JPS58136822A - Antimicrobial acrylic synthetic fiber and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain the titled fibers having improved antimicrobial properties and resistance to washing with low toxicity, by incorporating a specific diphenyl ether compound in an acrylic copolymer containing acrylonitrile and a basic monomer, and wet spinning the resultant mixture. CONSTITUTION:A solution containing (A) an acrylic copolymer containing (i) 40wt% or more acrylonitrile and (ii) 0.5-10wt%, preferably 1-5wt%, basic monomer, e.g. N,N-dimethylaminoethyl methacrylate, or an acrylic polymer mixture and (B) 0.01wt% diphenyl ether derivative, preferably 2,4,4'-trichloro-2'- hydroxydiphenyl ether, in an organic solvent is wet spun into an aqueous solution of the organic solvent to give the aimed synthetic fivers. Acrylic copolymer containing 80wt% or more acrylonitrile and 15wt% or less methyl methacrylate or vinyl acetate is preferred for the acrylic copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a synthetic thread of antibacterial acrylic yarn with good wear resistance and a method for producing the same.

Acrylic yarn synthetic fibers are widely used for clothing and electrical equipment, but in recent years they have been used in the sanitary field such as mats and carpets, as well as sports clothing, socks, and underwear that come into contact with external heat from the human body.

Things such as sheets and wool that have anti-resistance and anti-value properties are becoming more susceptible to electricity.

Contains natural or synthetic compounds with antibacterial properties.
Methods such as spraying or impregnating fibers with the compound butyric acid are known, but these methods have the drawback that their effectiveness is not long-lasting and the attached antibacterial agent easily falls off during subsequent washing. have. Furthermore, when resin processing is performed using a resin to which an antibacterial agent is added in order to impart washing resistance to the fibers, there is a drawback that the texture of the fibers is impaired.

For example, a method has been proposed in which a copper compound, metal powder of copper or zinc, or an azole conductor is added to an acrylic polymer, but the method using a copper compound has problems with the color of the copper itself, and the color of the product. Inconvenient problems such as the formation of copper-water gelatinization occur during use, and the addition of copper powder causes problems in p-permeability and decreases in thread properties during spinning, as well as strong elongation and warp.
East t! ! , the decline in the number of eyes cannot be denied. Additionally, azole d alone has problems with toxicity, which hinders its practical use.

On the other hand, diphenyl ether derivatives of the 244'-)lichloro-o-2'-hydrooxy/sinoenyl ether family are Gram-positive M, Gram-mutant bacteria 1. It is said to have a broad spectrum of anti-fungal properties against fungi and other organisms, and is said to have low toxicity and little irritation to the skin, but this diphenyl ether conductor and ordinary acrylic When wet-spinning a bath-control agent solution of a type of polymer, there are many diphenyl ether derivatives eluted in the spinning bath during spinning, so the diphenyl ether derivatives contained in the fibers have the disadvantage of increasing costs. There is.

Uninvented @ ◆ has completed the book as a result of intensive research in order to improve these shortcomings.

The purpose of the present invention is to provide an antibacterial acrylic synthetic fiber that has excellent anti-oxidant properties and anti-oxidant properties, has less 14111eIL to the skin and live wires, and is wash-resistant. Another object of the present invention is to provide a method for manufacturing such antibacterial acrylic synthetic fibers easily and inexpensively.

The fibers of the present invention contain less diphenyl ether anchor conductor represented by the following general formula for an acrylic co-polymer or acrylic polymer mixture containing at least 440xwt% acrylonitrile and LL5-101ii% salt monomer. It contains exactly 01% of tomoα01.

The general formula or 1 uninvented square is a mixture of acrylonitrile of at least 40 mm INN, a basic monomer of α5 to 10%, and an acrylic coelectric polymer or an acrylic thread mixture, and the following general formula 4, The diphenyl-able conductor and the special yarn are wet-spun during the bathing process.

The acrylic co-electrolytic polymer containing a basic 7-mer used in the present invention can be any polymer containing at least 40% by weight of acrylate and having fiber formation. It is also possible to use That is, 40% by weight or more of lye and 5 to 10% of basic monomers, other vinyl monomers such as acrylic acid, methacrylic acid, or alkyl esters thereof, beer acetate, and vinyl chloride. , vinyl chloride + J 7
A suitable combination of sodium allylsulfonate, sodium methallylsulfonate, vinylsulfone soda, styrene sulfone soda, etc. can be copolymerized in a proportion of up to 60%.

Acrylonitrile 85-% or more on the shaft and α1~10''
A polymer copolymerized with It% of a basic hexamer, up to 15% by weight of methyl acrylate or vinyl acetate, and up to 1.51% of a sulfone group-containing monomer, or at least 4o*iix of monocrylonitrile. And 05~
A copolymer obtained by copolymerizing 10 parts by weight of a basic monomer, 20 to 58 coul% of vinyl chloride and/or vinylidene chloride, and a monomer containing a sulfone tIt group at a yield of 5% or less is preferred.

The acrylic polymer mixture used in the present invention is a mixture of two or more polymers, each of which contains at least 40% by weight of polymerized acrylonitrile and ~10% by weight of basic monomer 'ICLs. Normally, an acrylic polymer not containing a basic heptamer and an acrylic polymer or a vinyl polymer containing a basic heptamer are mixed.

Acrylic polymers that do not contain clay-based heptamers are Aku I.
JQ nitrile is copolymerized with the above-mentioned vinyl monomer and, if necessary, with a sulfone group-containing monomer.For the acrylic polymer containing a basic monomer, the above-mentioned acrylic co-electropolymer can be safely used. It can be used as it is by increasing the content of basic hexamer depending on the situation.

Also, what kind of vinyl polymer contains Hanawamenshinanatsuma? lI
Alkyl esters of acrylic ridges, alkyl esters of methacrylic needles, and vinyl acetate.

It is mainly composed of vinyl monomers such as vinyl chloride, vinylidene chloride, and styrene derivatives, and is easily soluble in the organic solvent used and inseparable in an aqueous solution of the organic solvent. Among the vinyl monomers, particularly preferred are methyl methacrylate and styrene, which usually contain 50 to 90% of the vinyl monomer.
Contains 0 weight it%@&. Also included are vinyl polymers copolymerized with acrylonitrile.

Examples of the basic monomer used in the present invention include:

NN-dimethylaminoethyl methacrylate.

NN-diethylaminoethyl methacrylate.

NN-dipropylaminoethyl methacrylate.

NN-diethylaminoethyl acrylate, NN-diethylaminoethyl acrylate, and NN-N-dipropylaminoethyl acrylate are NN-dimenalaminosterene, or acrylamide, methacrylamide, and derivatives of these amides, vinylpyridine and some parts thereof. .

Vinylpyrrolidone and its conductors may be mentioned.

The content of basic hexamer in the acrylic copolymer or acrylic polymer mixture in this @mei is 0.5 to 10% by weight, preferably 1 to 5% by weight. a5 layer *96
If it is less than that, the effect of improving the yield of diphenyl ether conductor will be small.

Moreover, if it exceeds 103iii%, the fibers will become discolored and heat resistant.

Decrease in light resistance and physical properties for 1 meter of chess were markedly reduced.

1 lall of diphenyl ether used in the present invention is 2,
4.4'-)dichloro-2'-hydroxydiphenyl ether, 22'4-)! J/Roreau 5'-hydroxydiphenyl ether, 2.4.5'-triclog-2'-hydroxydiphenyl ether, or a mixture thereof, but 2,4.4'-) refugia in the kidneys. Rho 2'-hydroxydiphenyl ether is better.

Furthermore, it may also be used in combination with other known antibacterial or antibacterial substances. Diphenyl ether-conductor content i is more than 01 violet for acrylic 1 combination, preferably u, u
2~2j [1 for east.

Since the name of the 7th technique, ether, and the mother's body is αυ1Nm, it is not possible to obtain a light amount of resistance in the lecture, so one must be blessed.

Below is the invention! J! I will explain the method of manufacturing and selecting the iron to be used.

Organic solvents for the acrylic polymer used in the present invention and the spinning bath include dimethylformamide, dimethylacetamide, dimethylsulfoxide, and acetone.

The concentration of the miw agent solution for acrylic electrolyte is usually 18-
26] k storage%. Diphenyl ether - The conductor can be added as is or as a solution in a pre-prepared 411 bath solution.
When it is added to an acrylic polymer mixture, it is preferably blended in advance into a bath copper solution of an acrylic polymer or a vinyl electrolyte containing a basic polymer.

Transfer of organic solvent in an organic solvent aqueous solution that is a spinning bath
L employment wealth 60 m grave% ~ 65] [Ji to make a child.

The diphenyl ether conductor released during the spinning bath is reused in the form of mesh in the solvent recovery process so that it does not flow out of the yarn.

Stretching of the spinning yarn, washing with water, drying, and heat treatment are carried out, and it is preferable to carry out this combined drying at a temperature of 180°C or less.
〈It is preferable to perform the steaming treatment at a temperature of 120° C. or lower.

The anti-acrylic synthetic fiber of the present invention has a wide spectrum of resistance against microorganisms such as gram-resistant, gram-resistant, mold, and *mother, and has low toxicity and little irritation to the skin and mucous membranes. , The wax fiber performance of acrylic fiber in nine pieces,
It retains its texture and improves fiber properties by washing.Table 1
Even if the anti-cocoon agent f: tk is dropped, it does not become unstable due to self-pulsation, and the anti-cocoon agent bleeds out). It never loses its effectiveness.

The antibacterial acrylic synthetic fiber of the present invention can be used as it is, or by blending cotton and rayon with other animal fibers. Cloth, suits, clothing, underwear, etc., I-wide 8
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Hereinafter, the present invention will be specifically explained using examples. Note that (%) in the examples refers to "amount %".

*'hm Example 1 244'-
) 50% DMF solution M of 21-hydroxydiphenyl ether (Tl(DE)) was added and heated at 20℃50.
% DMF chickenpox solution, spun into 100 million strands with a final single denier of 50 d, then stretched in 20% DMF water I&A at 90°C, washed with water at 65°C, dried at 160°C with dry heat, 1 mechanical crimp. After applying this, crimp setting was performed at a steam temperature of 110°C.

I created the Koku, which was cut and spun from the much-scorned 1mk. This material was mixed with the original yellow grapes and the large vines, and was placed in the soil of 7'C cold weather at 57℃ for 24 hours. -Items where growth of - on one side of the object was not observed-
Those that were recognized to have grown were given a score of 10.

In addition, Tankoji's ↓'kiDitmFIL uses DMF-bathed turtle of fibers without THDM as a control, and the sample is subjected to the same ivific treatment as the control, and used in 10 pieces of quartz cell 1. 85 hmK and ultraviolet absorption glare FiL
is kept constant and its -
1 was analyzed.

Table 1 shows the spinning stock solution addition 1°HDJ%/poly)
To show 1° resistance, the TH and E content in the product must be
, 01 or more is required.

Also, due to the presence of a stiffening monomer, THDjli's Ayu-9 is different from normal acrylic yarn TG. st = M It was improved by about 2 times compared to Example 2 THLlk 24 was added to the DMF bath solution of acrylic copolymer a & 24+A having the composition shown in Table 2. 1.0% of DMF bath solution was added to the acrylic copolymer. Added 55% D at 18℃
The single thread denier of the shrimp end in the MF aqueous solution is 2. The fibers were spun to give Od, then stretched in a 15% DMF aqueous solution at 95°C, and washed with water at 60°C.

After drying with dry heat at 150°C, a mechanical crimp was applied and the crimp set was weakened with steam heat at 105°C. This fiber T
HDE content (yield) and antibacterial properties were investigated in the same manner as in Example 1.

The results are shown in Table 2.

Due to the presence of basic 7-mer, the yield of 'l'1 (DE) is improved by about twice that of acrylic fibers with current applied.

The fiber obtained with A17 is satisfactory in terms of yield and antibacterial properties, but fiber performance example 5 such as fiber coloration, heat resistance, light resistance, etc. AN/MA/SMAS = 91.3/aO/a7 Noah Ri! j k series co-arashi se body drama direct 224 pi) l) M)
22% of acrylic or vinyl-based rubber for mixing with kC-6 and T HD E
60% dissolved [3MN solution]
1"1-ILJ ratio 1.5 for mixed electric power and electric power
DMFfgM of the electric composite containing 15°C 55% D
Mθ゛Aqueous solution & spun until the final denier is iod, then 20: A 7-noise set meeting was held at a high temperature of 108°C. The yield and resistance of the treated fibers were investigated in the same manner as in Example 1.

Example 4 AN/MA/5MA3 = 9 Ll, 9/a5/
CJ, 6 F) 7cryl yarn co-merged mt 2υ% dimenal sulfoxide (DM!30) solution with 9 parts of styrene/
DEAgMA = 6 U electrolyte once 20% DMBO
tittic THDE203 p mixed with 1 part of solution
The uso solution was cut into rings and added to give a total concentration of 15%, and 1 ckt was added to the DMSO* solution at 45° C. at 15° C. at the end of 5. The yarn was spun to give Od, stretched in a 10% DMSO solution at 90°C, heated at 60°C on a wooden stake, dry-recorded at 155°C, then slowly mechanically crimped, and then crimped at 115°C for 7 nozzles. It is resistant to grape 41 and large V.
I missed it.

*Example 5 AN/6) [vinyl/SMAS =91.4/ao
/[L6 f; concave A/DEAkM due to dimethylacetamide (DMAC) bath for acrylic yarn co-merging 4525
A = 6Ll/4LI irises union 26% IITHom;
i: DMAC # & * which made Roshima bath 4 I4 ML Q6 which is 1.0 X against the combined dazzle 4 ubAkC% enemy i of the grouped group i 20℃.

55 mm of DMAC* There are 2.
15/is at 90℃ after a long time of spinning to become Lld
L) Stretched in MkC water bath, washed with water at 55°C, and dried for 16L
After drying with Lu, mechanical limp was applied, and clips were set at 112°C with steam heat. The obtained fibers are
It contained 0.42%. Knitted fabrics were created by cutting and spinning the fibres. Wash this house of things 1υ, 5, 10
, 15, Anti-d T41 after 2°C cycle: Examination was conducted in the same manner as in Example 1.

Claims (1)

[Claims] (1) At least 40% by weight of 7-crylonitrile and α5
At least one diphenyl ether conductor represented by the following general formula is added to an acrylic copolymer or an acrylic polymer mixture containing ~10% by weight of a basic monomer.
01 Ant-resistant acrylic synthetic castle fiber made with heavy metal. General formula (2) Acrylic copolymer is 7 Acrylonitrile tube 8
0% by weight or more, methyl acrylate or -1 vinyl
5] The fiber according to claim 1, containing 1i% or less. (6) The acrylic thread containing vinyl chloride and/or magnetized vinylidene contains 20 to 587% dVf4.
m water range 1st dust ml bandit fiber. (4) Patent 1 #Kyo-1 where the acrylic polymer mixture is a mixture of an acrylic copolymer that does not contain a basic heptad and an acrylic electropolymer or a vinyl spinning wheel combination that contains a basic heptad. Line fibers in the first shelf ml area. (5) Basic seven-mer is NN-dimethylamine ethyl methacrylate), NN-7 methylaminoethyl acrylate, NN-diethylaminoethyl methacrylate, NN
-Metalized with diethylaminoethyl acrylate, acrylamide or methacrylamide/Claims-IJ
Other axis of J entry ◎ (6) ji II of the patented ice that contains 1 to 5% violet of the sparrow monomer! Fibers listed in 1 volume. (Ha diphenyl ether derivative is 244'-)lichloro-2'-hydroxydinenyl ether The content of the 1i+6+7 phenyl ether spindle of the first horizontal writing is 0.02 to 2 iris. The fiber according to item 1, which is made of ice cream. 191 Contains an acrylic copolymer or acrylic polymer mixture comprising at least 140% by weight of acrylonitrile and 0.5 to 10% by weight of a basic monomer, and a diphenyl ether #conductor represented by the following general formula: A method for producing a resistant acrylic synthetic fiber by wet spinning an organic solvent solution into a brewing organic solvent solution. General formula (button) Acrylic copolymer is 7crylonitrile td
0% or more, 1 liter of methyl acrylate or vinyl vinegar
Claim 9 JJ containing t5 heavy lid % or less! IC
! manufacturing method in the area. (11) The manufacturing method according to claim 9, wherein the acrylic co-containing member is a co-container containing vinyl chloride and/or vinylidene cyclide t-20 to 58-t-1. Claim 9, wherein the polymer mixture is a mixture of an acrylic polymer that does not contain a basic hexamer and an acrylic polymer or a vinyl yarn polymer that contains a basic hexamer. Production method. (15) The basic monomer is NN-dimethylamine ethyl methacrylate, NN-dimethylaminoethyl acrylate, NN-diethylaminoethyl methacrylate, N
9. A method for producing a N-diethylaminoethyl acrylate, acrylamide or methacrylamide. (15) The production method according to claim 8, wherein the basic monomer content is 1 to 5 μm. The organic 1 wound fluid was pre-blended with diphenyl ether-conductor, and the patent claims that the basic monomer was added to the non-metallic acrylic polymer Unantan bath solution. Production method. (Yu) Diphenyl ether # conductor is 2a4'-)su/
口u-2'-ha4)
9. The manufacturing method according to claim 9, wherein (17) 44 solvent is NN-dimethylformamide. NN dimethylacetamide, dimethyl sulfoxide or acetone, the method according to claim 9.