JPS58144176A - Antistatic 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 a fiber antistatic agent and antistatic method that imparts 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 remove these problems, but they generally have poor durability against washing, complicated processing operations, poor durability effects, hardening of texture, and problems with dyeing. At present, there are almost no antistatic agents that can be put to practical use because they tend to have negative effects on products, such as discoloration, fading, and a decrease in color fastness.

For example, there is a water-soluble cationic polymer compound as a well-known durable antistatic agent, but this has insufficient washing resistance.As an improvement method, after treatment with this type of cationic polymer compound, There is a two-step treatment method in which treatment is performed with an anionic surfactant, or a method in which a water-insoluble complex prepared by mixing a cationic polymer compound and an anionic surfactant is treated as an aqueous dispersion using a solvent solution or emulsifier. . However, the two-stage processing method requires complicated processing steps.

In addition, the treatment method using a solvent solution has problems with the smell of the solvent during treatment, and the treatment method using an aqueous dispersion has problems such as a decrease in the color fastness of the dyed object and the stability of the emulsion of the aqueous dispersion. A significant improvement in washability cannot be expected.

In addition, in Japanese Patent Publication No. 42-5280, a cationic polymer and an anionic compound are used in combination to treat fiber materials.
In this case, the anionic compound is used in an equivalent amount or more to the cationic polymer, so it must be carried out in a separate bath, which is slow and labor-intensive, and if carried out in the same bath, solvents, emulsifiers, etc. are required. There is a decrease in color fastness, 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 provides an antistatic agent for fibers (first invention) which is formed by using a vinyl polymer ial having a quaternary ammonium base in combination with a polycarboxylic acid and/or its salt 1b) and a water-soluble salt of an inorganic acid 1c). ) and vinyl polymer 1al with quaternary ammonium base and polycarboxylic acid and/or
or its salt fb) and a water-soluble salt of an inorganic acid fc).
This is a method for preventing static electricity on fibers (second invention), which comprises heat-treating the fibers after application.

The vinyl polymer 1a) having a quaternary ammonium base used in the present invention has the general formula % formula %: 2) [wherein R1 is H or a methyl group, R2, R3, and R4 are alkyl, alkenyl, hydroxy Organic groups such as alkyl, aracyl, alkoxyalkyl (number of carbon atoms: usually 1 to 2
0) R3 and R4 may optionally be connected to each other via an oxygen atom or a nitrogen atom to form a cyclic group together with eN. or halide anion, alkyl (usually 01-4) sulfate anion, aryl or alkyl/L/, (usually C□~
, ) is a counter anion such as an aryl nulfonate anion. ] Examples include water-soluble polymers of vinyl compounds shown in the following.

Specific examples of the compound include the following vinyl compounds.

■ Compound of general formula (1) Quaternary nitrogen-containing (meth)acrylate: 2-(meth)acryloyloxy, alkyltrialkylammonium salt For example, 2-(meth)acryloyloxyenal trimethylammonium sulfate, 2-(meth)acryloyloxy, alkyltrialkylammonium salt, ) Acryloyloxyethyldiethylmethylammonium ethosulfate, 2-(meth)acryloyloxyethyltrimethylammonium chloride, 2-(meth)acryloyloxypropyldiethyl! Quaternary nitrogen-containing (meth)acrylamide such as remethylammonium methosulfate: 2-(meth)
Acrylamidoalkyltrialkylammonium. ! :, 2-(meth)acrylamidoethyltrimethylammonium methosulfate, 2-(meth)acrylamidoethyldimethylethylammonium ethosulfate, 2-(meth)acrylamidopropyltrimethylammonium tosylate, etc.■ General formula (3 ) compounds β-vinyloxyalkyltrialkyl or alkenylammonium salts (β-vinyloxyethyldiethylmethylammonium methosulfate, β-vinyloxyethylallyl biveridinium chloride, etc.) ■ Compound N of general formula (4) -Alkylvinylpyridinium salt (N-methy)v-4
-vinylpyridinium methosulfate, N-lauryl-4-vinylpyridinium chloride, etc.) Compounds of general formula (5) Vinylbenzyltrialkylammonium salts (P-vinylhensyltrimethylammonium chloride, P-vinylbenzyldimethyllauryl ammonium bromide, etc.), etc. ■ Compounds of general formula (6) Vinyl dialkylimidazolinium halide (N-viny/L/-2.8-dimethyl reimidazolinium deromide), etc. ■ Compounds of general formula (7) Allyltrimethylammonium chloride and other monomer components having a quaternary nitrogen atom as described in Japanese Patent Publication No. 11847/1984 can also be used.

Although it is essential that the vinyl polymer contains one or more vinyl compounds having a quaternary ammonium base as shown in the above example as a monomer component, it is necessary to contain one or more vinyl compounds having a quaternary ammonium base as a monomer component. It is also possible to contain other copolymerizable vinyl monomers as copolymerization components. Examples of copolymerizable bi=)V monomers include nonionic monomers such as EVA hydrophilic (meth)acrylic acid amide, (meth)
Examples include acrylic A/filk, hydroxy lower alkyl/I/(meth)acrylate; lipophilic (meth)acrylic acid esters, acrylonitrile-1-styrene, vinyl acetate, and mixtures of two or more thereof. Preferred among these are nutylene, acrylamide and vinyl acetate. In the (co)polymer, the content of the vinyl compound 1aj having the quaternary ammonium base is usually 50 mol% or more, preferably 90 mol% or more.

The molecular weight of the polymers ranges over a wide range; (e.g. 1000
~ millions or more) can change but 30%
An aqueous solution having a viscosity (at room temperature) of 2,000 to 10,000 centimeters is preferable.

A vinyl polymer having a quaternary ammonium base can be obtained from these vinyl compounds by polymerization or copolymerization using a conventionally known method. In this case, the vinyl polymer having a quaternary ammonium base may be the above vinyl compound having a quaternary ammonium base, or the vinyl polymer having a quaternary ammonium base may be used.
After polymerization or copolymerization using a vinyl compound having a primary amino group, it is also possible to react the tertiary amino group with a quaternizing agent such as an alkyl halide or alkyl sulfate to form a quaternary ammonium base. be.

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

If the molecular weight is greater than 1000, the compatibility with the cationic polymer, which is a polymer having a quaternary ammonium base, will be poor and it will be impossible to use it in the same bath. Water-soluble polycarboxylic acids can be used in the form of acids or salts, and specifically, aliphatic polycarboxylic acids [dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, and tartaric acid] Acid; trioxybutyric acid, propane-1.2.8=tricarboxylic acid, butane-1,2,8,4
- polycarboxylic acids of tri or higher such as tetracarboxylic acid and citric acid], aromatic polycarboxylic acids (dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, naphthalene-1, (4,5-) dicarboxylic acids, tri- or higher polycarboxylic acids such as pyromellitic acid), nitrogen-containing polycarboxylic acids such as trilotriacetic acid, ethylenediaminetetraacetic acid, etc.), and mixtures of two or more thereof. The number of carboxyl groups is usually 2 to 10.

Among these, preferred are tri or higher polycarboxylic acids having three or more carboxyl groups in the molecule, and particularly preferred are tetra or higher polycarboxylic acids having four or more carboxyl groups in the molecule. be.

The positive carboxylic acid may be in the form of the acid itself, but the salt form is preferred from the viewpoint of water solubility, and examples of the salt include salts of alkali metals, ammonia, and/or lower amines. Examples of alkali metals include Li';'N
Examples of lower amines include lower alkylamines (trimethylamine, tributylamine, etc.), alkanolamines (togetanolamine, jetanolamine, monoethanolamine, etc.), which have a strong effect on salts. Preferred are alkali metal salts, particularly preferred are Na and/or K salts.
It is.

Monocarboxylic acid salts (saturated or unsaturated fatty acid salts such as IJa laurate, ammonium myristate,
(g) When sulfuric acid ester salts, sulfonic acid salts, phosphoric acid ester salts, etc. are used, the excellent washing resistance and antistatic effect obtained in the present invention is not observed.

Water-soluble salts of inorganic acids 1c) include inorganic acid salts of guanidine, lithium, calcium and /l tahmagnesium. Any inorganic acid salt that can be used as a water-soluble salt includes hydrochloride, bromate, sulfate, nitrate, and phosphate. Among the inorganic acid salts, preferred is hydrochloride in the case of guanidine;
In the case of lithium, calcium and magnesium, these are hydrochloride and nitrate; specifically, inorganic acid salts of guanidine include guanidine hydrochloride, guanidine bromide, guanidine sulfate, and guanidine dinitrate; inorganic acid salts of linium include chloride. Lithium, lithium bromide, lithium sulfate, lithium nitrate, lithium phosphate, etc.; Inorganic acid salts of calcium include calcium chloride, calcium nitrate, etc.; Examples of inorganic acid salts of magnesium include magnesium chloride, magnesium nitrate, etc. be able to. Among these, preferred are inorganic acid salts of guanidine and inorganic acid salts of lithium and calcium, and particularly preferred are:
These are guanidine hydrochloride, lithium chloride, lithium nitrate, calcium chloride and calcium nitrate.

Two or more of these salts fc) can also be used in combination.

In the present invention, the ratio of vinyl polymer (al and polycarboxylic acid and/or its salt (b) is 1 cation of lal)
Based on the equivalent weight (the number of carboxyl groups is usually 0.001~
0.05 equivalent, preferably 0.002 to 0.8 equivalent. If Ib) is less than 0.001 equivalent, the antistatic effect and washing resistance will be poor, and if it is more than 0.5 equivalent, it will not be possible to perform the same bath treatment with the cationic polymer laJ.

0.05 equivalent, preferably 0.02 to 0.8 equivalent. tc) is 0. If the amount of O11 is less than 11 equivalents, the antistatic effect and washing resistance will be insufficient, and if the amount is more than 0.5 equivalents, the antistatic effect and washing resistance will be poor.

Also, the sum of the carboxyl group equivalent of 1 bl per 1 equivalent of cation of la) and the equivalent of lc) (fb) + (c)
, l is usually 1:0.01 to 1, preferably 1:
The ratio of the carboxyl equivalent of 1b) to the equivalent of Ic) is usually 1:9 to 941, preferably 2:8 to 8:2.

The antistatic agent of the present invention is used as an antistatic agent for fibers, and the above-mentioned fibers to which this antistatic agent is applied include:
Synthetic fibers such as polyester, polyamide, polyester ether, polyacrylic (polyacrylonitrile, etc.), polyvinyl chloride, polyolefin (polypropylene, etc.), hybrids of natural fibers such as wool, cotton, silk, etc. Examples include inorganic fibers such as galanu fiber. Further, examples of the textile product or fiber structure include cotton, tow, thread, woven fabric, knitted fabric, nonwoven fabric, felt, carpet, and the like.

The amount of antistatic agent to be applied can vary depending on the degree of antistatic property, the form of the fiber structure to be treated, and the type of fibers constituting it, but it is usually 0.01 in terms of solid content based on the weight of the fibers. 5%, preferably 01-2%. If the applied amount is less than 0.01%, the antistatic property will not be sufficient, and if it is more than 5%, the texture of the treated fiber structure may become rough and hard.

Antistatic agents are applied to fibers as treatment liquids, and the process liquids are created 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. Any method is possible, such as preparing each compound, directly creating a treatment bath for fibers with a multi-concentration treatment, and using the treatment bath containing an antistatic agent to treat the fibers. Methods for applying such a treatment solution to fibers or fibrous structures include conventional methods such as padding, spraying, and dipping.

Application is often carried out on fibers or fiber structures that have been subjected to dyeing processes such as bleaching, dipping, printing, etc., but is not limited to this. For example, in the case of filaments, spinning It can be applied afterward, or it can be applied by impregnating or bringing the filament into contact with a solution containing the antistatic agent before or after the heating step in fabricated yarn production. The temperature of the treatment solution may be - normal temperature. After treating the C fiber with the treatment solution, it is usually dried at 40 to 130°C for 80 minutes to 1 minute, and then heat-treated at 150 to 200°C for 8 minutes to 30 seconds.

In addition to antistatic agents, for the finishing of textile products, sizing agents, resins, softeners, smoothing agents, water repellent agents, oil repellent agents, water absorbing agents, and antifouling agents are used to impart texture and other properties to textile products. -1 Although processing agents such as lubricants, flame retardants, polishing agents, matting agents, and dye fastness improvers are used at the same time, the antistatic agent of the present invention does not preclude its use in combination with these agents; It may be used in combination with any processing agent depending on the purpose.

The antistatic agent and antistatic method of the present invention have the following effects.

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

Stop.

(2) The treatment is simple because antistatic treatment can be performed in the same bath.

(3) There is no need to use solvents, so there is no solvent odor 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 deterioration of color fastness or emulsion stability.

The present invention will be further explained below with reference to Examples. The physical property values of the processed fabrics shown in the examples are based on the following measurement method.

(Physical property value measurement method) 1. Electrified voltage generated at room temperature 20℃, relative hot water temperature 40% R, H, under, using a Kyoto University Kaken type rotary static tester (Koa Shokai tank), tightening under the conditions of 400rpm・, load 500F. It was rubbed against Cloth No. 2, and the electrostatic voltage of 1 Vl generated after 1 minute was measured.

2. Washing resistance Two knee 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.

8. Rubbing fastness In accordance with JISL-0849, the sample was rubbed against the target cloth cotton and 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 was dyed under the following conditions before being treated with an antistatic agent.

Sample fabric: Polyester taffeta and polyester processed yarn fabric Dyeing conditions: Dye: Re5oline B]-ue FB
L temperature x time = 130°C x 60 minutes bath ratio: 1:20 Salinity x time: 80°C x 20 minutes bath ratio: 1:20 Water washing: 20 minutes under running water Example 1 Dimethyl sulfate of dimethylaminoethyl methacrylate 150 parts of a 20% aqueous solution (viscosity: approximately 20,000 ape) of quaternary ammonium [polymer (a-1)], 100 parts of a 10% aqueous solution of sodium trimellitate, and 100 parts of a 10% aqueous solution of guanidine hydrochloride at room temperature. The mixture was stirred and mixed for 80 minutes to obtain a pale brown and transparent aqueous solution of the antistatic agent of the present invention. Next, a 2% aqueous solution of the solution was prepared, a polyester processed yarn fabric dyed cloth was padded at room temperature, and the mixture was squeezed with a mangle to a squeezing rate of 80%, dried at 110°C for 3 minutes, and then heated to 180°C.
Heat treatment was performed for 30 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 raw fabric (Comparative Example 1), the quaternary ammonium salt polymer (a-1) (Comparative Example 2), and the commercial product @ the complex of the quaternary ammonium salt polymer (a-1) and anionic activator were As a comparison, performance measurements were also conducted when a product dispersed with an ionic activator (Comparative Example 3) was treated at the same solid content concentration. The results are shown in Table 1. From Table 1, it can be seen that the composition according to the present invention exhibits good antistatic properties and excellent durability. In addition, compared to the original fabric, there was less decrease in fastness to rubbing.

Table 1 Example 2 NufVn and 2-methacryloyloxyethyldimethylethylammonium ethosulfate ratio 1:10
A 20% aqueous solution (viscosity: about 15,000 cps) of a copolymer (a-2")' of The antistatic agent solution of the present invention was prepared by blending a 10% aqueous solution of (listed in Table 2).

A 2% aqueous solution of this solution was prepared, padded with polyester taffeta (dyed) at room temperature, squeezed to 80% with a mangle, dried at 110°C for 3 minutes, and dried at 180°C. This shows that the material according to the present invention is a good antistatic agent and has excellent durability. Furthermore, there was little decrease in fastness to rubbing.

Claims (1)

[Claims] 1. Vinyl polymer fa having a quaternary ammonium base
An antistatic agent for fibers formed by using a combination of J, a polycarboxylic acid and/or a salt thereof (tb), and a water-soluble salt of an inorganic acid fcl. 2. The antistatic agent according to claim 1, which is used in combination in a ratio such that the carboxyl group of (b) is o, ooi to 0.5 equivalents per equivalent of the 1alO cation. For 1 equivalent of cation of la) (cl is 0.
The antistatic agent according to claim 1 or 2, which is used in combination in a proportion of 0.01 to 0.5 equivalent. 4. Any one of claims 1 to 4, wherein lc) is an inorganic acid salt of cesium according to any one of claims 1 to 3, wherein lc) is an inorganic acid salt of guanidine. Antistatic agent described in Crab. 6. The antistatic agent according to any of claims 1 to 5, wherein (b) is a polycarboxylic acid having three or more carboxyl groups in the molecule and/or a salt thereof. 7. Vinyl polymer 1a with quaternary ammonium base number
), a polycarboxylic acid and/or its salt lbl, and an inorganic acid water-soluble salt 1 cl of an antistatic agent is applied to the fiber in an amount of 0.01 to 5% by weight in terms of solid content, and then heat-treated. A method for preventing static electricity on fibers.