JPH0280051A - Sterilizing and deodorizing high molecule - Google Patents

Abstract

PURPOSE:To obtain an excellent sterilizing effect and deodorizing effect by anionizing a high molecular substance and connecting to it a substance having cation or both nature sterilization or sterilizing function reacting for a functional group having the anion. CONSTITUTION:A high molecular substance is anioized, and a substance, having a cation or both nature sterilization or sterilizing function reacting for a functional group having the anion, is connected to the anionized high molecular substance. The high molecular substance may be a natural high molecule such as fiber, plastic or wood. A reaction type anionizing agent is a reaction object of a compound (A) having an active hydrogen atom and anion radical simultaneously in the same molecule and of a compound (B) having a reaction quality with the compound (A), using acid sodium sulfite, sodium isothionic acid, etc., as the compound (A) and epichlorohydrin, epibromhydrin, etc., as the compound (B). The cation or both nature sterilizing or deodorizing substance is metal ion of copper, iron, etc., and the compound, having cation quality sterilizing and deodorizing function, is a compound having a nitrogen contained radical of tertiary amine and quadratic ammonium or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polymer having a sterilizing or deodorizing function.

[Prior Art] Recently, various attempts have been made to impart sterilizing and deodorizing functions to polymeric substances such as various textile products and plastic films. This plays a part in the development of functional fibers for medical and other new uses, and is also responsible for the development of textile products closely related to daily life, such as underwear and futons, based on the recent development of hygiene concepts and improvement of lifestyles. This is in response to demands for quality improvement. Furthermore, it is ideal to eliminate bad odors at the source, and in order to cope with the increasing demand for deodorizing functions for clothing, garbage bags, etc., and the expansion of fields that require sterilization and deodorization, such as food preservation. It is.

To provide these functions, thin copper wires have been woven into socks for some time to suppress the growth of athlete's foot fungi and prevent bad odors through the action of copper ions. Recently, various organic and inorganic chemicals and natural substances with sterilizing and deodorizing functions are directly mixed (in the case of synthetic fibers and plastic films), and resin liquids mixed with disinfectants and deodorizing agents have been used. Fibicides and deodorizers are applied by impregnating textiles and films, or directly applying disinfectants and deodorants to textiles.

Note that sterilization originally refers to killing microorganisms such as bacteria and mold, but in the present invention it is used as a concept that also includes sterilization, which inhibits the growth and activity of microorganisms. In addition, deodorization refers to making odor less noticeable to humans, and is carried out by adsorbing and removing malodorous substances, masking them, making them odorless through chemical reactions, and preventing the generation of malodorous substances through sterilization.

[Problems to be Solved by the Invention] However, all of the conventional methods of imparting sterilizing and deodorizing functions have drawbacks. That is, in the method (2) above, most of the disinfectant and deodorant are sealed inside the fibers or film, so the effectiveness is greatly reduced. Moreover, many organic substances decompose when the resin melts (there are restrictions on the types of fibers and resins that can be mixed in, as well as the disinfectants and deodorants used. In the case of (2) above, disinfectants and deodorizers are also Since it is wrapped, it is difficult to achieve sufficient effect, and the hardened resin deteriorates the texture of the textile product.In the case of ■, the adhesion strength to the fiber or film is weak and the amount of adhesion is small, so the sterilization is not sufficient. In many cases, they do not exhibit deodorizing or deodorizing effects, and their washing resistance and abrasion resistance are poor, making them unsuitable for practical use.

Recently, in order to solve the above-mentioned problem of poor adhesion to fibers, a method has been developed to synthesize a polymer with a functional group that can bind to a substance that has a deodorizing function, and to bind the substance to it to make a deodorant fiber. It has been devised. However, because this method requires the synthesis of a special polymer that becomes the fiber, it cannot be used for the fiber (polymer) inside the shell, and the special fiber itself has poor physical properties as a fiber. It also has the disadvantage of

Furthermore, in order to increase the binding force of the deodorizing substance to the fibers, a method has been devised in which the fibers themselves are not stretched, leaving a large amount of amorphous portion. However, with this method, the tensile strength of the fiber itself is very low, and it is not practical as a fiber.
It could only be used for very special purposes.

Due to the above circumstances, this industry has developed products such as sterilizing and deodorizing fibers and films that have high adhesion efficiency for sterilizing and deodorizing substances, do not reduce their sterilizing and deodorizing abilities, and are highly durable and can withstand long-term use. There has been a desire for the emergence of polymeric substances.

[Means for Solving the Problems] In view of the above-mentioned current situation, the present inventor has completed the sterilizing and deodorizing polymer of the present invention as a result of intensive research. The point is that a cationic or amphoteric sterilizing or sterilizing substance that reacts with the anionized functional group is bonded to the anionized polymer.

That is, it is characterized in that a substance having a sterilizing or deodorizing function is not directly attached (bonded, etc.) to a polymer such as fibers, but the polymer is anionized.

Here, the polymer substance refers to a normal polymer and its use is not limited. That is, it may be used as a fiber or as a plastic. Alternatively, it may be a natural polymer such as wood.

For example, natural fibers such as cotton, silk, and wool, chemical fibers such as rayon, acetate, and cupro, synthetic fibers such as nylon, and polyester, as well as paper, leather, valves, starch,
Other examples include polyvinyl alcohol, chitosan (a polysaccharide obtained by deacetylating chitin, which is present in large amounts in nature as a component of the outer shell of crustaceans), and various films made of natural polymers and synthetic resins.

Examples of uses for this type of product include the following.

Fibers are used for clothing, bedding cotton, diapers, sanitary socks, etc., and plastics are used for various packaging containers, wrapping films, etc.

The deodorizing polymer of the present invention can be used not only in fibers and other polymers, but also as a part thereof. For example, in the case of fibers, it is used by blending or interweaving with other fibers, and in the case of plastics, it is used by melt-mixing.

Anionization refers to adding an anion to a polymer, and any method, anionization agent, etc. may be used for this purpose. Adding an anion includes adding an anion to a polymer molecule by bonding (reacting) an anionic functional group to the molecule, or adsorbing/fixing an anion-containing molecule to a polymer. It is a concept.

Reactive anionizing agents mainly react with natural polymers such as cellulose fibers, silk, wool, wood, and chitosan. Adsorption-fixing type anionizing agents are mainly adsorbed and fixed to synthetic polymers such as polyester fibers, nylon fibers, acrylic fibers, and vinyl chloride resin films, and are themselves polymers.

There are various types of reactive anionizing agents, but the anionizing agent developed by the present inventor (Japanese Patent Application No. 60-22742)
No. 1) reacts well with various natural fibers, recycled fibers, and semi-synthetic fibers. This includes a compound (A) that simultaneously has an active hydrogen atom and an anionic group in the same molecule, and a compound (A) that has reactivity with the compound (A) and has reactivity with other active hydrogen atoms, or has reactivity with other active hydrogen atoms. Group-generating compound CB)
It is a reaction product with. Specific compounds include (A) sulfonic acid salts such as acidic sodium sulfite, sodium isethionate, sodium phenolsulfonate, taurine, sodium aniline sulfonate, sodium hydroxyacetate, sodium hydroxybenzoate, sodium aminobenzoate, and tartaric acid. Examples include carboxylic acid salts such as soda, but are of course not limited to these. As the compound (B), epihalohydrins such as epichlorohydrin, epibromohydrin, and epicotehydrin, or cyanuric halides such as cyanuric chloride, cyanuric bromide, and cyanuric chloride are used.

The reaction between the addition reaction product of compound (A) and epihalohydrin and the substitution reaction product of compound (A) and cyanuric halide with the polymer (fiber) is performed by reacting the addition reaction product or substitution reaction product with the polymer (fiber). This is an addition reaction or substitution reaction with active hydrogen atoms contained in the molecular (fiber) material. These reactions are carried out without a catalyst or in the presence of an alkaline compound such as soda ash or caustic soda. In addition, these reactants are anhydrous mirabilite,
It reacts more efficiently with polymers (#J!A fiber) using an alkali catalyst in the presence of an inorganic salt compound such as common salt.

Adsorption-fixing type polymer anionizing agents include polymerization type polymers and condensation type polymers. Examples of the former include (a) styrene sulfonic acid (or its salt), tertiary-butylacrylamide sulfate (TBAS), (C)
Sodium sulfoprobyl acrylate) (SSPA)
and (d) homopolymers of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride.

Furthermore, there are copolymers of the above substances (a) to (d) with ethyl acrylate, propyl methacrylate, N-methylol acrylamide, olefinic monomers such as ethylene and propylene, and the like.

Examples of the latter (condensation type polymer) include (formalin condensate of al-naphthalene sulfonic acid (or salt)), (b) sulfofucuric acid or its methyl ester, etc., and polyols such as ethylene glycol, polyethylene glycol, glycerin, and polyglycerin. Examples include condensates with.

The above-mentioned anionizing agent is just an example, and any agent that can anionize a polymeric substance may be used.

The method of anionization is also not particularly limited, and any conventional method may be used.

Next, a cationic or amphoteric bactericidal or deodorizing substance to be reacted and bonded with an anionized polymer will be explained.

The cationic or amphoteric sterilizing or deodorizing substance refers to a compound that is cationic or amphoteric and has a sterilizing or deodorizing function, or a metal ion such as copper or iron. If the sterilizing or deodorizing substance does not exhibit cation or amphoteric properties, it may be synthesized by introducing a cationic group through a chemical reaction.

Most of the compounds with cationic bactericidal and deodorizing functions are those having nitrogen-containing groups such as tertiary amines and quaternary ammonium salts. For example, amidines such as formetanate, guanidines such as guazatine and chlorhexidine,
Quaternary ammonium salts such as benzalkonium chloride, pyridines such as acrotiben and omedine, acridines such as acriflavine and ribanol, ethyrimol,
2 Pyrimidines such as (3,5-dimethylpyrazolyl]-4-hydroxy-6-phenylpyrimidine, pyrroles such as noformicin, imidazoles such as 2-(4-thiazolyl)benzimidazole (thiabendazole), benzoxa 3-(5
Examples include nitrofurans such as '-nitro-2'-furfurindene)-oxindole.

Metal ions such as iron, copper, manganese, cobalt, and nickel also act as cationic disinfectants.

As an amphoteric bactericidal and deodorizing substance, mercaptobenzthiazole monoethanolamine salt (Vancide-
20,-20S), lauryl pyridinium chloride salt (cyancide-26.-26EC), and hydroxamic acid-based amphoteric surfactants.

All of these are disinfectants, and their deodorization results from inhibiting the growth and killing of microorganisms that produce malodorous substances. In contrast, there are few cationic substances that exhibit direct deodorizing functions. Therefore, there is also a method of using a deodorizing substance that does not have a cationic group but into which a cationic group is introduced. As an example of this, a phthalocyanine derivative such as iron phthalocyanine tetracarboxylic acid may be esterified with an alcohol amine such as N,N-dimethylaminoethanol, and then quaternized with an alkyl halide or dimethyl sulfate.

A phthalocyanine derivative directly cationized may also be used.

In the present invention, the sterilizing and deodorizing substance is firmly and efficiently bound to the polymer by anionizing the polymer and binding the cationic part of the sterilizing and deodorizing substance to the anionized part. It is distinctive in that the anionizing agent and the sterilizing and deodorizing substance themselves may be conventional ones, and no rights are claimed for them.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Example 1 As an anionizing agent, an equimolar compound of acidic sodium sulfite and epichlorohydrin developed by the present inventor (patent application No. 6 O
-227421), and 5% caustic soda is added to an aqueous solution containing 20% (weight %, same hereinafter) of the treatment liquid.

The scoured broad cotton cloth was immersed in the above treatment solution at room temperature for 1 minute (bath ratio 1:30), squeezed with a roll to a squeezing rate of 80%, and immediately dried at 110° C. for 10 minutes. This was thoroughly washed with water, neutralized with an acetic acid solution, further washed with water, and dried.

Next, the monoethanolamine salt of mercaptobenzthiazole (Vancide-
The treated cotton broadcloth was immersed in a 10 g/l aqueous solution of 20, -20S) at 60°C for 30 minutes (bath ratio 1:
30) After drying, the fabric was dehydrated and dried to obtain an anti-mildew-treated fabric.

In a comparative example, a white cotton broadcloth that had not been anionized was treated by soaking it in the antifungal solution in the same manner.

Each sample obtained by the above method was tested for mold resistance before and after washing (JISZ-2911-1).
981) was carried out. Before washing, both the Examples and Comparative Examples were good (4th to 5th grade), but after washing, there was no change in the Examples, but in the Comparative Example, the mold resistance was 1st grade and almost lost.

In each example, the washing conditions were as follows: 2 g/l of detergent (Lion ■, household detergent "Top") was added, stirred at 40°C for 5 minutes (bath ratio 1:100), and washed with water for 2 minutes. , 110
One cycle of drying for 10 minutes at °C was repeated three times.

Example 2 As an anionizing agent, an equimolar compound of taurine and cyanuric chloride developed by the present inventor (Japanese Patent Application No. 6O-227
421), and 5% caustic soda is added to an aqueous solution containing 20% of the solution to prepare a treatment solution.

The wool yarn was immersed in this treatment solution at 30° C. for 2 hours (bath ratio 1:30), washed with water, neutralized with acetic acid solution, washed with water, and air-dried.

The treated yarn was then soaked in a 10% aqueous solution of copper sulfate for 40 minutes.
The yarn was immersed at ℃ for 60 minutes (bath ratio 1:30), washed with water, dehydrated and dried to obtain a sterilized wool yarn.

The comparative example was immersed in a copper sulfate solution under the same conditions and dried without anionization treatment.

For each sample obtained by the above method, an antibacterial test (halo test) was conducted before and after washing. That is, Staphylococcus aureus at a concentration of 1 x 10 ca/g was added to 100 n 11 L of Tryptotsuya agar Q, l + nl.
Use the mixture in the following ratio. Next, put 10
m1 to make a thin layer medium, samples were arranged on it in a size of 3 x 3 cni, and cultured at 37°C for 24 hours. Then, the state of bacterial growth was visually observed to determine the antibacterial properties.

As a result, in the example, a bacterial growth inhibition zone was clearly visible and transparent under the sample before and after washing, but in the comparative example, there was a bacterial growth inhibition zone under the sample before washing. However, it was somewhat opaque, and no inhibition zone was visible after washing.

Example 3 A copolymer of sodium acrylate, ethyl methacrylate, and N-methylol acrylamide (molar ratio 4:1:0.2) was used as an anionizing agent, and a 20% aqueous solution thereof was used as a treatment liquid.

A polyester nonwoven fabric was immersed in this treatment solution at room temperature for 5 minutes, squeezed with a roll to a squeezing rate of 80%, and immediately dried for 10 minutes in a hot air dryer kept at 110°C.

Subsequently, the pretreatment was completed by heat treatment at 160'C for 5 minutes.

Next, as a deodorant solution, N,N-dimethylaminoethanol ester of iron phthalocyanine tetracarboxylic acid was prepared as a quaternary ammonium salt with dimethyl sulfuric acid.
% aqueous solution was prepared. The pretreated polyester nonwoven fabric was immersed in this solution at 60°C for 30 minutes (bath ratio 1:20).
After that, it was dried to obtain a deodorizing nonwoven fabric.

In a comparative example, a polyester nonwoven fabric that had not been anionized was similarly immersed in a deodorant solution.

For each sample obtained by the above method, a deodorization test was conducted before and after washing. Deodorization test is 1010
A test cloth (100 g) was placed in a 0O flask, and trimethylamine was injected as a malodorous substance to a concentration of 10 PI'M. Then, the concentration of trimethylamine immediately after injection and 24 hours after injection was compared to determine the rate of decrease in the concentration. In the fabric of the example, it was 98.5% before washing and 82.3% after washing.
%, and in the comparative example, it was 90% before washing and 23.5% after washing.

Example 4 A copolymer of sodium methacrylate, N-methylolacrylamide, and propyl acrylate (molar ratio 4:0.3:0.8) was used as an anionizing agent.
A 0% aqueous solution was made into steel and used as a treatment liquid.

Nylon socks were immersed in this treatment solution for 1 minute at room temperature, squeezed to 80% using a centrifugal water heater, and dried at 100° C. for 10 minutes. Next, heat treatment was performed at 150° C. for 5 minutes to obtain anionized socks.

Treated nylon socks are treated with disinfectant for 2 (3
, 5-dimethylpyrazolyl]-4- and droxy-6-phenylpyrimidine in a 10% solution of isopropanol (room temperature, 60°C), washed with water, and dried to obtain sterilized socks.

The comparative example is nylon socks that have not been anionized.
It was treated in the same way by immersing it in a disinfectant solution.

For each sample obtained by the above method, an antibacterial test was conducted in the same manner as in Example 2 before and after washing.

As a result, the sample of the example was transparent with a clear bacterial growth inhibition zone under the sample before and after washing, while the comparative example had a bacterial growth inhibition zone under the sample before washing. It was somewhat opaque and no inhibition zone was visible after washing.

Example 5 As an anionizing agent, an equimolar mixture of 4-sulfofucuric acid and ethylene glycol was linearized at 200 to 250° C. for 8 hours, and a 15% aqueous solution thereof was prepared as a treatment liquid.

Leather (cow tanned leather) was immersed in this treatment solution at 40° C. for 30 minutes, squeezed to 80% with a roll, and then dried.

The treated leather was immersed in a 10% aqueous solution of 2-(4-thiazolyl)benzimidazole (thiabendazole) at room temperature for 5 minutes, squeezed to 100% with a roll, and dried to obtain sterilized leather.

A comparative example was immersed in the above sterilization solution without anionization treatment and dried in the same manner.

An antibacterial test (staphylococcus) was conducted in the same manner as in Example 2 for each sample obtained by the above method. As a result, the sample of the example was transparent with a clear bacterial growth inhibition zone under the sample before and after washing, while the comparative example had a bacterial growth inhibition zone under the sample before washing. It was somewhat opaque and no inhibition zone was visible after washing.

Example 6 An equimolar compound of sodium tartrate and epichlorohydrin was used as an anionizing agent, and an aqueous solution containing 15% thereof was
5% caustic soda was added to surround the treatment solution.

Wood chips are mixed with this treatment solution and stirred at 70° C. for about 60 minutes. Thereafter, the chips were taken out and dried.

The treated wood chips were dissolved in an 8% aqueous solution of 3-(5'-nitro-2'-furfurindene)-oxindole.
It was immersed at 0°C for 30 minutes and subjected to antibacterial treatment.

In the comparative example, only antibacterial treatment was performed under the above conditions without anionization treatment.

The antibacterial-treated wood chips had a seedling reduction rate of 96% against Staphylococcus aureus using the shake flask method.

This value indicates sufficient antibacterial performance. In addition, even when soaking and drying in warm water (50°C) were repeated 3 and 5 times, the reduction rate of seedlings hardly decreased.

On the other hand, in the comparative example, the seedling reduction rate was 65% at first, but
After 5 times of immersion drying in warm water, the value became almost 0. This indicates that almost no fungicide was attached to the wood chips that had not been anionized.

Example 7 Tertiary-butylacrylamide sulfate (TBAS), ethyl acrylate, and N
- Copolymer with methylol acrylamide (molar ratio 5
: 1 : 0.3), and its 10% aqueous solution was used as the treatment liquid.

This treatment solution was applied to a vinyl chloride film (thickness 50μ).
(10 g/rrf) and dried at 100° C. for 5 minutes to complete the pretreatment.

Next, a 10% aqueous solution of guazatine was applied to the anionized film (5 g/nr) at 100°C.
and dried for 5 minutes. In a comparative example, a 10% aqueous solution of guazatine was applied and dried in the same manner without pretreatment.

The reduction rate of seedlings on this sterilized plastic film is
It was 86% by shake flask method.

This value is sufficient to withstand use as a sterilizing film. In addition, even when soaking and drying in warm water (50°C) were repeated 3 and 5 times, the reduction rate of seedlings hardly decreased.

On the other hand, in the comparative example, the seedling reduction rate was 58% at first, but
After 5 times of soaking and drying in warm water, the film became almost O. This shows that almost no germicide was attached to the film that had not been anionized.

[Effects of the Invention] As detailed above, the sterilizing and deodorizing polymer of the present invention is a substance that anionizes a polymeric substance and has a cationic or amphoteric sterilizing or sterilizing function that reacts with a functional group having the anion. is bound to the anionized polymer. Therefore, as is clear from the experimental results, it shows superior sterilizing and deodorizing effects compared to the case where these sterilizing or deodorizing substances are attached without anionization, and even after repeated washing. It can be seen that although the effect significantly decreases in the comparative example, the polymer of the present invention shows very little decrease and has very high washing fastness.

This makes it possible to impart sterilizing and deodorizing functions to various textile products. It can also be used for plastic films, etc., and is a useful invention with a wide range of applications.

Claims (1)

[Claims] 1. A polymer substance is anionized, and a cationic or amphoteric substance having a bactericidal and/or deodorizing function that reacts with the anion-containing functional group is bonded to the anionized polymer. Sterilizing and deodorizing polymer.