JPH02112483A - Production of antimicrobial fibrous product having improvds susceptibility to discoloration - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial fibrous product having improved susceptibility to discoloration by treating a fibrous material with an organosilicone containing a quaternary ammonium base and then partially hindering the cation with an anionic surfactant. CONSTITUTION:Natural fiber or synthetic fiber is an organosilicone containing a quaternary ammonium base shown by the formula (R is alkoxy, halogen, acyl, etc.; R' is <=20C bifunctional hydrocarbon; R'' is lower alkyl; R''' is 1-20C alkyl, alkenyl, cycloaliphatic hydrocarbon group, aromatic group, etc.; n is 1-3; X is anion) and then with an anionic surfactant to prevent reduction in whiteness degree and yellowing of cloth especially treated with a fluorescent brightening agent and to obtain an antimicrobial fibrous product having excellent durability.

Description

DETAILED DESCRIPTION OF THE INVENTION More specifically, it is an object of the present invention to provide an antibacterial fiber product which can improve discoloration such as reduction in whitening and yellowing of fluorescently dyed products and has improved durability.

Microorganisms such as various molds and bacteria live in the atmosphere and have harmful effects on textile products and the human body. For example, human sweat, food and drinks, etc. adhere to a wide range of textile products, including not only clothing and bedding, but also interior products, exterior products, etc., and the ingredients in these become a source of nutrition, causing mold and bacteria to grow. Cultivated. These microorganisms and the waste discharged from the microorganisms cause serious hygienic problems such as discoloration of the fibers, embrittlement of the fibers themselves, and generation of bad odors. Particularly in socks, underwear, casual wear, bed sheets, covers, etc., the growth, reproduction, and spread of bacteria attached to the fibers are of course harmful to human health.

Conventionally, in order to solve such problems, methods of treatment with m6M compounds, organic mercury compounds, halogenated phenol compounds, methods of treatment with cationic surfactants containing quaternary ammonium bases, and methods of treatment with quaternary ammonium ring groups have been proposed. A method of treating with a vinyl polymer having the following is known.

However, these known methods have problems such as toxicity to the human body, pollution problems of treated waste liquid, lack of durability,
The reality is that no satisfactory method is known due to problems such as discoloration due to processing. In particular, cationic polymers with quaternary ammonium bases are attracting attention because they have fewer problems such as toxicity (for example,
-45485). However, these processing agents not only have problems with durability and texture, but also lose their fluorescence, especially when processed into fluorescent whitening products, since most of the fluorescent brightening agents are dyes containing anionic groups. It has drawbacks such as yellowing and yellowing.

As a result of intensive research, the present inventors have solved these drawbacks and obtained a textile product that maintains excellent antibacterial properties, improves the durability of antibacterial properties, and prevents white skin deterioration and yellowing. , arrived at the present invention. That is, it is characterized in that the quaternary ammonium cation in the organosilicone is at least partially blocked by treatment with a left anionic surfactant.

The textile product according to the present invention retains the excellent antibacterial properties of organosilicone containing a quaternary ammonium base, has improved washing durability, and can prevent deterioration of white skin and yellowing due to treatment. In addition to these advantages, it has many other features such as improved water absorption. Another major feature is that the treated product has an excellent texture.

The organosilicone having a quaternary ammonium base used in the present invention includes a tertiary nitrogen-containing group,
For example, an organosilicone having a structure obtained by quaternizing a diorganopolysiloxane having a siloxane unit having a dialkyl-substituted aminoalkyl group, the general formula % is a lukoxy group, a halogen atom, an acyl group, and even if the U is a hydroxyl group. good. R': A divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent, or a divalent hydrocarbon group having 20 or less carbon atoms containing an oxygen atom or a nitrogen atom. Good too. f: lower alkyl group, R
″′: An alkyl group, alkenyl group, cycloaliphatic hydrocarbon group, aromatic group, aralkyl group, or alkaryl group having 1 to 20 carbon atoms.

n: a positive integer of 1 to 3, X: anion such as a chlorine atom, a bromine atom, etc. ) is exemplified. Furthermore, the latter is preferred. These compounds form a film on the fibers, and the latter compound in particular reacts with active hydrogen present in the fibers to introduce quaternary ammonium cations, resulting in excellent bactericidal and antibacterial properties against various molds and bacteria. It has a bactericidal effect. - Molds such as Black mold, Aspergillus aspergillus, Chaetomium, Arachnoid mold, Escherichia coli, Staphylococcus aureus, Corynebacterium, Durham negative rods, Bacillus, Bacillus, Coccus, etc., to name a few. Shows antibacterial and bactericidal effects against.

The fiber materials that are the object of the present invention are not particularly limited, and include natural fibers such as cotton, linen, wool, and silk, recycled fibers such as viscose rayon, ammonium rayon, and semi-synthetic fibers such as acetate. Pro-mix fibers such as protein/acrylonitrile, single or mixed fibers such as polyamide, acrylic, polyester, and polyolefin synthetic fibers, composite fibers, yarns, knitted materials, nonwoven fabrics, rugs, sewn products, etc. made of these fibers. is exemplified. Alternatively, it may be a composite product of fibers and other materials.

Textile products treated with the above-mentioned organosilicon have excellent antibacterial properties and maintain good durability against general home washing and dry cleaning. at 70°C10
The durability of the effect is still insufficient for minute treatment or high temperature treatment in an autoclave. Furthermore, when the object of treatment is white goods, especially fluorescently dyed cellulose fibers, treatment with the compound may reduce white discoloration or accelerate yellowing due to A1 aging, resulting in problems with product quality and commercial value. significantly impairs The reason for this is not clear, but it is thought to be due to poor compatibility between the processing agent and the fluorescent dye. Furthermore, when treated with the organosilicone, it becomes extremely hydrophobic, making it unsuitable for processing towels, sheets, underwear, etc. In the present invention, these drawbacks are solved at once.

The amount of the organosilicone applied is usually 0.1 to 3% by weight based on the weight of the fiber in terms of solid content, preferably 0.5% by weight. The treatment method may be any method such as submerged treatment, pad/dry treatment, spray/dry treatment, pad/steam treatment, etc., and further heat treatment may be performed as desired. However, submerged suction treatment is particularly advantageous. Processing conditions are usually bath ratio 1
: 5 to 00, room temperature to 80°C, preferably 40 to 7
Exhaustion treatment is carried out at 0°C for 30 minutes or more, and finished by hot air drying at a temperature of ao'c or more.

This is essential. Examples of anionic surfactants used include higher fatty acid salts, higher alcohol sulfate ester salts, higher alkyl sulfonates, sulfated oils, sulfated fatty acid esters, sulfated olefins, alkylbenzene sulfonates, and alkylnaphthalene sulfonates. , Paraffin Sulfin Sulfonate, Igebon T1 Aerosol OT.

Examples include higher alcohol phosphate ester salts, and these may be used alone or in combination of two or more.

The amount of anionic surfactant used is at least 1 part, preferably 50% or more, of the cationic groups possessed by the organosilicone.
More preferably, the amount is such that the entire amount is blocked. Note that effects such as water absorption and sweat absorption can be further improved by using an amount greater than the amount of blocking cationic groups, for example, 1.5 times or more.

In the present invention, the layer to which the treatment agent is applied is also important, and it is impossible to obtain excellent effects even if the treatment agent is used in the same bath.

The treatment method using an anionic surfactant may be any arbitrary method such as a dipping method or a pad method. However, when organosilicone treatment is performed by submerged treatment (immersion), after the organosilicone is absorbed into the fibers, an anionic surfactant and optionally salts and other auxiliary agents are added to the remaining bath for several minutes.
It is preferable to treat for several minutes. Therefore, the processing operation is simple and no special equipment is required, which is a great advantage.

On the other hand, in the pad method or continuous method, it is preferable to pad dry with an organosilicone solution and then pad dry again with an anionic surfactant treatment solution. However, the present invention is not limited to these processing methods; for example, the pre-process may be performed by a dipping method and the post-process may be performed by a pad method, or vice versa.

The present invention will be explained below with reference to Examples.

Example L A quaternary ammonium group-containing organosilicone represented by the following formula was prepared using a wince dyeing machine using scouring, bleaching, and fluorescent dyeing cotton 7 rice knit and rotating it in water at a bath ratio of 1:20. .2% OWF was added in portions over 10 minutes.
After that, the temperature was raised to 50°C for 15 minutes, and after processing at that temperature for 15 minutes, 1.2% OWF soap was added, followed by processing for 15 minutes, centrifuged for hydrophilization, and dried at 120°C using a short loop dryer. Treated with antibacterial treatment. In addition, a sample without soap was also prepared for comparison. The white leather, light resistance, and durability of these treated fabrics were compared. White skin is number one in Japan
A and b were measured and evaluated using a colored colorimeter. Light resistance was determined by irradiating the film with a fade-o-meter for 1.3.5 hours and comparing discoloration and fading. Durability: 50 home washes and 50 ppm
A sample treated with an aqueous solution of sodium hypochlorite at 70°C for 10 minutes was treated as Tl5-Z・291.

Antibacterial properties were tested and evaluated using the mold resistance test method of 19'76. The results are shown in Table 1. Antibacterial treated fabric without soap added has b
The value is high and the white skin is bad. Even in the fade-o-meter irradiation test, the color tends to change and fade in a short period of time. The antibacterial test results show that the antibacterial properties are good after 50 home washings, but the antibacterial properties are clearly degraded when treated with a 50 ppm sodium hypochlorite solution for 70'CX:L0 minutes. On the other hand, the antibacterial treated fabric with soap added has no decrease in white skin and no difference in light resistance compared to the untreated fabric. Furthermore, excellent antibacterial durability was observed after treatment with sodium hypochlorite.

Table 1 Examples of characteristics and effects of soap-added antibacterial treated fabric 2 Scouring, Freset and dyed polyester chassis'
Immediately after use in Example 1 of J(U%owf), immerse it in an aqueous organosilicone solution containing a quaternary ammonium base:
After raising the temperature to 60-C and treating for 20 minutes, 1% owf of sulfated fatty acid ester was added, and after treating for 10 minutes, dehydration and drying were performed to test the antibacterial durability in the same manner as in Example 1 without the addition of tf oxidized fatty acids. , and reeds, it was confirmed that the antibacterial properties of the latter did not decrease even when treated with hypochlorous acid Lada.

Examples & Coating, bleaching, mercerizing, and fluorescently dyed cotton fabrics in a 1.5% by weight solution of an organosilicone containing a quaternary ammonium base represented by the following formula:! Then, squeeze it with a mangle to a pick-up rate of about 70%, then dry it and apply an antibacterial treatment to completely adhere the organosilicon to about 1% owf'. Next, 0 to 5% by weight of dialkylsulfosuccinate
Parallel and Efi were obtained using a solution containing . When examining the relationship between the amount of attached dialkyl sulfosuccinate, white discoloration (b value), and water absorption, the results shown in Figure 1 were not obtained.
Water absorption was evaluated by dropping water droplets on a treated cloth held horizontally and measuring the time it takes for the water droplets to disperse and disappear (wicking).

0□H.

Sample 7-1 not treated with dialkyl sulfosuccinate: high b value and poor white discoloration. It also has poor water absorption.

When 7M ffi with dialkyl sulfosuccinate (■) is mixed with organosilicone at 1% owf, whitening reaches equilibrium and good whitening can be obtained. The wicking property also improves as the amount of anionic surfactant used in the soil increases.

Furthermore, the antibacterial properties of these treated fabrics were tested using the BIOAF7 method. The Bioaf 7 method is to soak a cloth with a bacterial solution containing a certain number of Durham-negative bacteria, leave it at the same temperature as body temperature for a certain period of time, measure the number of bacteria after that, and calculate the increase or decrease in bacteria as a ratio. There is a tendency to increase in untreated cloth, but it decreases in antibacterial treated cloth. The antibacterial treated fabrics according to the present invention all showed a reduction rate of 95% or more regardless of the amount of attached dialkyl sulfosuccinate, and good antibacterial effects were obtained. However, even here, the durability of antibacterial properties is limited by home washing.
There is no problem with so times, but as in Example 1, 500
When treated with ppm sodium hypochlorite solution at 70°C for 10 minutes, the amount of dialkyl sulfosuccinate deposited was 0.5.
%OWf or less, the bacterial reduction rate was 50% or less, and the effect of post-treatment was also recognized here.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the amount of dialkyl sulfosuccinate and white discoloration and wicking of a quaternary ammonium base-containing organosilicone x % owf M cloth.

Claims (1)

[Claims] 1. By treating the textile product with an organosilicone having a quaternary ammonium base and subsequently treating it with an anionic surfactant, at least a portion of the quaternary ammonium cations in the organosilicone are removed by the anionic surfactant. A method for producing an antibacterial textile product with improved discoloration property, characterized in that the product is made of antibacterial fibers.