JPS62250277A - Antibacterial treatment of fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of the Invention The present invention relates to a method for applying an antibacterial agent to fibers to produce fibers having an antibacterial effect. More specifically, the present invention applies a treatment solution containing an organosilicon quaternary ammonium salt as an antibacterial agent to fibers, and in the subsequent steps of scouring, dyeing, and finishing, the antibacterial effect is substantially reduced or eliminated. Concerning antibacterial treatment methods that do not.

Cans) Conventional technology Antibacterial and sanitary treated textile products have been known for a long time, but
In general, the following three characteristics are required in this case.

(1) ° High hygiene effect (ii) Durability Gi) High safety However, for example, the organosilicon quaternary ammonium salt represented by the following formula satisfies the above three requirements. Known as an antibacterial, antifungal, and antialgal agent, it is described in Japanese Patent Laid-Open No. 57-51875 that it can be used in textile products such as BCF nylon yarn after dyeing.

H3 CC1aHsy N (CH*)s-81(OCH
s) s) "α-Hs More recently, in order to maintain the antibacterial effect of the quaternary ammonium salt, electrolyte salts and C8
- A method of coexisting CtS with an unsaturated fatty acid or its salt (Japanese Patent Application Laid-Open No. 181364/1982), and a method of adding a final cation treatment to the above treatment (Japanese Patent Application Laid-open No. 185866/1986), etc. Proposed.

The forms of fibers to be processed here are raw cotton, yarn (all, cheese, etc.), and the forms of fabrics include fabrics such as M* items, and piece items such as carpets, curtains, and mats that have become textile products. It is. By the way, the present inventors have come to know a fact that was not recognized at all in the above-mentioned proposals regarding treatment with the above-mentioned antibacterial agent. In other words, scouring occurs when an antibacterial agent is applied to the fiber or cloth in advance during scouring, dyeing, or finishing, or even when an antibacterial agent is added during the scouring, dyeing, or finishing process.

During treatments such as dyeing and finishing, the antibacterial effect changes significantly depending on the PHK of each treatment solution.

(c) Purpose of the Invention Therefore, the purpose of the present invention is to prevent the use of antibacterial agents, even when the antibacterial agent is applied to fibers or fabrics in advance, or even when the antibacterial agent is applied through so-called post-processing such as scouring, dyeing, and finishing. The object of the present invention is to provide an antibacterial treatment method that effectively adheres to fibers or fabrics and maintains the antibacterial effect.

(d) Structure of the Invention The present inventors have discovered that when treating an antibacterial agent consisting of an organosilicon quaternary ammonium salt, the antibacterial effect can be sustained by controlling the treatment liquid to an appropriate pH. This is what I did.

Thus, according to the present invention, there is provided a method for antibacterial treatment of fibers or fabrics, which comprises: (1) controlling the pH of the treatment solution to 7 or more when treating the fibers with an antibacterial agent consisting of an organic silicon quaternary ammonium salt; is provided.

In the present invention, which will be described in detail below, the organosilicon quaternary ammonium salt, which is an antibacterial agent, may be applied at any step of the spinning process, but when synthetic fibers are melt-spun, the organic silicon quaternary ammonium salt is applied to the fiber structure. It is expected that if the antibacterial agent is applied during or after oiling in a loose spinning process, the antibacterial agent will be more easily adhered to the fibers and the antibacterial effect or durability will be higher. Also, carpets and curtains made of raw cotton, yarn, fabrics such as knitted fabrics, and textile products.

Antibacterial agents may be added to piece products such as mats in a separate process.

FIG. 1 is a route diagram of a process for attaching an antibacterial agent made of an organic silicon quaternary ammonium salt using a polyamide direct-spinning stretching heat treatment process.

FIG. 2 is a route map of a process in which texturing is further incorporated after the stretching heat treatment in the process of FIG. 1.

In FIG. 1, a polyamide filament 2 discharged from a nozzle 1 is cooled and solidified, then coated with a spinning oil containing an antibacterial agent by an oiling roller 3, and then applied to a godet roller 4.
．． 5 (5' is a separate roller), the film is wound between a heating row 26 and a separate roller 6', and is heat-treated at the same time as stretching.

Next, the drawn yarn 7 is passed through an oiling roller 8 as necessary.
After oil is added to the winder 9, the winder 9 winds the winder.

Generally, it is preferable to apply the antibacterial agent to the spun yarn before the godet roller 4 in the same bath as the spinning oil or in a separate bath, and this also applies to the process shown in FIG. 2 below.

Further, FIG. 2 shows an embodiment in which the process shown in FIG. 1 is applied to direct spinning, stretching, and processing (so-called 5DTY). That is, in the device shown in FIG.
The yarn 22 spun through the spinneret 21 is passed through the oiling roller 23. Godets Troller 24. Supply rollers 25, 25
The heated rollers 226 and 26' rotate at a constant circumferential speed several times faster than the rollers 225 and 25', and are wound several times around the heated rollers 226 and 26', and are stretched between the rollers 25 and 25' and the rollers 26 and 26'. After that, it is introduced into the heated fluid processing nozzle 27 and crimped, and then oiled by the oiling roller 28 as necessary, and then pulled out by the roller 29° 29'.
It passes through a guide 30 and is wound into a winder 31.

In Figures 1 and 2, the characteristics are that the antibacterial agent is applied to the spun yarn whose molecular structure is not completely stabilized;
In the subsequent heat treatment process, these agents are thermally fixed to the filament surface, and all of these agents are applied using the filament spinning process, resulting in the so-called built-in (
built-in) to obtain the desired yarn package.

As used herein, built-in refers to applying the antimicrobial agent to the fibers at any step during the fiber-forming polymer being expelled from the spinneret and initially wound into a package.

Although FIG. 1 shows the direct spinning drawing process, instead of this, it is possible to heat the godet rollers and stretch the fibers by several tens of inches between the godet rollers during high-speed spinning of 3000 m/min or higher. Alternatively, a method may be adopted in which the antibacterial agent is heat-fixed and rolled up.

Furthermore, in the steps shown in FIGS. 1 and 2, the workability (fuzz) of the uniform adhesion of the antibacterial agent and the stretching step is further improved.

U.S. Patent No. 3.80 to improve the prevention of plastic wrap
As shown in the specification of No. 3,282, an entangling nozzle is provided between the oiling roller 3 (23) and the first godet roller 4 (24) to impart slight entanglement to the yarn. Good too. On the other hand, the yarn after drawing or texturing is subjected to normal interlacing (5 pieces/m to 40 pieces/m) before the winder.
By imparting the yarn with a diameter of 100 mm/m), subsequent handling of the yarn is ensured. Regarding this confounding process and the number of confounds, [U.S. Pat.
It is detailed in the specification of No. 151.

Also, in Figure 1, the rollers are a separate roller type, a Nelson roller type (Figure 2).

26, 26'), etc., but combinations of these may be selected as appropriate.

Furthermore, as the texture processing method, a heated fluid processing method that is excellent in high-speed processability is often adopted because it is incorporated into high-speed winding called a direct spinning drawing method. Examples of these methods include a method in which yarn plasticized by heated fluid is deposited in a pad or wad shape and crimped in a nozzle (U.S. Pat. No. 4,188,699).
Specification No. 1, Specification No. 4,268,940''8), a method in which the yarn plasticized by heated fluid in a nozzle is taken out as a loop yarn, cooled, and then drafted and opened (U.S. patent Specification No. 3,186,155.

No. 3,543,353) A method in which yarns plasticized by heated fluid in a nozzle are buckled and deposited on an air-permeable impact surface, cooled in this state, and then dammed (U.S. Patent No. 3,543,353). Specification No. 3,255,508.

British Patent No. 1,273,797) is adopted.

Of course, Figure 1 or Poly7 wound as a high speed spun yarn
Thereafter, the midflat yarn may be subjected to a texturing process such as a crimping process typified by a false twist process, a crimping process typified by a crimping process, or a composite process with polyurethane, as required.

The antibacterial agent used in the present invention is an organosilicon quaternary ammonium salt represented by the following general formula.

General formula: R (where R is a C1-C2□ long-chain alkyl group, R1@
R.

and R4 is a lower alkyl group, X is CI, Br,
Represents I or CH, Coo. ) This compound is an alkyl, 7-aryl, alkenyl, aralkyl dimethylamine such as lauryl (Cu-),
It is obtained by heating reaction of tertiary amine such as myristyl (C14-), cetyl (Ct*-) dimethylamine and r-halopropyl trialfukidisilane, such as dimethyl, offdecyl, (3-)rimethoxy Cyril)
-Propylammonium chloride is manufactured by Dow Corning (product name DOW-CORNING 5700 antimicrobial treatment agent), Shin-Etsu Chemical, and PETRACH8YS in the United States.
It is commercially available from TEM Co., Ltd. 1. Normally, a methanol solution with an effective acid content of about 50% and 1. are supplied.

Such an antibacterial agent is applied in an amount of 0.05 to 1.0%, preferably 0.1 to 0.8% by weight of the fiber. If it is less than 0.05%, the desired antibacterial effect cannot be obtained, while if it exceeds 1.0%, it is disadvantageous in terms of cost. As shown in the figure, it is advantageous in terms of the process to normally add 5 to 8 Oi of such an antibacterial agent to the spinning oil. The method of applying the spinning oil or antibacterial agent is not limited to the oiling ruler method, but any method commonly used in the art such as metered oiling or spraying may be employed.

In either case, it is important to control the PM of the treatment solution containing the antibacterial agent to 7 or higher. If this PT-T is less than 7, particularly 6 or less, the antibacterial effect will substantially disappear when subjected to a subsequent scouring finish, as shown in the Examples described later. Further, as the pH regulator, those commonly used in this field can be used, but phosphoric acid (primary phosphoric acid, secondary phosphoric acid) is preferably used for 41.

(Action/effect of invention) Usually, fabrics such as raw cotton, yarn, or knitted fabrics.

We also perform scouring, dyeing, finishing, etc. on piece textile products such as carpets, curtains, and mats. At that time, it is common to use various auxiliary agents, but when auxiliary agents such as anionic scouring agents and leveling agents are used, the organosilicon quaternary ammonium salt of the antibacterial agent is It is known that ammonium ions are masked and the antibacterial effect is reduced. On the other hand, in processes such as scouring, dyeing, and finishing, each processing solution is usually used to achieve the desired dyeing and finishing. Q adjustment is being carried out. When dyeing with an acidic dye or the like, the pH is usually maintained at 6.0 or less in order to improve dye adsorption. And this thing
The antibacterial effect of antibacterial-treated fibers or fabrics was lost before one knew it. In other words, they were being used without knowing the mechanism by which they exert their antibacterial effects.

However, according to the present invention, an organic silicon quaternary ammonium salt is used as an antibacterial agent. .

was found to have a significant effect. That is, when applying an organosilicon quaternary ammonium salt as an antibacterial agent, the pH of each treatment liquid needs to be 7 or higher. PI (7
The totally unexpected fact was discovered that the antibacterial effect is significantly reduced at pH below 11, while the antibacterial effect is maintained as it is at pH 7 or higher. The reason why the antibacterial effect noticeably decreases when the pH drops below a certain level is when the Il side becomes active.

It is presumed that this is because the silicon quaternary ammonium salt is activated, that is, becomes easily dissolved in an aqueous solution, and easily falls off from the fiber or fabric.

As described above, according to the present invention, the pH of the treatment bath containing an antibacterial agent is
It is possible to provide antibacterial fibers or textile products whose antibacterial properties are not equally affected by post-finishing steps by extremely simple means of adjusting the antibacterial properties, and the economic advantages thereof are considerable.

Hereinafter, the present invention will be explained in detail with reference to Examples, and the antibacterial test in the Examples follows the definitions below.

<Antibacterial test> (1) Test method AATCCTe5t Method 100 The sterilization rate is determined by the shake flask method, which is an improved version of the bioassay method.

AATCCTes+t Method 100 methods are used for autoclave sterilized unprocessed fabrics and processed fabrics! A certain number of bacterial fluids (1-2 x 10' Colony Fo
rming Unit/Ill)
After permeating CCBroth medium and culturing at 37°C for 18 hours, the solution was shaken and extracted with phosphate buffer solution for 1 minute, and the number of viable bacteria was counted before and after culture using the plate dilution method. This is a quantitative method that evaluates antibacterial activity by displaying the number of bacteria on the fiber as a reduction rate.

Shake flask method (Shake F1a5k method)
The sample was placed in a dilute phosphorous buffer solution inoculated with ny Forming Unit/d), and the sample was kept at room temperature or at
After shaking at 5°C to 30°C, the number of viable bacteria in fBl before (4) and after contacting the test bacteria to the processed cloth was measured by the plate dilution method, and expressed as a reduction rate relative to the number of viable bacteria before contact. 1- It is a quantitative method for evaluating antibacterial activity.

Sterilization rate ■=((A-B)/A)xto.

A: Number of bacteria at 0 hours B: Number of bacteria after shaking for 1 hour (2) Bacterial species Klebsiella pneumoniae ATC
C-4352 Example 1゜In the process shown in Fig. 1, the hole diameter was 0.4 fl, and the number of discharge holes was 24.
The polycabrame 1' (nylon 6) polymer was melted and extruded through a spinneret with a 100 mm diameter.

After cooling and solidifying, 3-(
) Rimethoxysilyl)-purvyldimethiotadecyl ammonium chloride containing antibacterial antibacterial agent was applied, and then the godet was rotated at a surface speed of 1000 m/min.
--Received from Ra41C. Subsequently, the oil-treated yarn was rotated 1.5 times at a surface speed of 10507+1/min. Supply roller 5 heated to 50°C and surface speed 3150
After being stretched 3.0 times with a stretching roller 6 which rotated at a speed of m/min and heated to 180° C., it was kneaded with an inder 8.

0H.

Adhesion amount: 0.6% by weight Next, a tube-knitted fabric using the above-mentioned far drawn yarn was immersed in dyeing bath C shown below and dyed at 98°C for 30 minutes, and the antibacterial properties of the dyed fabric were measured.

Dyeing Bath A Dye Lanasin Black BRL
0.100'% o
wf(Lanaayn Black BRL v
Product name manufactured by Sandoz Co., Ltd.) Ilgaron Yellow 2B e
R.L. 0.012%owf
(Irgalon Yellow 2BRL Ciba Geigy Co., Ltd. Unasin Bordeaux RL 0.003% owf Cellpol DR-80 (Sanyo Kasei Co., Ltd. product name) 2.0
00% owf C bath ratio lnia 0 d Bath PH adjuster Primary phosphoric acid Secondary phosphoric acid The results are shown in Table 217,1. ° If the pH during dyeing is 7 or higher, it has an antibacterial effect, and if the pH is 6 or lower. It can be seen that the antibacterial effect is significantly reduced by 1-<.

Table 1 Example 2 In the process shown in Figure 2, polyamide zolamide (nylon-
6) After the polymer is melted and discharged, cooled and solidified, the same oil agent (containing antibacterial agent ■) as in Example 1 is applied using an oiling roller 23, and then a godet roller rotates at a surface speed of 800 m/min. It was taken over by 24.

Subsequently, the oil-treated yarn was rotated at a surface speed of 820 m/min and a supply roller 25 heated to 150° C. and rotated at a surface speed of 2600 m/min, and
After being heat-treated for stretching by 3.2 times with a stretching roller 26 heated to 26°C, the fluid is heated to a temperature of 210°C by supplying a fluid pushing nozzle as shown in Figure 1 of U.S. Pat. No. 4,268,940. After being made into a shrunken yarn, it was taken up by a pull-out roller 29 that rotates at a surface speed of z4oom/min, and thereafter passed through a guide 30 and wound up on a wine goo 31. Next, BCF obtained by the above method (Bulky Continuoa1
i'ilament) was used to make a carpet, immersed in the dye bath shown below, and then steamed at 98° C. for 5 minutes to fix the dye, the antibacterial properties (sterilization rate) of the dyed carpet were measured. The results are shown in Table 2. This shows that in order to maintain the antibacterial effect, it is necessary to maintain the pH at 7 or higher. The present invention has revealed the mechanism by which the antibacterial effect occurs.
-It was swept away.

a Dye Tectilon Izgyri 4R (Tectilon
Yellow4R): Ciba Geigy product name)
o,osos%owfTeetilonRed FR
LL: Ciba Geigy product name) 0.014%ow
f Tectilon Blue 6G (Tectilon B
lu@6G: Product name manufactured by Chipa Geigy)
o, 1 ots%owfb Leveling agent 7 Ionic leveling agent Mikregar 2N (Nippon Someka ■Product name) 2-0%owf C bath ratio -1:100 d PH adjuster: Primary phosphoric acid Secondary phosphoric acid

[Brief explanation of drawings]

FIG. 1 and FIG. 2 both show antibacterial Boria according to the present invention! This is a process route map for manufacturing a built-in yarn. FIG. 1 (FIG. 2) K, l (21)...Spinneret. 2 (22)...Discharge filament 13
(23)・・・Oiling sealer. 4 (24)...Godetstroller. 5 (25)... Supply roller. 6 (26)...-Stretching roller. 7 ・・・・・・Ivy drawing thread. 8 (28)...4th 5th grade poison 1-ra. 9 (31)...Wine goo In Fig. 2, 27...Fluid processing nozzle 29...Drawer p-ler.

Claims (4)

[Claims] (1) A method for antibacterial treatment of fibers, which comprises controlling the pH of the treatment solution to 7 or more when treating fibers with an antibacterial agent consisting of an organic silicon quaternary ammonium salt. (2) The antibacterial treatment method according to claim (1), wherein the fibers are polyamide yarns. (3) The antibacterial treatment method according to claim (2), wherein the polyamide yarn is in a state after spinning but before winding. (4) The antibacterial treatment method according to claim (1), wherein the organosilicon quaternary ammonium salt is an antibacterial agent represented by the following general formula. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 is a long chain alkyl group from C_6 to C_2_2,
R_2, R_3 and R_4 are lower alkyl groups, X is Cl
, Br, I or CH_3COO. )