JPH02307976A - Anti-fungus agent for textile and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title anti-fungus agent with high washing fastness by making metallic ions having anti-fungal effect adsorb to a phenolic chelate resin. CONSTITUTION:Firstly, phenolic chelate resin powder is prepared by polycondensation between a phenol, aldehyde and chelating agent (e.g. diethylenetriamine, iminodiacetic acid) at the molar ratio: chelating agent/phenol = 0.1-1.0 (pref. 0.2-0.5). The present powder is then mixed with an aqueous solution containing an anti-fungal metal (pref. silver, copper or zinc) salt, thus obtaining the objective anti-fungus agent. A textile is coated with this anti- fungus agent together with a resinous binder to obtain a cloth having anti-fungal effect with both high washing fastness and persistence.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antibacterial agent for textiles and a method for producing the same.

(Conventional technology) Traditionally, it has been used as a method to impart antibacterial properties to fibers.

A method of mixing an antibacterial agent such as an organosilicon quaternary ammonium salt or an aromatic halogen compound at the time of fiber production, a method of impregnating it into a fiber fabric, or a method of mixing an antibacterial agent with a resin that has an affinity for the antibacterial agent. Coating or laminating methods have been used on fabrics. However, since the antibacterial agents used in the fabrics with antibacterial properties obtained by these methods have a low molecular weight, the antibacterial agents elute when washed, resulting in lack of long-lasting antibacterial effects and poor durability. It had drawbacks.

(Problems to be Solved by the Invention) The present invention was made in view of the current situation, and an object of the present invention is to obtain an antibacterial agent for textiles that has excellent washing durability.

(Means for Solving the Problems) The present invention achieves the above object and has the following configuration.

In other words, the present invention is directed to ``an antibacterial agent for textiles prepared by adsorbing metal ions having an antibacterial effect to a phenolic chelate resin'' and ``a part of phenol obtained by polycondensing phenols, aldehydes and a chelating agent. ``A method for producing an antibacterial agent for textiles, which comprises immersing a polycondensate in which chelate groups are bonded to all parts thereof in an aqueous solution of a metal salt having an antibacterial effect, followed by washing with water and drying.'' be.

The present invention will be explained in detail below.

What is the phenolic chelate resin referred to in the present invention?

For polycondensation of phenols and aldehydes.

It is a polymer obtained by binding a chelating agent to part or all of phenol.

Phenols here include phenol, alkyl-substituted phenols such as cresol and xylenol, polyhydric phenols such as resorcinol and catechol, and compounds with phenolic hydroxyl groups such as α-naphthol, and one or more of these may be used alone or in combination. A mixture of these may also be used.

Aldehydes include aldehyde derivatives such as formaldehyde, paraformaldehyde, and hexamethylenetetramine, aliphatic aldehydes such as acetaldehyde and propionaldehyde, aromatic aldehydes such as benzaldehyde, and heterocyclic aldehydes such as furfural. Of these, one or a mixture of two or more may be used.

In addition, the chelating agent referred to in the present invention is a compound that coordinates with a heavy metal ion to form a chelate compound, and includes amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine, iminodiacetic acid, Aminocarboxylic acids such as reaction products of the above amines and halogenated acetic acid, and jetanolamine.

Alcohol amines such as propatool amine, etc.
These may be used alone or in a mixture of two or more.

Among general phenolic resins, resol resins that harden only by heat treatment, and novolac resins that harden by adding aldehydes, etc., are well known.However, even in phenolic chelate resins, the molar ratio of aldehydes and phenols is (below.

It is abbreviated as F/P. ), it is possible to produce resol type or novolak type resins. That is, in order to obtain a resol-type phenolic resin that cures only by heat treatment, the F/P should be in the range of 1.1 to 2.5, and in the case of a novolac-type phenolic chelate resin that requires crosslinking treatment other than heat treatment, F/P 0.5-1.1
It is necessary to

In addition, the amount of chelating agent added is as follows for both resol type and novolak type phenolic chelate resins:
The molar ratio of chelating agent/phenols is 0.1 to 1.0.
Preferably, it is in the range of 0.2 to 0.5.

The phenolic chelate resin is produced as follows. First, a mixed aqueous solution consisting of phenols, aldehydes, and a chelating agent is maintained at a temperature of 20 to 90°C, preferably 30 to 50°C.

The reaction is allowed to proceed with stirring for 2 to 3 hours. Furthermore, phenols and aldehydes are added to proceed with the condensation reaction. It is desirable that the reaction temperature here be controlled at 50 to 90°C and gradually raised. Finally, the temperature is maintained at 90 to 110°C, and the reaction is allowed to proceed under reflux. The viscosity of the reaction solution increases with each reaction time, and when the desired first stage of condensation is reached, it can be washed with water and dehydrated under reduced pressure or normal pressure to obtain a resin composition. Here, if the resin is a resol type.

The obtained resin was pulverized and dried in a hot air dryer at 120℃ for 2 to 3 minutes.
Allow time to cure. In addition, if it is a novolac type, the obtained resin is crushed and then immersed in an aqueous aldehyde solution for one day and night.
Next, after heating and mixing at 90°C for 1 hour, the resin was heated at 120°C.
Heat at ℃ for 2 hours.

Further, in the case of crosslinking a novolak type resin, in order to increase the crosslinking rate, it is preferable to add an acid such as hydrochloric acid or oxalic acid as a catalyst to the above-mentioned aldehyde aqueous solution.

The antibacterial agent of the present invention is obtained by adsorbing metal ions having an antibacterial effect on the above-mentioned phenolic chelate resin.

Here, examples of metal ions having an antibacterial effect include ions of silver, copper, iron, zinc, tin, chromium, nickel, mercury, cadmium, lead, bismuth, and the like. Among these, especially silver.

Copper and zinc ions are preferred.

As a method for adsorbing these metal ions to the phenolic chelate resin, a known method may be used.
An antibacterial agent of the present invention can be obtained by soaking for 24 hours, washing with water, and drying. The concentration of the aqueous metal salt solution and the immersion time may be appropriately determined depending on the number of adsorption seats and particle size of the chelate resin.

The present invention consists of the above-mentioned constitution. 1. By using the antibacterial agent of the present invention, antibacterial fibers having excellent washing durability can be obtained.

(Function) The antibacterial agent for textiles of the present invention is made by adsorbing metal ions having an antibacterial effect onto a phenolic chelate resin. 1. Why the antibacterial agent of the present invention has excellent washing durability. 2. The present inventors speculate as follows regarding the reason.

In the antibacterial agent for textiles of the present invention, the metal ion having antibacterial effect and the ion exchange group in the phenolic chelate resin are coordinately bonded, and the metal ion exists stably, so that it does not come off when washed. It is thought that the antibacterial effect with excellent durability will be exhibited.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples, and the measurement of antibacterial performance in the Examples will be as follows.

It was done in the following way.

(1) Antibacterial shake flask method (bacterial count reduction rate test) Test bacterial strain> Staphylococcus Aureus
Test method> Sterilized non-antibacterial treated cloth (or chelate resin) and antibacterial treated cloth (or metal ion adsorption chelate resin of the present invention).

Add the suspension buffer of the test bacteria to each, and place in a sealed container for 1 hour.
The number of viable bacteria was measured after shaking at 50 times/min for 1 hour, and the rate of decrease in the number of bacteria in the suspension injected to antibacterial-treated cloth was compared to the number of bacteria in the suspension injected to non-antibacterial-treated cloth. (%) was calculated.

Example 1 First, the phenolic chelate resin used in the two examples was manufactured by the following method.

23.5 parts of phenol, 33.3 parts of iminodiacetic acid.

Mix 20.3 parts of 37% formalin and 80 parts of water.

Stir at 70°C for 3 hours, then add 23.5 parts of phenol,
12.2 parts of 37% formalin was added and reacted at 90 to 95°C for 3 hours. After the reaction is completed, the two reaction mixtures are heated to 100~
It was heated to 110°C and dehydrated. The obtained resin is crushed,
After immersing in a 1:1 mixture of 35% hydrochloric acid and 37% formalin for one day and night, and then heating and mixing at 90°C for 1 hour,
The resin was dried at 120°C for 2 hours to obtain a phenolic chelate resin powder.

using the phenolic chelate resin powder described above.

The antibacterial agent for textiles of the present invention was obtained by the following method.

After immersing 45 g of the above phenolic chelate resin in 250 ml of a 2M silver nitrate aqueous solution adjusted to pH 4 for 6 hours, it was filtered, washed with water and dried, and the powder was further ground to an average particle size of 10 μm to give 95 mgA g/g-Dr.
An antibacterial agent for textiles of the present invention having an adsorption amount of yRe5in was obtained.

An antibacterial coated fabric was produced using the above-mentioned antibacterial agent according to the following method.

First, as a base fabric, both the warp and weft are made of nylon 70 denier/34 filament with a warp density of 120 threads/
A plain woven fabric (taffeta) with a weft density of 90 threads/inch is prepared, and after scouring and dyeing with acid dye in the usual way, it is coated with Asahi Guard 710, a fluorine-based water repellent.
(Asahi Glass ■Product) Padding with 3% aqueous solution (aperture rate 3
5%).

Heat treatment was performed at 160° C. for 1 minute. Next, using a calendering machine with mirror-finished rolls, the temperature was 160°C and the pressure was 30kg/crf1. Calendar processing was performed at a speed of 20 m/min, and then a coating amount of 30 m/min was applied using a knife-over roll coater with the resin solution shown in Formulation 1 below.
After application at g/m'.

It was dried at 80° C. for 3 minutes to obtain a coated fabric containing the antibacterial agent for fibers of the present invention.

[Formulation 1] Methyl ethyl ketone 15 parts toluene
15 parts water
40 parts silver ion-adsorbing phenolic chelate resin 3 parts 9 for comparison with the present invention Sanitized 1977 was used in place of the silver ion-adsorbing phenol chelate resin in Formulation 1 of this example.
(Silicon quaternary ammonium salt 9 Japan Sanitize @J
A comparative coated fabric was obtained in exactly the same manner as in Example 1, except that the following product was used.

The antibacterial performance of the coated fabric using the antibacterial agent of the present invention obtained as described above and the comparative coated fabric were measured, and the results are shown in Table 1.

In Table 9, after washing, JIS L-0217103
Indicates that washing according to the method is repeated 20 times.

As is clear from Table 1, the coated fabric using the antibacterial agent of the present invention has antibacterial properties with excellent washing durability.

Example 2 37.6 parts of phenol, 26.6 parts of iminodiacetic acid.

A mixed aqueous solution of 16.2 parts of 37% formalin and 80% water was gradually heated from room temperature to 70°C, stirring was continued for 3 hours, then 32.4 parts of formalin with a concentration of 37% was added, and the temperature was raised to 90°C. The temperature was maintained at ~95°C and the reaction continued for 3 hours. Next, after washing with water, one reaction system was dehydrated under reduced pressure to obtain 73 parts of a pale yellow resin.

The powdered resin obtained by crushing this was dried in a hot air dryer.
The mixture was cured at 20° C. for 2 hours to obtain a phenolic chelate resin powder.

Using this phenolic chelate resin powder.

The antibacterial agent for textiles of the present invention was obtained by the following method.

1.5M copper sulfate aqueous solution adjusted to pH 4.5 30.0ml
After immersing 50 g of phenolic chelate resin in 1 liter for 8 hours, filtering, washing with water, and drying, 100 mg Cu/
An antibacterial agent for textiles of the present invention having an adsorption amount of g-Dry Re5in was obtained.

The antibacterial properties of the phenolic chelate resin powder of the present invention obtained as described above were measured.

It showed excellent antibacterial properties with 99% antibacterial properties.

In order to measure the antibacterial washing durability of this phenolic chelate resin powder, when producing the coated fabric in Example 1, the above phenolic chelate resin powder (
A coated fabric using the antibacterial agent of the present invention and a comparative coated fabric were obtained in exactly the same manner as in Example 1, except that copper ion adsorption) was used. Performance was measured in the same manner below, and the results are shown in Table 2.

In addition, in Table 2, after washing, JIS L-0217103
Indicates that washing according to the method is repeated 20 times.

As is clear from Table 2, the coated fabric using the antibacterial agent of the present invention has antibacterial properties with excellent washing durability.

(Effects of the Invention) The antibacterial agent for textiles of the present invention is obtained by adsorbing metal ions having antibacterial properties to a phenolic chelate resin, and according to the present invention having such a structure.

It is possible to obtain an antibacterial agent for textiles that has excellent washing durability.

Claims (2)

[Claims] (1) An antibacterial agent for textiles made by adsorbing metal ions with antibacterial activity onto a phenolic chelate resin. (2) A polycondensate obtained by polycondensing phenols, aldehydes, and a chelating agent, in which a chelate group is bound to part or all of the phenol, is immersed in an aqueous solution of a metal salt having antibacterial activity, and then A method for producing an antibacterial agent for textiles, which comprises washing with water and drying.