is supplied or formed such that the prepolymer concentration is from about 1 to about 70 weight percent, preferably from about 5 to about 50 weight percent.
Außer dem vorstehend genannten Aminoplast-Harzen können die erfindungsgemäßen Mikropartikel weitere Stoffe enthalten, die in Abhängigkeit des Verwendungszweckes allgemein bekannt und üblich sind. Hierzu gehören einerseits entsprechende Bindemittel und Filmbildner, wie Polyacrylate, Polystrolacrylate oder Siliconharze, andererseits bekannte Hilfsstoffe, wie Pigmente; Füllstoffe wie Calciumcarbonat, Talkum, Kaoline, Silikate, pyrrogene Kieselsäure und/oder Zeolithe; Lösemittel; Verdicker wie Polysaccharide und/oder Celluloseether; Entschäumer; Weichmacher; Dispergiermittel wie Phosphate und/oder Acrylate; Emulgatoren wie Fettalkoholethoxylate, EO/PO Blockpolymere und/oder Sulfonate; Stabilisatoren wie UV Stabilisatoren, Färbende oder verfärbungsvermeidende Stoffe.In addition to the abovementioned aminoplast resins, the microparticles according to the invention may contain further substances which are generally known and customary depending on the intended use. These include on the one hand corresponding binders and film formers, such as polyacrylates, polystyrene or silicone resins, on the other hand, known auxiliaries, such as pigments; Fillers such as calcium carbonate, talc, kaolins, silicates, fumed silica and / or zeolites; Solvents; Thickeners such as polysaccharides and / or cellulose ethers; defoamers; plasticizers; Dispersants such as phosphates and / or acrylates; Emulsifiers such as fatty alcohol ethoxylates, EO / PO block polymers and / or sulfonates; Stabilizers such as UV stabilizers, dyes or discoloration-preventing substances.
Die Polykondensation des Aminoplast-Harzes kann an einer beliebigen Stelle innerhalb des Bereiches von etwa 20 bis etwa 95 °C durchgeführt werden, bevorzugt zwischen etwa 50 und 80°C.The polycondensation of the aminoplast resin may be conducted anywhere within the range of about 20 to about 95 ° C, preferably between about 50 and 80 ° C.
Die Reaktion wird allgemein innerhalb weniger Stunden beendet sein, obwohl die Reaktion bei hoher Temperatur innerhalb weniger Minuten beendet sein kann.The reaction will generally be completed within a few hours, although the reaction at high temperature may be completed within a few minutes.
Sobald die Mikropartikel gebildet sind, können sie als Dispersionen gelagert und verwendet werden oder als getrocknete Partikel filtriert gewonnen werden. In jeder Form sind die Partikel nützlich und wirksam in der gesteuerten Freisetzung des bioziden Wirkstoffes.Once the microparticles are formed, they can be stored as dispersions and used or filtered as dried particles. In any form, the particles are useful and effective in the controlled release of the biocidic agent.
Die folgenden Beispiele sind erläuternd sowohl für die Verfahren als auch für das Produkt der vorliegenden Erfindung, aber sind nicht zu ihrer Definition oder Beschränkung in irgendeiner Weise gedacht.The following examples are illustrative of both the methods and the product of the present invention, but are not intended to be in any way limiting or defining them.
Die Herstellungsbeispiele erläutern die Herstellung von Mikropartikeln, in denen der biozide Wirkstoff eingeschlossen ist.The preparation examples illustrate the preparation of microparticles in which the biocidal active ingredient is included.
Unter Einsatz der nachfolgenden Stoffe wurden Mikropartikel aus Melamin-Formaldehyd hergestellt, in denen der biozide Wirkstoff 2-n-Octyl-4-isothiazolin-3-on eingeschlossen war.
Zur Herstellung der Mikropartikel wurde das Wasser mit dem Melaminharz vorgelegt. Darin wurden Polyacrylat, Gummi Arabicum, Siliconentschäumer und das 2-n-Octyl-4-isothiazolin-3-on eingerührt. Das erhaltene Gemisch wurde auf 90°C erwärmt und während 1 h Salzsäure bis zu einem pH-Wert von 4 zugetropft. Nachfolgend wurde das Gemisch 2 h bei der gleichen Temperatur nachgerührt.To prepare the microparticles, the water was initially charged with the melamine resin. In it were stirred in polyacrylate, gum arabic, silicone defoamer and 2-n-octyl-4-isothiazolin-3-one. The resulting mixture was heated to 90 ° C and added dropwise over 1 h hydrochloric acid to a pH of 4. Subsequently, the mixture was stirred for 2 h at the same temperature.
Das enthaltene Gemisch enthielt die gewünschten Mikropartikel in denen der biozide Wirkstoff eingeschlossen ist.The contained mixture contained the desired microparticles in which the biocidal active ingredient is included.
Die nachfolgend aufgeführten Beispiele und Vergleichsbeispiele belegen den Effekt des eingeschlossenen OIT. Hierzu werden Textilien, welche mit den erfindungsgemäßen Mikropartikeln ausgerüstet sind, mit Textilien, die mit dispergiertem OIT ausgerüstet sind, verglichen.The following examples and comparative examples demonstrate the effect of the trapped OIT. For this purpose, textiles which are equipped with the microparticles according to the invention are compared with textiles which are equipped with dispersed OIT.
Um den Effekt des erfindungemäß ausgerüsteten Textils zu untersuchen, wurden verschiedene Textilmuster mit einer Größe von 40 x 40 cm jeweils in wässrigen Flotten mit 30 g/l einer ca. 10% igen Mikropartikel enthaltenden Zusammensetzung beziehungsweise einer entsprechende Menge eines Vergleichsproduktes mit herkömmlich dispergierten OIT imprägniert. Als Appreturhilfsmittel wurden 30 g/l Quecophob GAR (Fluorcarbonharz; Fa. THOR GmbH) zugesetzt. Die Textilmuster wurden anschließend über eine Foulardwalze abgequetscht, bei 120°C eine Minute getrocknet und bei 150°C für eine Minute kondensiert. Vor dem Trocknen wurde die Auflage bestimmt, und hiermit die theoretische Wirkstoffkonzentration berechnet.In order to investigate the effect of the fabric according to the invention, various textile samples having a size of 40 × 40 cm were impregnated in each case in aqueous liquors with 30 g / l of a composition containing about 10% microparticles or a corresponding amount of a comparison product with conventionally dispersed OIT , As finishing aid, 30 g / l of Quecophob GAR (fluorocarbon resin, Fa THOR GmbH) were added. The textile samples were then squeezed off on a padder roll, dried at 120 ° C for one minute and condensed at 150 ° C for one minute. Before drying, the overlay was determined and used to calculate the theoretical drug concentration.
Von den imprägnierten Stoffen wurden anschließend Proben entnommen und mittels HPLC auf deren Wirkstoffkonzentration hin untersucht. Die erhaltenen Ergebnisse sind in Tabelle 1 aufgeführt.
Ferner wurden einige der nach dem Beispiel ausgerüsteten Textilmuster über einen Zeitraum von 24 Stunden gewässert und anschließend auf ihren Wirkstoffgehalt hin untersucht. In Tabelle 2 sind die Wirkstoffkonzentrationen vor und nach der Wässerung aufgeführt.
Aus den in den Tabellen 1 und 2 aufgeführten Werten geht deutlich der Vorteil des erfindungsgemäßen Einschlusses des Wirkstoffes in die Mikropartikel hervor. Bei dem mit eingeschlossenem, beziehungsweise verkapseltem OIT ausgerüsteten Textil ist nach der thermischen Nachbehandlung und Wässerung erheblich mehr Wirkstoff nachweisbar als bei dem herkömmlich ausgerüsteten Textil. Anhand der vorstehenden Versuchsergebnisse wird ersichtlich, dass sich durch den Einschluss des bioziden Wirkstoffes der Verlust an biozidem Wirkstoff und der Eintrag in die Abluft/Umwelt reduziert und darüber hinaus deutlich mehr Wirkstoff auf den Textilien verbleibt.The values listed in Tables 1 and 2 clearly show the advantage of the inclusion according to the invention of the active ingredient in the microparticles. In the case of the textile which is provided with enclosed or encapsulated OIT, considerably more active substance can be detected after the thermal aftertreatment and washing than in the textile which has been conventionally finished. On the basis of the above test results, it can be seen that the inclusion of the biocidal active substance reduces the loss of biocidal active substance and the entry into the exhaust air / environment and, moreover, significantly more active substance remains on the textiles.
Die nach dem Beispiel 1 und Vergleichsbeispiel hergestellten Polyester-Muster wurden auf ihre pilzhemmenden Eigenschaften nach DIN 53931 untersucht. Die Ergebnisse sind in der Tabelle 3 dargestellt.
Die mit eingeschlossenem OIT ausgerüsteten Textilproben zeigen hervorragende pilzhemmende Eigenschaften. Diese pilzhemmenden Eigenschaften sind auch nach der Wässerung der Textilien noch vorhanden.The trapped OIT textile samples show excellent antifungal properties. These antifungal properties are still present even after the washing of the textiles.
Claims (9)
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DE102012003943A1 (en) | 2012-02-24 | 2013-08-29 | Innovent E.V. Technologieentwicklung | Preparing antimicrobial nano-layers on substrate material, in the form of e.g. fiber- or yarn materials, comprises surface modifying the substrate material by flame-pyrolysis process, and depositing a thin layer on the substrate material |
WO2013150085A1 (en) * | 2012-04-05 | 2013-10-10 | Basf Se | Amino plastic containing porous particles |
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WO2010121606A2 (en) | 2009-04-24 | 2010-10-28 | Chemische Werke Kluthe Gmbh | Method, formulas, and product for biocidal treatment of a cooling lubricant |
CN104884704A (en) | 2012-08-23 | 2015-09-02 | 绿色主题科技有限责任公司 | Chemical stick finishing method and apparatus |
US9079119B2 (en) * | 2013-01-28 | 2015-07-14 | King Fahd University Of Petroleum And Minerals | Flexible belt evaporator |
CN103451954B (en) * | 2013-07-24 | 2016-01-13 | 安徽华强羽绒有限公司 | down detergent and preparation method thereof |
CN103451957B (en) * | 2013-08-09 | 2016-01-27 | 安徽华强羽绒有限公司 | Fungus and mildew resistance eider down care agent and preparation method thereof |
US9790640B2 (en) | 2014-02-24 | 2017-10-17 | Gary S Selwyn | Composition and process for applying hydrophobic coating to fibrous substrates |
CN105088766A (en) * | 2015-09-07 | 2015-11-25 | 王璐 | Mould-proof antibacterial agent for fabric |
CN105568674A (en) * | 2015-12-16 | 2016-05-11 | 常熟市中宏针织厂 | Finishing process of bedsheet fabric |
CN105568683A (en) * | 2015-12-16 | 2016-05-11 | 常熟市中宏针织厂 | Finishing process of garment fabric |
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- 2007-06-28 US US12/308,551 patent/US7700502B2/en not_active Expired - Fee Related
- 2007-06-28 WO PCT/EP2007/056492 patent/WO2008000796A2/en active Application Filing
- 2007-06-28 MX MX2008016282A patent/MX2008016282A/en unknown
- 2007-06-28 EP EP07786889A patent/EP2038473A2/en not_active Withdrawn
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WO2004000953A1 (en) * | 2002-06-19 | 2003-12-31 | Thor Gmbh | Coating material with biocide microcapsules |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102012003943A1 (en) | 2012-02-24 | 2013-08-29 | Innovent E.V. Technologieentwicklung | Preparing antimicrobial nano-layers on substrate material, in the form of e.g. fiber- or yarn materials, comprises surface modifying the substrate material by flame-pyrolysis process, and depositing a thin layer on the substrate material |
WO2013150085A1 (en) * | 2012-04-05 | 2013-10-10 | Basf Se | Amino plastic containing porous particles |
Also Published As
Publication number | Publication date |
---|---|
CN101479425A (en) | 2009-07-08 |
MX2008016282A (en) | 2009-01-15 |
WO2008000796A2 (en) | 2008-01-03 |
EP2038473A2 (en) | 2009-03-25 |
AU2007263697A1 (en) | 2008-01-03 |
JP2009541610A (en) | 2009-11-26 |
BRPI0713948A2 (en) | 2012-12-04 |
US7700502B2 (en) | 2010-04-20 |
US20090318044A1 (en) | 2009-12-24 |
WO2008000796A3 (en) | 2008-02-14 |
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