DE1146618B - Process for the treatment of fibrous materials or compact masses of organic material to achieve antimicrobial properties - Google Patents

Description

GERMAN

PATENT OFFICE

116376IVa / 3Oi

REGISTRATION DATE: MAY 4, 1959

NOTICE
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: APRIL 4, 1963

Process for the treatment of fibrous materials or compact masses of organic material for Achieving antimicrobial properties are widely known. In particular, it is known that zinc and some of its compounds are highly antimicrobial active against a wide range of microorganisms. In procedural terms, the procedure is usually so that the material with a z. B. aqueous Solution of the agent treated by spraying or dipping. The fixation of the funds on the treated However, materials, especially in smaller quantities, are usually unsatisfactory in this way, so that the antimicrobial properties prematurely through loss of the antimicrobial acting Funds are lost. This also applies to means or processes in which, in addition to zinc salts, so-called Sequestering agents are added.

The object of the invention is to provide a method for achieving antimicrobial properties in the case of textile, protein, cellulose or similar materials to be indicated with the specified Materials are given permanent antimicrobial properties.

The invention relates to a method for achieving antimicrobial properties in textile, protein, cellulose or similar material, the material being treated in a zinc salt solution in the presence of a sequestering agent. The invention consists in treating the material with an amine simultaneously with the first or subsequent to the first treatment and thereby fixing the zinc or zinc compounds and the sequestering agent. According to a preferred embodiment of the invention, urea is used as the amine. The pH value of the Behändlungslösung is suitably adjusted to not higher than 8, while desired to operate at a temperature of about 50 ⁰ C as possible.

The advantages achieved by the invention are mainly to be seen in the fact that according to the invention Method in a simple way zinc or zinc salts and sequestering agents effective on materials, the antimicrobial properties should be able to be fixed, regardless of whether it is Textile, protein, cellulose or similar materials are involved. This affects the invention suggested fixatives the antimicrobial properties of zinc salts or the sequestering agent in no way. These advantages are attributed to the fact that after treatment with the invention Process the active complex is likely to be in chemical bond with the process to protect for the treatment of fibers or compact masses of organic material to achieve antimicrobial

properties

Applicant:

Yardney International Corp., New York, N.Y. (V. St. A.)

Representative: Dipl.-Ing. Dr.-Ing. H. Idel

and Dipl.-Phys. Dr. W. Andrejewski, patent attorneys,

Essen, Kettwiger Str. 36

Claimed priority:

V. St. v. America of June 2 and September 15, 1958 (No. 738 967 and No. 760 857)

Dr. Meyer Mendelsohn, New York, N.Y.

(V. St. A.),
has been named as the inventor

the polymer structure is located or is directly associated with it, so that it is made up of the polymer Material can no longer be removed. It has been found that fabric so treated is anti-microbial Retains properties despite repeated washing. In fact, they allow due to this Treatment achieved improved physical properties, yet antimicrobial effects after to show a larger number of washing processes that would otherwise suffice, untreated control fabric to weaken and destroy. At the same time, the treatment according to the invention has an influence the physical properties of the clothes, fibers and sheet material are not detrimental in terms of smoothness, flexibility, hardness, handiness, washability and wettability.

To treat the objects under nearly neutral or acidic conditions are preferred Boric acid, alkali acetates or other common buffer substances added. Some of the commonly used at Textiles used surfactants of the ionized or non-ionized types can be used as Wetting agents or cleaning agents are used, e.g. B. including the various sulfonated, long-chain Alcohols and esters, as well as phenolates,

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Sorbates, quaternary salts and naphthenates. It was also found that the procedure

can any zinc salt soluble in the medium as well and the baths used with the various the amine as soluble in the treatment medium those treatments (washing and finishing) that • Source are used. are currently used in textiles, in

The one-step treatment bath or the fixing bath, 5 are to be brought into line. These known treatments, which depend on the treatment with the zinc complex salt solution, consist of an impregnation of the textiles, at least ¹ Iz ⁰ Ip urea or an amine with polymeric, resin-like materials with a dissociation constant (K _B ), of the thermoplastic or thermosetting type. that is greater than 1 ■ 10 ~ ¹⁴ are included. The panel I at the. thermoplastic treatment resins contain a large number of such amines. io usually used in the form of emulsions,

while the thermosetting-type materials in Table I are in the form of aqueous solutions of resin-poly-

,, ... , . _DD _ ._, _DD . .. _TTT merisaten (prepolymers) are used, which

Monoathanolamm HO (CHa) ₂ NH _{2 gich} ^ _in ^ _{Ge e under the infiuence the inh} i _rk ene

n-Fropylarnin ^ ³ " ⁷ ™ 15 then remove the heat. The treatment .after the

Athylamin ^ TfK χ _ΤΐΙ invention can be used before or during the application

Diethanolamine (HOC ₂ H ^) ₂ NH _{äeser "Au} srüstungs" treatment without loss in

Athyldiamm 9 £ **? Ί? & _Τ ^the effectiveness of each of these treatments out-

Tnathanolamm (HOC ₂ H ₄ ) SN are carried out.

Triethylamine ^ ² JJJ ³ StT ^z ° ^The one-stage treatment process is on

Diatüylamm (C ₂ Hs) ₂ JNH most effective practically carried out in aqueous

^,. ° / 4t7Vu xTxj baths with a wide variety of components, the

T ^ 1 λ- xtt ^ tFxtS ² can be present in the following concentrations:

p-phenylenediamine NH ₂ CeH ₄ NH ₂

Chelating agents or sequestrants

_CH2 _ _CHax ²⁵ medium V10 up to 10%

Morpholine O <> NH Soluble zinc salt. 1/2 to 50%

\ Cfj9 CHf / Ammating agent (for introducing

NH ₂ groups) 1/2 to 30%

NH ₂ \ cleaning or wetting agent 0 to 15%

■> C = N _X ³⁰ buffer substances 0 to 25%

Melamine N ^ _y .C - NH ₂ . _. ,. .

^ CN ^ I ^m two-tier verianren the individual

Factors such as concentration, duration and temperature, both of the zinc bath and of the fixation

The treatment concentrate can be varied within wide limits with or without a bath. The minimum

Amine, which itself can serve as a commercial article, would have to temperature at 20 ⁰ C and the duration

can either be dry granules or one could be on the order of about ¹ ^ second

be liquid concentrate. To make the former, lie. The amine concentration will of course vary

the dry ingredients are mixed and in with the dissociation constant of the used

granulated in a known manner. To the treatment bath 40 amines. Urea at a concentration of 1%

A necessary part of doing this is a 20 second immersion time at 40 ° C

Granules dissolved, whereupon the liquid concentrate is required.

Various modifications of the procedure can be made to be diluted to the desired degree

can. The bath is then heated and this is described in the following examples. The two

material to be treated is immersed in it. The contra- 45s are to be understood in such a way that the preferred

centering of the bath depends on the desired, species only in relation to the specific applied

Describe the zinc complex material to be incorporated into the end product. Modifications of the special

salary from. fish formulations can be changed by changing the

Furthermore, a control over the deposition, starting materials, duration or temperature can be achieved.

of the zinc amino polymer in the fiber through the 50 are required.
Amount of wetting agent and the temperature at which the

Fixation of the complex in the fibers required Example 1

is to be exercised. A measure of the degree of the approach b7w 7usat7 ΑΪ

Wetting and penetration of the reaction ^ approach dzw. addition A)

components is the inclusion of the bath liquid 55 tetra-sodium salt of ethylenediamine

through the fibers. This intake is defined as 1 part tetraacetic acid

the ratio of the difference between standard and zinc chloride 23 parts

Dry weights: dry weight of the fibers. 7 parts of each sodium acetate

The greater the degree of absorption, the less boric acid 1 part

the required initial concentration of the complex 60 detergents of the quaternary type .. 2 parts

educational means. It was also found that urea 33 parts

the higher the fixing temperatures used

- Either in the bath or in the wetted 30 g of the above mixture are in 1 1

Tissues that have been hung up to dry or that have been dissolved in water to form the treatment bath,

were transported on conveyor belts - goods, 65 The bath is ^{heated to 50 0} C, then one immersed

the lower the concentrations of the knitted cotton socks would have been in the for 10 minutes

complexing agents (zinc, sequestering bath, pulls them out, rinses in water and dries,

and aminating agents). Samples show that there was contact with the treated

Socks inhibit the growth of test bacteria. In addition, this effect persists in the socks even after they have undergone automatic washing treatment about 50 times. Untreated control socks did not develop these inhibitory properties. It even became observed that 20% of the controls had holes due to daily use (wear and tear) and were solely the result of the washing process. Treated socks did not show any Holes.

Example 2

15 g of batch A (example 1) are added to 600 cm ^{3 of} a prepared resin bath, as is customary in the wash-and-wear treatment of cotton fabrics, and the mixture is stirred until batch A is completely dissolved. The tissue to be treated (shirt cloth) is immersed in the prepared solution at room temperature until it is completely moistened (30 to 60 seconds) and then pulled out of the bath. The liquid is allowed to drain from the tissue or is squeezed out until the liquid absorbed by the bath is 70 to 120%. The fabric is then z. B. dried for 1 minute at 180 ° C and then washed in a bath containing a detergent such as sodium perborate. The tests show an inhibition of bacterial growth in the treated tissue. This property of the treated material was observed after the treated fabric was subjected to 50 wash cycles with standard soaps. Untreated controls did not have these inhibitory properties, either before or after the washing processes. Similarly, it was found that towels treated with the "finishing" resins without formulation A did not have any antibacterial properties.

Example 3
(Approach B)

Tetra-sodium salt of ethylenediamine

Tetraacetic acid 3 parts

Zinc chloride 20 parts

Sodium acetate 8 parts

Boric acid 1 part

Urea 20 parts

Non-ionized detergent 1 part

15 g of batch B are dissolved in 1 l of water. Then wool socks are dipped in this solution, until they have absorbed 90 to 120% of their weight from the solution. Then they are on Heated to 50 ° C and left at this temperature for at least 15 minutes or until dry are. The residue from the bath is then washed off the socks or rinsed off. the Socks treated in this way retain their antimicrobial properties over 30 washing processes. Control attempts show these microbe-inhibiting properties neither before nor after washing.

Example 4

A bath corresponding to Example 3 is used to treat a cotton-polyester (Dacron) 65-35 shirt fabric used. The fabric is immersed in the 40 ° C bath for 2 minutes, until the dry weight absorption of the bath through the shirt fabric is 70%. The tissue will then dried at 80 ° C. The finished fabric (after rinsing and drying) prevents the growth of bacteria in connection with previous or subsequent washing processes.

Example 5

ίο Fabric made from rayon tricot is used in the style of Example 3 with the exception that the fixing and drying are carried out at 60 to 80.degree will. The fabric shows anti-bacterial properties before and after 30 washing processes.

Example 6

Tetra-sodium salt of ethylenediamine

Tetraacetic acid 1 part

Non-ionized detergent 1 part

Sodium acetate 6 parts

Boric acid 2 parts

Zinc Nitrate Hexahydrate (Zn (NO ₃ ) ₂ · 6H ₂ O) .. 10 parts

The above mixture is easy to granulate and is stable in a granulated form. Part of this

Mixture, dissolved in 6 parts of water, results in a solution with a pH value of about 6. One immerses cellulose-containing material in a bath of this solution at its boiling point, this has a zinc content of up to 3 percent by weight, which of course depends on the duration of the dive. Retains such material - without further fixation - its antimicrobial properties up to about 10 washes.

Example 7

The product according to Example 6 with a zinc content of 3% _ is fixed by for 5 minutes immersion in a 2% urea solution at 8O ⁰ C. A certain product treated in this way, such as hospital linen, retains its antimicrobial properties even after 50 washes against normal skin bacteria, as was shown in the inhibition zones in the standard agar test in Petri dishes.

Example 8

The product according to Example 6 with a zinc content of 2% is dipped for 7 minutes until 65 ° C fixed in a bath with 3% monoethanolamine. Handkerchiefs treated in this way retain their antimicrobial properties even after long use and many washes.

Example 9

A product that was treated as in Example 6, 3 minutes, fixed in 10 volumes of peroxide at 25 ⁰ C for. The product, knitted breeches, withstood 50 washes and retained its antimicrobial properties, as demonstrated by a zone of inhibition in the test in Petri dishes on common skin bacteria.

Example 10

Tetra-sodium salt of ethylenediamine

Tetraacetic acid 1 part

Non-ionized detergent 1 part

Sodium acetate 5 parts

Borax 2 parts

Zinc chloride 10 parts

The above mixture easily granulates by exchanging the crystal water between borax and zinc chloride. A part of this mixture, dissolved in 9 parts of water, results in a bath with a ρκ of about 8. Protein-containing material such as wool, silk, leather and catgut seams that is immersed in the bath will be absorbed up to 4% zinc within the protein molecule. The zinc can be in the molecule by any of the fixing baths that are used in conjunction with cellulose-containing! Material with similar antimicrobial results mentioned should be permanently fused. It it could be observed that the protein substances do better at lower temperatures, but for a longer period of time are to be handled. Wool fabric shows after 15 minutes Immersion time in the above solution at 65 ° C a zinc content of over 1%, fixed in the tissue. It has also been observed that treated dyed fabrics have a greater resistance to active rays when tested in the fadeometer showed as untreated colored material. The presence of a chelating agent seems to have the double effect of facilitating the introduction of zinc into the molecules of the organic material and the detoxification of the product obtained by rendering each one harmless To have excess zinc salts which have come into contact with it in some other way could be.

Claims (4)

PATENT CLAIMS: 1. A method for treating fibrous materials or compact masses of organic material such as cellulose, egg white and the like. To achieve antimicrobial properties, the material being treated in the presence of a sequestering agent in a zinc salt solution, characterized in that the material is simultaneously with the first or subsequent to the first treatment is treated with amines. 2. The method according to claim 1, characterized in that that urea is used as the amino group carrier substance. 3. The method according to claims 1 and 2, characterized in that the ρπ value of the Treatment solution is set not higher than 8. 4. Process according to claims 1 to 3, characterized in that it is carried out at a temperature of over 50 ^° C. Considered publications:
U.S. Patent No. 2,594,384;
Martell Calvin: Die Chemie der Metallchelatverbindungen, 1958, pp. 459/460;
TAPPI, 39, 1959, pp. 557 to 567. © 309 548/317 3.63