WO1990010746A1 - Antibacterial fiber and resin and production thereof - Google Patents

Abstract

This invention relates to: (1) antibacterial polyacrylonitrile or polyester fiber and resin containing 1 to 1,000 ppm, preferably 10 to 1,000 ppm, of silver in the form of silver sulfonate, (2) a method of producing the antibacterial polyacrylonitrile or polyester fiber or resin by reacting polyacrylonitrile or polyester fiber or resin having sulfo and/or sulfonate groups in its structure with a water-soluble silver compound in water, characterized in that said reaction is carried out at a temperature above the glass transition point of the polyacrylonitrile or polyester, (3) a method of producing the antibacterial polyacrylonitrile or polyester fiber or resin characterized by reacting polyacrylonitrile or polyester fiber or resin having sulfo and/or sulfonate groups in its structure with a water-soluble silver compound in water at a temperature above the glass transition point of the polyacrylonitrile or polyester and treating the reaction product with a reducing agent, and (4) antibacterial polyacrylonitrile or polyester fiber and resin produced by the above method (2) or (3).

Description

 Ming TO Antibacterial fiber, resin and manufacturing method

 The present invention relates to an antibacterial polyacrylonitrile or polyester fiber or resin and a polyacrylonitrile or polyester fiber or resin. The present invention relates to a method of processing a resin to impart antibacterial properties.

 Antibacterial materials are widely used and used today in every corner of life. It is also becoming indispensable in the food industry, such as meat factories, medical sites, and the manufacturing of pharmaceuticals. In the future, as society ages, its importance is likely to increase further

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Polyacrylonitrile fiber or resin (hereinafter abbreviated as PAN) is a highly versatile material, not only clothing, but also a product made by Toiletries, Inc. Because of its widespread use in one field, research on antibacterial processing of PAN has been active and many methods have been proposed, but still remain. There is nothing definitive. The idea of treating a PAN having a carboxylic acid group and a Z or sulfonate group in its structure with metal silver or a silver compound to impart antibacterial properties has been known for a long time and is well known. is there . However, the reactivity of silver ion is seemingly fast, and there is no literature that examined the reaction conditions in detail. As a result, in the prior art, when attaching a silver compound to PAN, fibers using an increased amount of sulfonate groups and / or sulfonate groups were used. Alternatively, the effectiveness of PAN is only proven by increasing the amount of carboxyl groups in the fiber by partial hydrolysis of PAN or by increasing the amount of silver attached. It was too short. On the other hand, polyester fibers and resins (hereinafter abbreviated as PET) are also highly versatile materials, and are widely used in various industrial fields as well as clothing. However, for PET, after molding, there are almost no effective methods of imparting antibacterial properties to the material by surface treatment, and the development of this technique has been awaited for many years. .

Japanese Patent Application Laid-Open No. 52-92000 describes a method for imparting antibacterial properties to PAN, but the effective concentration range of silver is 0.1 milliequivalent or more than Z gram fiber. In this embodiment, silver of 0.69 milliequivalent gram fiber is used. This results in the use of large amounts of silver, 1% and 7% per fiber, respectively. This is 絰 There is a practical problem in terms of cost.

In the case of imparting antimicrobial properties to PAN, the conventional technology required that fibers be manufactured in a special form, or that treatment such as hydrolysis was required in advance. These treatments do not only have to be complicated as an operation, but also have a significant effect on the strength and physical properties of the fiber. Another problem is the large amount of silver used, as described above. Furthermore, the present inventors have conducted intensive studies on PANs to which silver has been deposited by a conventional method. The precipitated silver was aggregated and found to be present with a large particle size. Thus, it was found that the silver surface attached to the PAN had a small surface area, but that many of the silver particles could fall off quickly after several washes. It was also found that a stable effect could not be obtained unless a large amount of silver was used because the adhesion was uneven, while PET was chemically active in its structure. It has no basic group. However, for the purpose of improving the dyeing properties in part, sulfonate groups and / or sulfonate groups were introduced into the structure in which sulfonate groups and / or sulfonate groups were introduced. There is a so-called dye dyeable polyester fiber or resin (hereinafter abbreviated as CDPET). However, sulfonate groups that can be introduced without impairing the performance of fibers and resins And the amount of Z or sulfonate groups is very small. Therefore, surface treatment of fibers or resins with silver ion or silver using conventional techniques is not considered as a practical method, and antimicrobial treatment of PET is not considered. Conventionally, a method with many limitations of imparting antibacterial properties by infiltrating a hydrophilic compound has been employed.

 As described above, PET has a small amount of sulfonate and / or sulfonate groups in the fiber (CDPET) in order to improve the dyeability. However, even if they are treated to attach or bind silver ions and metallic silver in a conventional manner, most of the silver does not adhere to the fiber or resin and remains slightly attached. Even so, the adhesion state of silver is not uniform, the surface area of silver is small, and the aggregated silver is easily released by washing etc., so that the antibacterial activity is weak. However, the sustainability of the effect is hardly recognized.

Disclosure of the invention

 The present inventors have conducted intensive studies on a method of uniformly attaching or bonding silver by preventing silver aggregation on PAN or CDPET, and as a result, completed the present invention. I did.

 That is, the present invention

(1) Silver in the form of silver sulfonate l ~ 100Gppni, preferably 10 ~ Antibacterial polyacrylonitrile or polyether fiber or resin containing lOOOppm

 (2) Polyacrylonitrile or polyester fiber or resin having a sulfonate group and a Z or sulfonate group in the structure, When reacting a water-soluble silver compound in water, the reaction should be performed at a temperature equal to or higher than the glass transition temperature of polyacrylonitrile or polyester. A method for producing an antibacterial polyacrylonitrile or polyester fiber or resin,

 (3) Polyacrylonitrile or polyester fiber or resin having a sulfonate group and / or a sulfonate group in the structure, in water, It is characterized in that a water-soluble silver compound is reacted at a temperature equal to or higher than the glass transition temperature of polyacrylonitrile or polyester, and then treated with a reducing agent. Process for the production of antibacterial polyacrylonitrile or polyester fibers or resins,

 (4) When reacting a water-soluble silver compound in water with polyacrylonitrile or polyester fiber or resin, the pH of the aqueous solution must be 5 or less. And (2) or (3).

(5) antibacterial polyacrylonitrile or polyester fiber or resin obtained by the method of (2), U) or (4) above; It is related to

 The PAN (polyacrylonitrile fiber or resin) used in the present invention is a fiber in which the amount of sulfonate groups and Z or the number of sulfonate groups is particularly increased. Or resin can be used, but it is possible to use sulfonate groups such as power spot, trelon, exlan, veslon, bonnel, kanecaron, etc. And commercially available PANs having Z or sulfonate groups are sufficient. As the PAN, resin of various shapes such as sheet-like, powdery, granular, etc. can be used in addition to yarn-like, cloth-like, and other fibers. Can be processed.

 These PANs used in the present invention usually contain at least 60 mol% of acrylonitrile and a vinyl group-containing copolymerizable with the acrylonitrile. It consists of a copolymer with an unsaturated compound, and adheres or binds 1 to 1 Gppra or more of silver when the above-mentioned treatment (2), (3) or (4) is performed. Any PAN having a sulfonate group amount and / or a sulfonate group amount that can be used can be used.

The CDPET (polyester fiber or resin having a sulfonate group and a Z or sulfonate group in the structure) used in the present invention is specifically a sulfonate group. And / or the use of fibers or resins with an increased amount of sulfonate groups is possible, but is commonly available commercially. Cation dye-dyeable polyester (CDPET) and the polyester fabric or yarn in which those yarns are blended are used. I get it. As the resin, various shapes such as a sheet-like resin, a powdery one, a grainy one, and the like can be used.

 CDPET is usually obtained from polyester fiber or polyester obtained mainly by the dehydration polycondensation reaction of terephthalic acid and / or phthalic acid (derivative) with polyhydric alcohol. Is a resin which has a sulfonate group or a sulfonate group in the structure, and is subjected to the treatment of (2), (3) or U) above. CDPET with an amount of sulfonate and / or sulfonate groups capable of adhering or binding i-1000ppin or more silver when Any of them can be used. Examples of phthalic acid (derivatives) include phthalic acid, isophthalic acid, paraoxybenzoic acid, 2-sulfoterephthalic acid, and 5-sulfoisofu Tallic acid, etc., and polyhydric alcohols include ethylene glycol, pentaerythritol, and oligoethylene glycol. It is used .

As the water-soluble silver compound to be used, silver nitrate is usually used, but silver fluoride, silver perchlorate, silver sulfate, silver lactate, silver tetrafluoroborate, silver silver sulfate, etc. are also used. You can do it. The glass transition temperature of PAN varies depending on the type of PAN, but is generally 60 to 90 ° C. Therefore, when PAN is used, the reaction temperature (treatment bath temperature) must be 9 ITC or more. In this case, the temperature is higher than the glass transition temperature of PAN. The reaction may be carried out while boiling the treatment bath at normal pressure. Also, the reaction may be carried out at a temperature of 1 ° C or more under pressure. The reaction temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of PAN, but is preferably 130 or less so as not to impair the properties of PAN. In particular, a glass transition temperature of about 10 G ° C is preferable.

On the other hand, although the glass transfer temperature of commercially available CDPET differs depending on the type of CDPET, it is generally 7 (! ~ 9Q.C. Therefore, the use of CDPET is not possible. In some cases, if the reaction temperature (treatment bath temperature) is higher than the glass transition temperature, it will be higher than the glass transition temperature of CDPET, even if the reaction is carried out while boiling the treatment bath at normal pressure. It is also possible to carry out the reaction under pressure at a temperature higher than 100. The reaction temperature is not particularly limited as long as it is higher than the glass transition temperature of CDPET. in the eyes of the properties had snare a loss, rather than the preferred and an der Ru this below at 200, is not the good or especially in 90~ 14 Q _c In the following explanation, PAN and CDPET are collectively referred to as CDFR.

 In order to carry out the method of the present invention, CDFR is generally added to an aqueous solution of a water-soluble silver compound, and the mixture is heated with stirring to react at a temperature equal to or higher than the glass transition temperature of the added CDFR. . Alternatively, the aqueous solution of the silver compound may be heated in advance to a temperature equal to or higher than the glass transition temperature of CDFR, and then the reaction may be performed by adding CDFR. The bath ratio (CDFR: silver compound aqueous solution) is appropriately from 1: 1G to 4G (weight ratio). The heat treatment time is not particularly limited, but usually 1 (! To 60 minutes is sufficient.

 The amount of the water-soluble silver compound used depends on the amount of silver to be attached or bound to CDFR, the type of CDFR, and the reaction conditions. Normally, in the case of commercially available CDFR, a water-soluble silver compound may be used in such an amount that the amount of silver becomes 1 to 5 times the amount of silver to be attached or bound to CDFR. When using PAN, it is preferable to pay attention to the control of the bath temperature after the treatment in order to avoid the PAN characteristics such as the texture of the fiber. Immediately, it is desirable to cool slowly until the solution is cut off by 60.

According to the above method, the antibacterial agent of the present invention having a silver sulfonate group Sex CDFR can be obtained.

 The antimicrobial CDFR having a silver sulfonate group of the present invention has little coloration, and has almost no discoloration due to sunlight, reduction with a detergent, etc. It is very advantageous for thinking.

 If coloring is a problem, such as on a white cloth, it is preferable to adjust the pH and react in an acidic aqueous solution. The pH can be adjusted by using a buffer solution, an acid, or the like, but the use of a compound that reacts with silver and precipitates, such as hydrochloric acid, is not preferred. Usually, the pH is adjusted using a lactic acid or acetic acid buffer solution. The preferred pH range is 1-5.

 If the acid is used alone, the acid concentration is determined by the pH. The concentration of the buffer solution is not specified, but is usually 0.01 πιο_β /

(齚 酸) 程度 足 十分。 About (齚 acid) is sufficient. The antimicrobial CDFR thus obtained can be further reduced, if necessary, to obtain an antimicrobial CDFR with silver particles attached thereto. . In the case of performing the reduction treatment, a relatively strong reducing agent is preferred as the reducing agent. Examples of the reducing agent include hydroxylamine, hydrazine and hydrazine. Lucari, sodium borohydride and the like can be used. An aqueous solution of preferably 0.05 to 5% by weight of the reducing agent has a silver sulfonate group. The antibacterial CDFR is preferably used at 2 to 30 times by weight, and preferably subjected to reduction by heating at 95 to 1 G fl for at least 5 minutes. I can do it. The antibacterial CDFR having the silver sulfonate group of the present invention thus provided with silver and the antibacterial CDFR to which silver fine particles are adhered have a silver content of l to 1000 ppm. The antibacterial effect is sufficient even at a concentration as low as 1 (! To lQ ppm.) As described above, the conventional method is used to impart antibacterial properties to the fiber. In contrast, it was necessary to incorporate silver into the fiber at a very high concentration of 1% or 7%, whereas according to the present invention, the silver concentration was unexpectedly increased. The antibacterial CDFR of the present invention shows a strong antibacterial effect even at a low concentration of 1 to 1000 ppm, and a very good washing fastness. Alternatively, silver is uniformly adhered or bound on the resin, and silver precipitated as metallic silver does not agglomerate, and silver This is because they exist in very fine particles.

What has been reduced according to the method of the present invention into metallic silver fine particles is pale yellow, and turns blackish brown. The fibers and resins obtained by the method of the present invention are advantageous. The antibacterial CDFR having a silver sulfonate group and the light yellow antibacterial CDFR to which silver fine particles are adhered according to the present invention are dyed with a cationic dye in an arbitrary color tone by a usual prescription. It is possible. Alternatively, CDFR may be first stained with a cationic dye in a conventional manner, and then imparted with antibacterial properties by the method of the present invention. Furthermore, antibacterial properties can be imparted simultaneously with the dyeing according to the method of the present invention by using a cationic dye excluding the halogen ion, which is contained carefully, in accordance with the method of the present invention. .

Since the antibacterial CDFR of the present invention exhibits a high antibacterial effect even though the concentration of silver is extremely low, it is sufficient to use a small amount of silver. Has no effect. Further, the antibacterial CDFR of the present invention can be used as an antibacterial material in any place where there is a possibility of being contaminated by harmful microorganisms. For example, for antibacterial PAN, nosmat, toilet mat, toilet seat cover, carpet, mop, air fin The production of olive oils and fungi can keep microorganisms clean. In addition, it can be used for gloves, work clothes, etc. used in food processing or manufacturing. For antibacterial CDPET, for example, surgical lab coats, hospital curtains, hospital wardrobes, software, pillowcases, slipper linings, Haoshime Kanokuichi, sanitation evening It can be used for components.

 The antibacterial CDFR of the present invention may be used alone as it is, or as a blended or mixed fabric with other fibers, and not as a fabric, knit product, or nonwoven fabric. Can also be used.

BEST MODE FOR CARRYING OUT THE INVENTION

 Next, the present invention will be described by way of specific examples. However, the present invention is not limited to these examples. The test for antibacterial activity is usually carried out by using Staphylococcus aureus (Stafirococcus aureus) suspended in a broth medium.

The bacteria of Klebs iella pneumoni ae (Klebsiella pneumonia) are adhered to the specimen, kept at 37 ° C for 18 hours, and then the viable bacteria adhered to the specimen This was done by counting numbers. Also, the washing fastness test

The antibacterial effect of the test piece obtained by repeating the method defined in JIS L 0217103 30 times was measured, and the amount of residual silver was measured by an atomic absorption method.

Example A 1

100 parts by weight of Casimirone (PAN made by Asahi Kasei) was immersed in 300 parts (1 part by weight) of water containing 0.126 parts by weight of silver nitrate. The heating was stopped at that time, left as it was, and cooled to 50 or less, and then Casimirone was taken out. When dried, Casimirone with silver-sulfonate group was obtained.

0.2 g of the treated cloth obtained by the above-mentioned method was used, and a suspension of Staylococcus au reus ATCC 6538P in normal bouillon (number of bacteria: 8) X 10 ³ / ml) 0.2 ml was applied. This was incubated at 37 ° C for 18 hours and extracted with 20 ml of buffered saline containing phosphate. The extract was inoculated on a standard agar medium and the number of bacteria was measured. As a result, 18 ml of bacteria were detected in the extract from the treated cloth according to the present invention. On the other hand, the extract of the untreated control cloth without silver contained 9 × iG ³ cells / ml.

Example A 2

 In Example A1, 100 parts by weight of trelon (PAN made by Toray) and Q'.G parts by weight instead of 0.126 parts by weight of silver nitrate were used instead of cashimilon. A test cloth (treated cloth) was obtained by treating in the same manner as in Example A1 except for the above. An antibacterial test was performed using the obtained toleron in the same manner as in Example A1. As a result, 35 Z ml of bacteria were detected from the extract, but no silver was contained. Bacteria were detected in the untreated cloth extract.

Example A3-A4

In the same manner as in Example A1, the amount of silver nitrate was changed to 0. 5 one

Parts, Q. 008 parts by weight, a test cloth (treated cloth) was obtained in the same manner as in Example A, and the test was performed in the same manner.

 Table A1 shows the results of Examples A1 to A4.

実施例 A 5 〜 A 8 A

Examples A5 to A8

100 parts by weight of the silver ion-containing cloth obtained in Examples A1 to A4 were each suspended in 0.5 parts by weight of sodium borohydride, and 500 parts by weight were suspended. In water, heated and boiled for 30 minutes. Next, the cloth was washed with water and dried to obtain a cloth in which silver ions were reduced and adhered as metallic silver. Each was evaluated in the same manner as in Example A1. The results are shown in Table A2. 6 one

A 2

実施例 A 9 〜 A 12

Examples A 9 to A 12

 The cloth to which silver obtained in Examples Al, A3, A5, and A7 was adhered or bound was repeatedly washed 30 times according to the method of 1SL0217103. The amount of each remaining silver and the results of the antibacterial test performed in the same manner as in Example A1 are shown in Table A3.

A 3

 Example Silver content in cloth (atomic absorption method) Number of bacteria after 18 hours at 37

A 9 (A 1) 713 p pm 25 ml

A 10 (A 3) 168 p pm 61 ml

A 11 (A 5) 699 p pm 38 pieces ml

A12 (A7) 162 ppm 30 pieces Z ml 7

Example A U to A 16

In Example A1, instead of S taphy 1 Qc Q cc U saur eus, the cloth to which silver obtained in Examples A 1, A 3, A 5, and A 7 was adhered or bound was used. Here, the same method as that of Example A1 was used except that 0.2 ml of a normal bouillon suspension of Klebs iella pneumon i ae ATCC4352 (9 x 1Q ⁵ cells / ml) was attached. Each was tested for antimicrobial performance. The results are shown in Table A4. The extract of the untreated control cloth containing no silver contained 10 ml of IX and Z ml of the bacteria.

A 4

実施例 A Π

Example A Π

A test cloth was obtained in the same manner as in Example A1 except that 0.124 parts by weight of silver lactate was used instead of silver nitrate in Example A1, and an antibacterial test was performed. became. The results were almost the same as in Example A1.

Examples A 18 to A 19

 In Example A5, except that sodium borohydride was replaced by 2.5 parts by weight of hydroxylamine or 2.5 parts by weight of hydrazine. A test cloth was obtained in the same manner as in Example A5, and an antibacterial test was performed in the same manner as in Example A1. The results were almost the same as in Example A5 in each case.

Example A 20

 500 ppm acetic acid containing 100 parts by weight of Xelan having a sulfonate group (PAN manufactured by Xelan Corporation of Japan) and 0.063 part by weight of silver nitrate The solution was immersed in 2500 parts by weight of an aqueous solution (pH = 3.4), and the temperature was increased to 100 with stirring. After stirring at 120 for lhr, the mixture was cooled, thoroughly washed with water, and dried to obtain a polyacrylonitrile cloth having a silver sulfonate group. The silver content of this polyacrylonitrile cloth was .368 ppm.

Example A 21

Example A In the same manner as in 2G, 2500 parts by weight of water (pH = 6.5) containing 0.063 parts by weight of silver nitrate was used instead of the SOOppm ^ acid aqueous solution containing 0.063 parts by weight of silver nitrate. Process and use silver sulfonate groups. 9

A rear clear nylon cloth was obtained. The silver content of the polyacrylonitrile cloth was about 4 ρ ρπι.

 Each of the polyacrylonitrile cloths obtained in Example A2G and Example A21 showed the same antibacterial effect as in Examples A1 to A4.

Example A 22

 The color difference between the untreated polyacrylonitrile cloth and the polyacrylonitrile cloth obtained in Examples A20 and A21 was measured using a color difference meter. did. The results are shown in Table A5.

上記、 表 A 5 中 A L , Δ a , △ !) は そ れぞれ、 未処理ポ リ ア ク リ ロ ニ ト リ ル布か ら の明度の差、 色相の差、 彩度の差を表わ す A 5

In Table A5 above, AL, Δa, △!) Represent the difference in lightness, hue, and saturation from untreated polyacrylonitrile cloth, respectively. I

As is evident from the results shown in Table A5, the polyacrylonitrile cloth obtained in Example A20 was untreated polyacrylonitrile in color tone. Although it is almost the same as the trill cloth, the polyacrylonitrile cloth obtained in Example A21 is similar to the untreated polyacrylonitrile cloth. The brightness has decreased, and both Δ1> have large values. An increase in the value of a indicates that it is reddish, and an increase in the value of a indicates that it is yellowish. The difference between the results in Examples A2D and A21 is due to the pH in the treatment solution, which is particularly problematic with white polyacrylonitrile cloth, for example. In such cases, it is possible to obtain an antibacterial polyacrylonitrile cloth with no color change by adjusting the pH and conducting the reaction with an acidic aqueous solution. .

Example A 23

 120 parts by weight of trelon having a sulfonate group (PAN made by Toray Co., Ltd.) is gradually heated and boiled by immersing it in 3600 parts by weight of water in which 0.24 parts by weight of silver nitrate is dissolved After holding for 30 minutes, the toleron was removed and washed with water.

Next, 0.4 parts by weight of cation dye glycerol light blue 4 GSL was dissolved in 3 parts by weight of water and treated with the silver nitrate solution in the previous step. Was soaked again. After adding 10 parts by weight of 10% S ^ acid, the mixture was heated and boiled. After holding for 20 minutes, slowly cool to 50 or below The toleron was removed from the flask, washed thoroughly with water and dried to obtain blue-colored torelon having silver-sulfonate groups.

Evaluation of antibacterial properties

Ri adopted the treated fabric from about 0. 2 g obtained by the above method, this is the Kl ebs iella neumoni common buoy Yo emissions suspension ae ATCC 435 (the number of ^{bacteria; .9 x l0 5 / ml)} 0. 2 ml was applied. This was left standing at 3 C for 18 hours, and then extracted with 20 ml of buffered saline containing phosphate. As a result, 43 Z ml of Klebs iella pneumotti ae was detected in the extract from the treated cloth according to the present invention. On the other hand, the untreated control cloth extract containing no silver contained ⁴ ml of IX 1Q bacteria.

Example A 24

 First, 120 parts by weight of trelon having a sulfonate group (PAN made by Toray) are turned to red with 100 parts by using 0.3 parts by weight of cation dye glycerol GL. Dyed. The bath ratio was 1: 3 G.

 Next, the cloth dyed red was soaked in 1200 parts by weight of water containing 0.2 parts by weight of silver nitrate, gradually heated, and kept at the boiling point for 30 minutes. After that, they were thoroughly washed with boiling water.

Furthermore, it was put into 1200 parts by weight of a 0.4% solution of hydroxyamine sulfate and boiled for 30 minutes. When the liquid has cooled to below 50, remove the treatment cloth. Discharged, washed thoroughly with water and dried.

 The antibacterial test using the Klebssiel la pneumoni ae on the red cloth to which the silver fine particles thus obtained were adhered was carried out in the same manner as in Example A23. When it was performed, it showed strong efficacy.

Example A 25

 In Example A1, polyacrylonitrile particles having a sulfonate group were used instead of cashimilone, and otherwise the same as in Example A1 Then, processing was performed. The obtained particulate polyacrylonitrile resin showed the same antibacterial effect as in Example A1.

Example B 1

 Cathode dyeable polyester fabric with sulfonate groups (at a standard dyeing temperature of 120) 1 GG parts by weight, and 0.18 parts by weight of silver nitrate Boiling water 3000 It was immersed in a weight part and kept in this state for 30 minutes. After cooling, the treated cloth was taken out, washed well, and dried to obtain a polyester cloth having a silver sulfone group. When the silver content of this cationic dyeable polyester fabric was measured by an atomic absorption method, silver of 840 ρρπι was found.

Evaluation of antibacterial properties

0.2 g of the treated cloth obtained by the above method was taken and used for Staphylococcus. Attach 0.2 ml of normal bouillon suspension of aureus ATCC65 P (8 x 10 bacteria ⁵ ml). This was kept at 37 ° C for a time, and then extracted with 20 ml of buffered saline containing phosphoric acid. This extract was inoculated on a standard agar medium, and the number of bacteria was measured. As a result, 120 bacteria / ml were detected in the extract from the cloth treated according to the present invention. Meanwhile extract control fabric silver-containing or not name untreated contained in 6 X 1 0 ⁸ or Z ml bacteria. Examples B 2 to B 4

 The procedure was performed in the same manner as in Example B1 except that the amount of silver nitrate in the reaction solution was changed to 0.09 parts by weight, 0.045 parts by weight, and 0.0 U parts by weight instead of 0.0 U parts by weight. In the same manner as in Example B1, treated cloths containing silver at each concentration were obtained. They were evaluated in the same manner as in Example B1. The results are shown in Table B1.

B

 Example Amount of silver in treated cloth (atomic absorption method) Number of bacteria after 18 li 37 ° C

B 1 840 p p m 120 pieces Z ml

B 2 14 p p m 95 pcs Z ml

B 3 193 p pm 145 pieces ml

B 4 6? P pm 135 pieces Z ml Example B5 to B8

 100 parts by weight of the silver ion-containing cloth obtained in Examples B1 to B4 were each immersed in 500 parts by weight of 0.5% aqueous solution of hydroxyamine, and boiled for 30 minutes did. Thereafter, the fabric was washed with water and dried to obtain a treated cloth in which silver ions were reduced and adhered as metallic silver. Example for each

Evaluation was performed in the same manner as in B1. The results are shown in Table B2

B 2

実施例 B 9 〜 B 12

Examples B 9 to B 12

The test pieces obtained in Examples Bl, B3, Β5, and 洗濯 7 were repeatedly washed 30 times according to the method of J IS L 0217103. The samples thus obtained were measured for silver S and evaluated for antibacterial activity in the same manner as in Example B1. Table 3 shows the results. B 3

実施例 B 13〜 B 16

Examples B 13 to B 16

 Example Bl, the treated cloth obtained in B3, B5, B7

Example B, except that 0.2 ml of Klebs iella pneumon iae ATCC 4352 ordinary bouillon suspension (several bacteria, Z ml) was applied instead of St aphylococcus aureus. The antimicrobial performance was tested in the same manner as in 1. The extract of the untreated control cloth without silver contained ⁸ × 10 ⁸ bacteria / ml. The results are shown in Table B4.

B 4

実施例 B Π

Example B Π

 A test piece was obtained and an antibacterial test was performed in the same manner as in Example 1 except that silver lactate was used in place of silver nitrate in Example B1. The results were almost the same as in Example 1.

Example Β 18 ~ Β 19

 In Example Β5, 5 parts by weight of an aqueous solution of hydrazine or 500 parts by weight of a 0.5% sodium borohydride suspension was used in place of hydroxyamine. A test cloth was obtained in the same manner as in Example B5 except for using the same, and an antibacterial test was performed in the same manner as in Example B1. The results were almost the same as in Example B5 in each case.

Example B 20

Cationic dyeable polyester fabric with sulfonate group (Standard dyeing temperature: 10 C) The iOG parts by weight were immersed in 2500 parts by weight of water containing G.05 parts of silver nitrate, and heated to boiling while stirring. After stirring for an additional 20 minutes, the mixture was cooled, the treated cloth was washed with water, and dried to obtain a polyester cloth having silver sulfone net groups. Was. When the silver content of the polyester cloth was measured by the atomic absorption method, 3 G 1 ppm of silver was found. Further, after washing the polyester cloth 30 times in the same manner as in Example B9, the silver content in the polyester cloth was ΠΟρριη. The anti-bacterial property of the unwashed polyester cloth and the one after washing 30 times were evaluated in the same manner as in Example B1. 135 ml of bacteria were detected in the extract from Riestell, and 118 ml of bacteria were detected in the extract of the polyester cloth after washing 30 times. On the other hand, 7 × 1Q ⁸ ml of bacteria were detected in the extract of the untreated control cloth containing no silver.

Example B 21

100 parts by weight of polyester dye-dyeable polyester cloth (at a standard dyeing temperature of 120) and 100 parts by weight of lOOppm acetic acid aqueous solution containing 0.063 parts by weight of silver nitrate (pH = 3.8) 1500 parts by weight Then, the mixture was heated to 120 under pressure while stirring. After expanding Ur at 120 ° C, cool down After washing and drying, a polyester cloth having a silver sulfonate group was obtained. The silver content of the polyester fabric was 344 ppm.

Example B 22

 In the same manner as in Example B21, water containing 0.0 parts by weight of silver nitrate instead of 1 part by weight of an aqueous solution of lQQppm acid containing 0.063 parts by weight of silver nitrate (pH = 6.5) The treatment was performed using 1,500 parts by weight to obtain a polyester cloth having a silver sulfonate group. The silver content in the polyester fabric was 354ρρπι.

 Each of the polyester cloths obtained in Example B21 and Example B22 showed the same antibacterial effect as Example B2Q.

Example B 23

 The color difference between the polyester cloth obtained in Example B21 and Example B22 and the untreated polyester cloth was measured using a color difference meter. The results are shown in Table B5

B 5

Acid concentration (ppm) pH △ Lum a △ b Example B 21 100 -3.8-0.26 0.31 0.17 Example B 22 0 6.5-2.68 0.70 3.96 In Table B5 above, AL, mua, and mub represent the difference in lightness, hue, and saturation, respectively, from the untreated polyester fabric.

As is evident from the results shown in Table B5, the polyester fabric obtained in Example B21 is almost the same as untreated polyester fabric in color. River Ri Do Iga, in the Po Li es Te le cloth obtained in Π example b, brightness compared to the non-processing lipoic Li et scan Te le cloth is reduced ^ to you is,厶_a, b厶both large It is a big value. The difference between the results in Examples B21 and B22 is due to the pH in the treatment solution, especially if coloring is a problem, such as a white polyester cloth. By carrying out the reaction with an acidic aqueous solution by adjusting the pH, an antibacterial polyester cloth without color change can be obtained.

Example B 24

 First, 120 parts by weight of a cation dye-dyeable polyester gel having a sulfonate group was first added to a cation dye GL0. Using 3 parts by weight, dyed red at UG ° C. The bath ratio was 1:30.

Next, the cloth dyed red was soaked in 1200 parts by weight of water containing 0.2 parts by weight of silver nitrate, gradually heated, and kept at the boiling point for 30 minutes. After that, if it is thoroughly washed with hot water and dried, it has silver-sulfonate groups. Polyester was obtained.

 Polyesters treated in this way also had strong antibacterial activity against Staphylococcus aureus and Klebselielneumoniae.

Example B 25

 35 parts by weight of the cation dye-dyeable polyester cloth to which the silver fine particles were attached obtained in Example B5 was added to the cation dye acryl light pull 4 GSL 0 .07 parts by weight were added to 400 parts by weight of dissolved water. Raise the temperature to 120 in a pressure vessel, hold for 40 minutes and dye.After cooling, take out the dyeing cloth and wash it thoroughly with water to obtain a blue-colored polyester cloth. And the antibacterial properties were maintained.

Example B 26

 In Example B1, a polyester resin particle having a sulfonate group was used in place of the cationic dye-dyeable polyester cloth, and the other conditions were the same as in Example B. And performed the processing. The obtained polystyrene resin having a low particle size is industrially applicable, exhibiting the same antibacterial effect as in Example B.

The antibacterial CDFR of the present invention exhibits a strong antibacterial effect, although the amount of silver attached or bound is extremely small as compared with the conventional one. Also, the washing fastness is excellent. Further, the antibacterial CDFR of the present invention has high safety and does not generate harmful substances due to the imparting of antibacterial property even in incineration. Furthermore, the antibacterial CDFR of the present invention has very little irritation to the skin and can be suitably used in applications such as clothing which come into contact with the skin.

 Further, according to the present invention, PAN and CDPET having a sulfonate group and / or a sulfonate group, or a blended or woven fabric thereof, can be easily and economically produced. Can impart antibacterial properties to the surface, and has few problems with the coloring of fibers or resins due to silver adhesion or bonding.

Claims

The scope of the claims  1. An antibacterial polyacrylonitrile or polyester fiber or resin containing i-lG ppm of silver in the form of silver sulfonate.  2. The fiber or resin according to claim 1, wherein the content of silver is 1 (! To 100 ppm).  3. Polyacrylonitrile or polyester fiber or resin containing sulfonate group and Z or sulfonate group in the structure, When reacting the water-soluble silver compound in the reaction, it is necessary to carry out the reaction at a temperature higher than the glass transition temperature of polyacrylonitrile or polyester. A method of producing a specialty antibacterial polyacrylonitrile or polyester fiber or resin.  4. Polyacrylonitrile or polyester fiber or resin containing sulfonate and / or sulfonate groups in the structure, water-soluble silver in water An antibacterial polysaccharide characterized by reacting the compound at a temperature above the glass transition temperature of polyacrylonitrile or polyester and then treating with a reducing agent. A method for producing fiber or resin of rear acrylic or polyester. 5. When reacting a water-soluble silver compound in water with a polyacrylonitrile or polyester fiber or resin in water, adjust the pH of the aqueous solution to 5 or less. 5. The method according to claim 3, wherein the method is characterized in that:  6. The fiber or resin is polyacrylonitrile, and the reaction temperature for reacting the water-soluble silver compound with the fiber or resin in water is polyacrylonitrile. 6. The method according to claim 3, wherein the temperature is not lower than the glass transition temperature.  III. The method according to claim 6, wherein the reaction temperature is a glass transition temperature or less.  8. The fiber or resin is a polyester, and the reaction temperature at which the water-soluble silver compound is reacted with the fiber or resin in water is higher than the glass transition temperature of the polyester. The method according to claim 3, 4, or 5.  9. The method according to claim 8, wherein the reaction temperature is 90 to H0 ° C.  10. The water-soluble silver compound is a compound selected from silver nitrate, silver fluoride, silver perchlorate, silver sulfate, silver lactate, silver tetrafluoroborate and silver sulfate. The manufacturing method according to any one of the above items.  11. An antibacterial polyacrylonitrile or polyester fiber or resin obtained by the method according to any one of claims 3 to 10.  12. The fiber or resin according to claim 11, wherein the silver content is l to 100 Qp pins. 13. The silver content is 1! ) To lOOO ppm.