JPS5887370A - Anti-static agent and method - 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 The present invention relates to an antistatic agent and an antistatic method. More specifically, the present invention relates to an antistatic agent and an antistatic method for fibers that impart an antistatic effect with excellent wash resistance to synthetic fibers, fibers containing the same, or textile products through simple processing.

Textile products made of synthetic fibers or fibers containing synthetic fibers generally tend to generate static electricity, which often causes problems in use. For example, it clings to the body when worn, attracts dust, etc. Various agents have been studied to eliminate these obstacles, but they generally lack durability against washing, are complicated to process,
Water-soluble cationic polymer compounds tend to have undesirable effects on products, such as poor durability, hardening of texture, discoloration of dyed products, and decreased color fastness. Yes, but it lacks washing resistance. As an improved method, a two-step treatment method in which treatment with this type of cationic polymer compound is followed by treatment with an anionic surfactant, or a water-insoluble complex prepared by mixing a cationic polymer compound and an anionic surfactant is proposed. There is a method of treating it as an aqueous dispersion using a solvent solution or an emulsifier. However, the two-stage processing method requires complicated processing steps.

Furthermore, processing methods using a solvent solution have a smell of the solvent during processing, and processing methods using an aqueous dispersion have problems such as a decrease in the color fastness of the dyed object and the stability of the emulsion of the aqueous dispersion.
I can't hope for a long wash-resistant product.

Also, in Japanese Patent Publication No. 42-5280, a cationic polymer and an anionic compound are used together to treat a miscellaneous substances.
In this case, anionic compounds are used more than once for cationic polymers, which requires a separate bath, which is time-consuming, and requires solvents, emulsifiers, etc. when carried out in the same bath, resulting in poor color fastness. There is a decrease in water resistance, washing resistance, etc.

The present inventors have arrived at the present invention as a result of intensive research into developing a durable antistatic agent that improves these drawbacks. That is, the present invention combines a vinyl polymer (a) having a quaternary ammonium base and a polycarboxylic acid and/or its salt (b) in an amount of 1 equivalent of the cation of (a) (in contrast to that of (b)).
An antistatic agent for fibers (first invention) and a vinyl polymer containing a quaternary ammonium base (a), which are used in combination in a ratio such that the carboxyl group of is 0.001-0.5 equivalent
and polycarphonic acid and/or its salt (b) (a
) The carboxyl group of mountain) is o for one equivalent of cation of
, 001 to 5% by weight solid content of an antistatic agent containing an equivalent of ooi to o5 is applied to the fiber, followed by heat treatment (second invention) ).

The vinyl polymer having a quaternary ammonium base used in the present invention has the general formula: Or, with a counter anion such as an aryl sulfonate anion via the nitrogen atom, the general formula (
1) Compound quaternary nitrogen-containing (meth)acrylate: 2-(meth)acryloyloxyalkyltrialkyl ammonium salt such as 2-(meth)acryloyloxyethyltrimethylammonium methosulfate-1-,2-(meth)acryloyl Oxyethyldiethylmethylammonium ethosulfate, 2-(meth)acryloyl oxyneethyltrimethylammonium chloride.

2-(Jri)acryloyloxypropyldiethylmethylammonium methosulfate■ General formula (2)
Compound quaternary nitrogen-containing (meth)acrylamide: 2-(meth)
Acrylamidoalkyl trialkylamonium salts such as 2-(meth)acrylamidoethyltrimethylanomonium methosulfate, 2-(meth)acrylamidoethyldimethylethylammonium ethosulfate + 2-(meth)acrylamidopropyltrimethylammonium tosylate, etc.■ General formula ( 3) Compound β-hinyloxyalkyltrialkyl or alkenylammonium salt (β-vinyloxyethyldiethylmethylammonium methosulfate, β-vinyloxyethylallylpiperidinium chloride, etc.) ■Compound N- of general formula (4) Alkylhinylviridinium m(N-/thiru-4-
Vinylpyridinium methosulfate N-lauryl-4
-vinylpyridinium chloride, etc.) Compounds of the general formula (5) vinylbenzyltrialkylammonium salts (r-hinylbenozyltrimethylammonium chloride, P-vinylbenzyldimethyllauryl ammonium bromide, tt > nato) etc. General formula (6 ) Compounds such as vinyldialkylimidazolinium halides (N-vinyl-2,3-dimethylimida'silinium furomite, etc.) ■Compounds with general formulas (allyltrimethylammonium chloride, etc.) Also described in Japanese Patent Publication No. 11347/1983 A vinyl polymer that can also be used as a monofilament component having a quaternary nitrogen atom containing one of the vinyl compounds having a quaternary ammonium base or a copolymer component (
It is also possible to contain 7.

Copolymerizable vinyl monomers include nonionic monomers such as hydrophilic (meth)acrylic acid amide.

(meth)acrylic acid, hydroxy lower alkyl (meth)
(i) Acrylates (i) Lipophilic (meth)acrylic acid esters, acrylonitrile, styrene, vinyl acetate, and mixtures of two or more thereof can be mentioned. Preferred among these are styrene acrylate and vinyl acetate.

In order to obtain a vinyl polymer having a base having the quaternary ammonium base in the (co)polymer, polymerization or copolymerization may be carried out by a conventionally known method. In this case, the vinyl polymer having a quaternary ammonium base can be polymerized or copolymerized by using the above vinyl compound having a quaternary ammonium base, or by using a vinyl compound having each of the tertiary amino groups. After that, an alkyl halide is added to the 8th amino group,
It is also possible to react with a quaternizing agent such as alkyl sulfuric acid to form a quaternary ammonium base.

In the present invention, the molecular weight of the polycarboxylic acid (polycarboxylic acid also includes oxybolycarphonic acid) is usually 1000 or less, preferably 500 or less. 5 molecules.

Carboxylic acids (malonic acid, succinic acid, glutaric acid) that are compatible with cationic polymers, which are polymers with quaternary ammonium bases, have a molecular weight of 1000 or more in dogs.

Dicarphonic acids such as adipinoic acid, linchoic acid, tartaric acid; trioquine butyric acid, propane-1,2,8-tricarboxylic acid, butane-1,2,8,4-tetracarboxylic acid.

tricarboxylic acids such as citric acid], aromatic polycarphonic acids (phthalic acid, isophthalic acid, etc.).

Dicarboxylic acids such as terephthalic acid and naphthalic acid.

Trimellitic acid, naphthalene-1,4,5-1-licarphonic acid, bilomerinodo acid, etc.), nitrogen-containing polycarphonic acids, and nitrogen-containing polycarphonic acids, preferably 3 or more in the molecule. The polycarfonic acid having tri or more carbon atoms has a carboxyl group, and particularly preferred is the polycarphonic acid having four or more carbon atoms having four or more carboxyl groups in the molecule.

The polycarphonic acid may be in the form of an acid as it is, but it is preferably in the form of a salt from the viewpoint of water solubility, such as salts of alkali metals, ammonia and/or lower amines. Examples of alkali metals include 1.i, Na, Ni, etc., and examples of lower amines include lower alkylamines (trimethylamine, tributylamine, etc.),
Examples include alkanolamines (triethanolamine, jetanolamine, monoethanolamine, etc.). Among the salts, preferred are alkali metal salts,
Particularly preferred are Na and/or K.

In place of polycarboxylic acids/or salts thereof in the present invention, monocarphonate salts (saturated or unsaturated fatty acid salts, such as sodium laurate, azmo-listinate, etc.
+t,, r, etc.), sulfuric ester salts, no visible traces.

In the present invention, the vinyl polymer (a) and the polycarboxylic acid and/or its salt (b) are combined so that the carboxyl group of 1 equivalent of the cation (a) is 0.001 to 0.5.
They are used in combination in an equivalent amount, preferably in a ratio of 0002 to 03 equivalents. If the amount of (1) is less than 0.001 equivalent, the washing resistance of the static protection II- effect will be poor, and if it is more than 0.5 equivalent, it will not be possible to process it in the same bath with the cationic polymer (a). becomes.

The antistatic agent of the present invention is used as an antistatic agent for fibers. The above-mentioned fibers to which this antistatic agent is applied include polyester, polyamide, polyester ether, polyacrylic (polyacrylonitrile), polyvinyl chloride, and polyolefin. Synthetic fibers such as (polyzoropyreno, etc.), semi-synthetic fibers such as triacetate, cyacetate-1, etc., and cotton as their fiber structures. Tow, yarn, and 9 knitted fabrics.

Non-woven fabrics, felt, carpets, etc. i) Can be produced.

The application amount of the antistatic agent can be varied depending on the degree of antistatic property, the form of the fiber structure to be treated, and the type of fibers constituting it (therefore, it can be varied in various ways). The solid content is 0.01 to 5%, preferably O1 to 2q6.If the applied amount is less than 0.0196, the antistatic IL property is not sufficient, and if it is more than 5%, the treated fiber The texture of the structure may become rough and hard.

Antistatic agents are applied to fibers as treatment liquids, but the process liquids are prepared by mixing concentrated aqueous solutions of each compound to form a concentrated antistatic agent, which is then diluted to the required concentration before use and used to treat fibers. A method for preparing each compound and directly preparing a treatment bath for fibers at a treatment concentration from both of them before use, and applying such a treatment liquid for antistatic purposes to fibers or fiber structures. Examples of this include conventional methods such as a putting method, a spray method, and a dipping method.

Application is often applied to fibers or fiber structures (often applied to fibers or fiber structures that have been subjected to dyeing treatments such as bleaching, dipping, printing, etc., but is not limited to this; for example, in the case of filaments, spinning The antistatic agent can be applied after the heating step or after the heating step in fabricated yarn production by impregnating or contacting the filament with a solution containing the antistatic agent. The temperature of the treatment liquid is usually It cannot be heated at room temperature.After treating the fiber with a treatment liquid, it is usually heated at 40 to 180℃.
Dry for t-1 minutes and heat treat at 150-200°C for 3 minutes-30 seconds.

In addition to antistatic agents, textile products also include antifouling agents, antifouling agents, anti-disaster agents, polishing agents, and matting agents.

The antistatic agent of the present invention does not preclude its use in combination with processing agents such as dye fastness improvers, and may be used in combination with any processing agent depending on the purpose. The antistatic agent and the antistatic method have the effects described in F.

(1) It has an excellent antistatic effect and good washing resistance.

(2) Antistatic treatment can be performed in the same bath, making the treatment simple.

(3) There is no need to use solvents, so there is no smell of solvents during processing.

(4) Since the antistatic agent does not need to be treated as an aqueous dispersion using an emulsifier, there are no problems with low color fastness or emulsion stability.

The present invention will be further explained below with reference to Examples. The physical properties of the processed fabrics shown in the examples were measured at a room temperature of 20°C1 using the following measurement method.
Relative temperature 40. //R0I1. Shimo Kyoto University / Using a Ken-type rotary static tester (manufactured by Koa Shokai), it was rubbed against cotton gold cloth No. 2 under condition F of 400 r, p, m, and a load of 500 y, and the electrostatic voltage generated after 1 minute ( v) was measured.

2. Washing resistance New Beads (manufactured by Kao Soap Co., Ltd.) were washed in a 0.5% aqueous solution at room temperature for 10 minutes, washed under running water for 10 minutes and dried, which was considered one wash, and the washing was repeated up to 10 times.

3. Rubbing fastness, 118T, In accordance with -0849, the sample was rubbed with the target cloth cotton gold cloth 100 times at a load of 200 f using a Gakushin type rubbing fastness tester. However, the test cloth used was one that had been dyed under the following conditions before being treated with an antistatic agent.

Staining conditions t1 (mi): Foron Rub
ine S-2GFL 5% o 0w, r.

Temperature x time: 130° (': x 60 minutes bath ratio:
1 2 20 Temperature x Time: 80° x 20 minutes Bath Ratio: ]: 20 Water Washing Under two streams of water for 20 minutes Example 1 100 parts of a 10% aqueous solution of potassium dimethitate in dimethylaminoethyl methacrylate was stirred at room temperature for 30 minutes. By mixing, a light brown transparent aqueous solution of the antistatic agent of the present invention was obtained.

Next (Create a 2% aqueous solution of this solution, pad it with polyester tack dyed cloth at room temperature, and use a mangle to achieve a squeezing rate of 80.
After drying at 110°C for 3 minutes, dry at 180'C for 3 minutes.
Heat treatment was performed for 0 seconds. The generated electrostatic voltage and abrasion fastness of the processed cloth obtained by this treatment were as shown in Table 1. In addition, the original (Comparative Example 1) PAEM (Comparative Example 2) and the commercial product (
Comparative Example B) (product in which a complex of PAEM and an anionic activator is dispersed with a nonionic activator) was also subjected to performance measurement when treated at the same solid content concentration for comparison. Results first
Shown in the table. From Table 1, it can be seen that the composition according to the present invention exhibits good antistatic properties and excellent durability. Also, compared to the original, there is less decrease in fastness to friction.

Table 1 Example 2 200 parts of a 10% aqueous solution of styrene and 2-methacryloyl oxyneethyl dicitric acid triuno were stirred and mixed at room temperature for 30 minutes to obtain a white transparent aqueous solution of the antistatic agent of the present invention. Ta. Next, prepare a 290 aqueous solution of the solution, put nylon tricot (scouring-L) on it at room temperature, squeeze it to 80% with Manoglu, dry at 1106C for 3 minutes, and then 170°C.
Heat treatment was performed for 30 seconds at C. Note that a comparison was made in the same manner as in Example 1. The results are shown in Table 2. The products of the present invention exhibited excellent durable antistatic effects as shown in Table 2.

Table 2 Examples 3-19 20% aqueous solution of PAPR4 or 20% polymer of quaternary ammonium salt with dimethyl sulfate of hinylpyridine
1 of aqueous solution and various polycarphonate salts (listed in Table 4)
An antistatic agent solution of the present invention was prepared by blending a 0% aqueous solution. A 2% aqueous solution of the above solution was prepared, and a polyester processed yarn fabric (dyed No. 5) was padded at room temperature, squeezed to 75% with a mangle, dried at 110°C for 3 minutes, and then heat treated at 180°C for 30 seconds. I did this. As a comparison, performance was checked including Comparisons 1 to 3 in the same manner as in Example 1, and the results are listed in Table 3. From the above, it can be seen that the material according to the present invention exhibits good antistatic properties and has excellent durability. Furthermore, there was little decrease in fastness to rubbing.

Claims (1)

[Claims] 1.1' Vinyl polymer with quaternary ammonium base (a
) and polycarphonic acid and/or its salt (II) in a ratio such that 0001 to 05 carboxyl groups of mountain) per 1 cation of I). antistatic agent. 2. The anti-banding agent according to claim 1, which is a polycarphonic acid and/or a salt thereof having three or more carboxyl groups in the molecule. 8 Quaternary ammonium cum base A vinyl polymer with (
a) and polycarphonic acid and/or its salt mountain) and wo(
After applying to the fiber an antistatic agent containing 001 to 05% by weight of the carboxyl group of (1)) in a proportion of 0001 to 05% by weight per equivalent of the cation of a). , a method for preventing static electricity from pongee which is characterized by heat treatment.