DE2134358A1 - ANTIMICROBIAL EQUIPMENT OF TEXTILES - Google Patents

Description

Antimicrobial finishing of textiles

It is already known to give textiles an antimicrobial finish, by treating them with organotin compounds such as tributyltin oxide or triphenyltin oxide (see "Textilver- ' edlung "5 (1970), 1 page 9). These compounds have the disadvantage that they are not washable and dry-cleaning resistant on textiles, especially textiles made of synthetic fiber materials can be fixed. The compounds also have no bacteriostatic activity. Another disadvantage is that when used in conjunction with anti-wrinkle finishes, they adversely affect dry wrinkle angles.

It has now been found that the disadvantages described of the known organotin compounds can be overcome if organotin compounds of the general formula I are used for an antimicrobial finish on textiles

«3

Sn-O-C-C = CH-CH-CH-R.

ι ι ⁴ CF _n -CF.

'/ η

: ο R,

(D

209884/1366

FARBWERKE HOECHST AG formerly Master Lucius & Brüning

new pages 2 to 4a J ^ sjfe ^ ^^ £ I & U **} £, S * JL "

is used in which IL, R ", R" and R _{4 are} alltyl or aryl radicals and R, are hydrogen or the methyl group.

In formula I, R-, U, R ₃ and R _{4 can} in particular represent Alley 1-. Radicals having 1 to 8 carbon atoms, phenyl radicals, or phenyl radicals substituted by lower alkyl radicals; preferably R-, R ~ and R ₃ denote butyl or phenyl radicals and R ₄ denotes the methyl, ethyl, butyl or phenyl radical.

The invention relates to a process for the preparation of organotin compounds of the general formula I

R_ _> Sn-O-C-C-CH-CH-CH-R-. (I),

² ^ Il I .II ' ⁴

Rg. 0 R ₅ . ^CF 2 " ^CF ?

in which R ₁ , R, R_ and R. denote alkyl radicals with 1 to 8 carbon atoms j phenyl radicals or phenyl radicals substituted by lower alkyl radicals, in which one mole of a bis-organic tin oxide of the formula II

Sn-O- Sn = ^ - R ₀ (II)

with about 2 moles of a carboxylic acid of the formula III

R ₄ - CH - CH - CH = C - COOH (III),

K- KK

where the radicals R- to R- dfe in the formula I meanings mentioned own, condensed.

The invention also relates to the use of organic zinc Compounds of the above general formula I for the antimicrobial armor of textiles.

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Compounds of the formula I to be used according to the invention are, without hereby expressing any restriction should, for example, called:

Tributyltin-ß-tetrafluorcyclobutylacrylat, triphenyltin ß-tetrafIuorcyclobutylacrylat, tributyltin-ß-methyl-tetrafluorcyclobutylacrylat, TriphenyIzinn-ß-methyl-tetrafluorcyclobutylacrylat, tributyltin ß-tetrafluorcyclobutylmethacrylat, Tributylziim-ß-methyl-ß-tßtrafluorcyclobutylmethacrylat _r triphenyltin tetrafluorcyclobutylmethacrylat, triphenyltin β-methyl-tetrafluorocyclobutyl methacrylate.

The compounds of the formula I have a good fungistatic and bacteriostatic effect. Also to be emphasized is the Resistance to washing as well as resistance to chemical cleaning with halogenated hydrocarbons or with the compounds finishes obtained according to the invention on textiles. The wash resistance of these finishes can be further increased if the connections are made on the textile material be subjected to an alkali treatment. A surprising advantage when using the compounds of the formula I is also that they are wash-resistant antimicrobial on synthetic fibers, such as polyamide and polyacrylonitrile fibers Effects result. On cellulose fiber textiles it is even possible to produce finishes that are resistant to washing at the boilers. Another ™ The advantage of using the compounds of the formula I is that these compounds do not lead to yellowing of the Lead textile material. They also have an effect, unlike many known antimicrobial agents, for example applied to textile floor coverings, no additional soiling.

Textiles and other materials made with the compounds of the Formula I can be given an antimicrobial finish, are, for example, woven, knitted and knitted fabrics, yarns, Nonwovens, solidified nonwovens, textile laminates, feathers, as well Oil synthetic leather. The textiles to be antimicrobial can

209884/1366

Made from natural fibers such as cellulose fibers, wool, or silk Synthetic fibers, such as, for example, polyamide, polyacrylonitrile, polyester fibers, polyvinyl chloride elastomer fibers, inorganic fibers Fibers, asbestos and glass fibers and mixtures of such fibers such as polyester fibers / cotton, polyester fibers / Rayon, polyacrylonitrile fibers / rayon, polyester fibers / Linen, polyester fibers / wool or polyamide fibers / cotton, etc. exist.

The preparation of the compounds of the formula I by reacting bis-organic tin oxides of the formula II, for example bis-tributyl tin oxide, with carboxylic acids of the formula III, for Example β-tetrafluorocyclobutyl acrylic acid or methyl tetrafluorocyclobutyl acrylic acid can by methods known per se in a suitable organic solvent, such as, for example Benzene, toluene, xylene. The reaction takes place at an elevated temperature, expediently at the boiling point of the solvent under reflux, with about 2 moles of the carboxylic acid of the formula III per mole according to the desired reaction of the bis-organic tin oxide of the formula II are used, The water resulting from the condensation is replaced by azec— tropic distillation removed along with the solvent. The substance remaining after the solvent has been distilled off can optionally be used directly without further purification antimicrobial finishing according to the invention can be used.

The organotin compounds of the formula I are soluble in many organic solvents. Particularly suitable solvents With regard to the textile application of these compounds are lower aliphatic alcohols, above all those with 1 to 4 carbon atoms. The organotin compounds according to the invention are also in the aqueous, alkaline-reacting medium, for example in aqueous solutions of Soluble alkali hydroxides, carbonates or bicarbonates. When applied to textiles, they can therefore be made from organic

209884/1366

Chemical solvents, from solvent-water mixtures, at pH values above 7, from aqueous solutions and from emulsions, for example those made from chlorinated or fluorocarbons with water or alcohol. For the antimicrobial finishing of textiles, solutions are generally used which have a content of about 10 to 100 g, preferably 15 to 40 g, of the inorganic compounds of the formula I per liter of liquor. With these concentrations of the equipment liquors, in most cases an effective amount depending on the squeezing effect is guaranteed. A minimum of 0.3%, based on the weight of the goods, is required. There is no upper limit to the amounts of organotin compounds to be applied. However, for economic reasons, a quantity of more than about 5 % is practically out of the question.

209884/1366

For the antimicrobial finishing of textiles, the organotin compounds of the formula I can be used both alone and also used together with other finishing and binding agents will. It is also possible to use the organotin compounds together with optical brighteners or antistatic to apply effective means. For finishing textiles made of or containing cellulose fibers, the organotin compounds are expediently applied to the textile material together with anti-crease agents. Particularly under dry crosslinking conditions achieve fungistatic effects that are good boil-wash resistant. The organotin compounds are also used possible with the known processes of moist and wet crosslinking of textiles. The use of the Organotin compounds together with alkaline crosslinking high-quality finishing agents. The organotin compounds can also used in the dyeing of textiles and for example

Pressure/
can be added to the dye liquor or paste. In this way, antimicrobial effects are achieved at the same time as dyeing or printing. The use of the organotin compounds together with alkaline fixable dyes is of particular advantage. Furthermore, it is also possible to apply the organotin compounds to the textile material together with water repellants, oil repellants and flame retardants.

The organotin compounds of the formula I can be based on any Way, for example by padding, paddling, spraying, Squeegee or applied to the goods to be finished using the exhaust method. Those with solutions or dispersions of the Textiles treated with organotin compounds are dried at room temperature or elevated temperature and are expedient briefly heated to high temperatures for about 1 second to 5 minutes. The Vfaiii of the temperature is dependent on the heating time and the textile material. In general, temperatures in the range from about 110 to 220 ° C are used. It has been found to be beneficial with the organotin

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Compounds of the formula I treated and dried textiles after-treating with solutions of dilute alkalis or to apply the compounds of the formula I to textiles which have been pretreated with alkalis and have an alkaline reaction.

The incorporation of the organotin compounds according to the invention into pastes, pigment mixtures and the like for coating purposes is possible. The joint use of organotin compounds with plastic dispersions, such as For example, polyacrylate, polyurethane, butadiene copolymer, polyvinyl acetate dispersions or natural latex is then special of importance when floor coverings, for example carpets, needle felts, mats or fleeces are fungistatic and bacteriostatic are to be equipped.

In the following examples, unless expressly stated otherwise noted, the parts are parts by weight and the percentages are percentages by weight.

Testing of the antimicrobial effectiveness of textile armor in the following examples was carried out according to the in the magazine "Textilveredlung" 5 (1970), pages 12 to 14, described method. Plastic petri dishes are used here each charged with 20 ml of malt extract dextrose agar and the germs applied as an inoculation line to the solidified surface. The ends of the inoculation marks are covered with a test patch (2 × 2 cm) of the finished product. After an eight day Incubation time at 28 C, the germ growth on the textile material and in its surroundings (inhibition zone) is assessed as follows:

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Finding. Rating

Agar layer over the Gev / ebeprobe shows the same growth rate of the test germ

like the environment 1

Only a few colonies grow on the agar layer above the sample, inhibition of the multiple turn compared to the surrounding area 2

On the agar layer over the tissue sample no colonies of microorganisms can be observed 3

The agar layer over the sample is not overgrown, so there is a distinct one around the sample Inhibition zone visible, the width of which is not 2 mm

exceeds "4

There is an inhibition zone around the tissue sample

formed by more than 2 mm 5

20988A / 1366

Example 1:

Samples of a knitted fabric made of polyamide fibers were each with impregnated with the following solutions:

Solution A 1.5 parts of tributyltin-ß-tetrafluorcyclo ^

butyl acrylate

24.5 parts of water and 74.0 parts of isopropanol

Solution B 1.5 parts of tributyltin-ß- (methyl) -tetra-

fluorocyclobutyl acrylate

24.5 parts of water and 74.0 parts of isopropanol

Solution C 1.5 parts triphenyltin-ß -. (Methyl) -tetra-

fluorocyclobutyl acrylate

24.5 parts of water and 74.0 parts of isopropanol

Solution D 1.5 parts tributyltin oxide (comparison) 24.5 parts water 74.0 parts isopropanol

The squeezing effect is «50 percent by weight. After padding, it is dried and fixed by heating at 180 ° C. for 1 minute. The ones with solutions A Textiles finished to C show an excellent fungistatic and a bacteriostatic effect. The results of the tests for growth inhibition against the skin fungus Trichophyton mentagrophytes 109 and the soil fungus Aspergillus niger 533 after three washes with a household washing machine are summarized in Table 1.

209884/136

ΛΑ

Example 2:

Samples of a polyacrylonitrile fabric are each given with the following Solutions covered:

Solution A Tributyltin β (methyl) tetrafluorocyclobutyl acrylate in isopropanol / water (3: 1 parts by volume)

Solution B triphenyltin β (methyl) tetrafluorocyclobutyl acrylate in isopropanol / water (3; 1 parts by volume) and

Solution C tributyltin oxide in isopropanol / water, (3 ti vol- (comparison) _{lumen parts)} <

The squeezing effect is 50 percent by weight

The fabric samples are ^{dried at 100 °} C. and fixed at 150 ° C. for one minute. The treatments with solutions A and B have excellent fungistatic effects against skin and soil fungi and yeasts.

In the following Table 2 are the antimicrobial effects set after three machine washes:

Table 2

Trichoph.
ment. Growth inhibition (grade) Candida
albicans
504 Aspergillus
niger 533 solution 3 Candida
albicans
St 1 3 3 A. 3 3 3 3 B. 1 3 1 1 C. 1

2QS8BA / T386

Table 1:

Growth inhibition (grade)

/ ο

sung Trichoph. ment. Asperg, niger A. 3 3 B. 5 3 C. 5 4th D. 1 1

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Example 3:

Samples of a cotton poplin are impregnated with solutions of the following composition:

Solution A 150 g / l dimethyloldihydroxyethylene urea (50%)

15, g / l Mg chloride

15 g / l. Tributyltin-ß-tetrafluorocyclobutyl acrylate

Solution B 150 g / l dimethyloldihydroxyethylene urea (50 %)

15 g / l Mg chloride -

IS g / l tributyltin β (methyl) tetrafluorocyclobutyl acrylate

Solution C 150 g / l dimethyloldihydroxyethylene urea (50%)

15 g / l Mg chloride

15 g / l triphenyltin-ß- (raethyl) -tetrafluorocyclobutyl acrylate

Solution D 150 g / l dimethyloldihydroxyethylene urea (50%)

(Comparison) _{15 g / 1 mg chloride}

15 g / l tributyl tin oxide

The squeezing effect is 70 percent by weight.

A mixture of 3 parts by volume of isopropanol is used as the solvent and 1 part by volume of water.

After padding, the samples are dried on the stenter at 100 ° C. and then condensed at 150 ° C. for 5 minutes. The samples of the finished tissue show a pronounced fungistatic effect Effect against skin, soil and sprout fungi as well as a bacteriostatic effect against Staphylococcus aureus.

After two machine washes there is still a noticeable inhibition

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AWAY

the growth of Trichophyton mentagrophytes (skin fungus) and Detect Aspergillus niger (soil fungus) in samples A to C. On the other hand, on sample D, there is no effectiveness of the equipment ascertain. While the organotin compounds in the Solutions A to C have practically no effect on the dry wrinkle angle of the fabric, the tributyltin oxide in sample D does one significant decrease in the dry wrinkle angle.

Example 4:

Samples of a cotton fabric are each made with a liquor

Solution A 10 g / l tributyltin-ß-tetrafluorocyclobutyl acrylate and Solution B 10 g / l triphenyltin-ß-tetrafluorocyclobutyl acrylate

impregnated, squeezed off to a weight increase of 70% and at 100.degree dried. Isopropanol / water (3: 1 parts by volume) is used as the solvent. The dried tissue samples are then treated with 5 g / l sodium hydroxide solution (32%) and rolled up and wrapped in foil. After storage for 18 hours in this Condition is rinsed, neutralized and dried.

The fabrics show an excellent fungistatic effect against skin fungi, yeasts and soil fungi, as well as a bacteriostatic effect Effect. It should be emphasized that in these samples, after two machine washings, there was still a strong inhibition of fungal growth both on the tissue sample and on the periphery of the sample in Trichophyton mentagrophytes, Candida albicans and Aspergillus niger, is still present in Staphylococcus aureus.

209884/1366

Example 5:

A polyester fiber fleece is impregnated with a liquor on the padder, the

25 parts of a 42% strength aqueous dispersion of a copolymer made of 52% butylate, 25% acrylonitrile, 21% styrene and 2% acrylamide,

2 parts tributyl tin-ß- (methyl) -tetrafluorcyclobutyl-

acrylate and
33 parts isopropanol

contains. After squeezing to 50% weight gain, 130 C dried. When tested, the consolidated fleece shows a fungistatic and bacteriostatic effect against Trichophyton mentagrophytes, Aspergillus niger and Staphylococcus aureus.

209884/1366

Claims (9)

Sn - O - C - C claims: 1. Process for the preparation of organotin compounds of the general formula I. CH-CH-CH-R ₄ (I) CF ₀ - CF " in which R, R ₂ , R ₃ and R _{4 are} alkyl radicals having 1 to 8 carbon atoms, phenyl radicals or phenyl radicals substituted by lower alkyl radicals and R _{5 is} hydrogen or the methyl group, characterized in that one mole of a bisorganic tin oxide of the formula II Sn-O- Sn R "(II) with about 2 Hol of a carboxylic acid of the formula III R- -CH-CH- CH -C- COOK (III) ⁴ II I ⁰ V ⁰ ^ ^R 5 condensed, the radicals R- to R_ in the formula I. Have the meanings mentioned. 2. Process for the preparation of organotin compounds of the general formula I according to Claim 1, characterized in that that the reaction of the bis-organic tin oxide of the formula II with the carboxylic acid of the formula III according to claim 1 in an ox * -> Chemical solvent at elevated temperature, expediently at the boiling point of the solvent. 2098 8 4/1366 / f6 3. Use of organotin compounds of the general formula I according to claim 1 for antimicrobial finishing of textiles. 4. Use of organotin compounds of the general formula I for the antimicrobial finishing of textiles according to claim 3, characterized in that the organotin compounds are applied to the textiles in amounts of at least 0.3%, based on the weight of the goods. 5. Use of organotin compounds of general Formula I for the antimicrobial finishing of textiles according to claim 3 or 4, characterized in that the textiles treated with solutions or dispersions of the organotin compounds of the formula I and dried briefly heated to high temperatures. 6. Use of organotin compounds of the general formula I for the antimicrobial finishing of textiles Claims 3 to 5, characterized in that the treated with the organotin compounds and dried Textiles treated with solutions of diluted alkalis. 7. Use of organotin compounds of the formula I for the antimicrobial finishing of textiles according to patent claims 3 to 6, characterized in that the organotin compounds together with alkaline fixable dyes are applied to the textiles. 8. Use of organotin compounds of general formula 1 for the antimicrobial finishing of textiles Claims 3 to 7, characterized in that the organotin compounds together with anti-crease agents are applied to the textiles. 20 9 884/13 6 6 ORIGINAL INSPECTED 4t "" "/ 134358 9. Use of ζinnorganischen compounds of general formula I for the antimicrobial finishing of textiles according to claims 3 to 8, characterized in that the
Organotin compounds are applied to a textile material pretreated with alkalis. 209884/136.