JPWO2014156709A1 - Antistatic processing agent for fiber and method for producing antistatic processing fiber - Google Patents

Abstract

The present invention has been made in order to solve the problem of washing durability in such conventional antistatic agents, and can impart excellent antistatic properties to the fiber material, and also has excellent washing durability. It aims at providing the antistatic processing agent for fibers which has this. The antistatic processing agent for fibers of the present invention contains a polymer obtained by polymerizing a polymerizable component containing the monomer (A) represented by the following general formula (1) and water, and the polymerizable component includes The proportion of the monomer (A) occupied is 40 mol% or more. In the formula (1), R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 3 carbon atoms, and R3, R4 and R5 are each independently a hydrogen atom or a carbon atom. X- is a halide ion, hydroxide ion, RaSO3-, RbOSO3-, or RcCOO-, and Ra, Rb, and Rc are each independently an organic group. .)

Description

  The present invention relates to an antistatic processing agent for fibers used for imparting antistatic performance to a fiber material and a method for producing an antistatic processed fiber using the processing agent.

  In general, synthetic fibers are non-conductive and hydrophobic, and are easily charged with static electricity due to friction or the like. When synthetic fibers are used in clothing, the generation of static electricity not only causes a reduction in workability and a decrease in comfort, but also tends to cause dirt substances to adhere. For this reason, it is necessary to use an antistatic agent in clothing using synthetic fibers. Patent Document 1 discloses an antistatic agent using a quaternary ammonium salt having a long-chain alkyl ester group. In addition, inorganic antistatic agents such as calcium chloride and guanidine hydrochloride may be used. However, the antistatic agent and the inorganic antistatic agent using such a surfactant have a problem that the antistatic agent easily falls off by washing and the antistatic property is lowered.

Japanese Unexamined Patent Publication No. 7-82669

  The present invention has been made in order to solve the problem of washing durability in such conventional antistatic agents, and can impart excellent antistatic properties to the fiber material, and also has excellent washing durability. It aims at providing the manufacturing method of the antistatic processing fiber for fibers which has this, and the antistatic processing fiber using this processing agent.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved if the antistatic processing agent for fibers contains a polymer obtained by polymerizing a specific polymerizable component and water. The inventors have found that this can be solved and have reached the present invention.

  That is, the antistatic processing agent for fibers of the present invention includes a polymer obtained by polymerizing a polymerizable component containing the monomer (A) represented by the following general formula (1) and water, and the polymerizable property. The proportion of the monomer (A) in the component is 40 mol% or more.

(In Formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an alkylene group having 1 to 3 carbon atoms. R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, X ⁻ is a halide ion, a hydroxide ion, R ^a SO ₃ ⁻ , R ^b OSO ₃ ^— or R ^c COO ^— R ^a , R ^b and R ^c is each independently an organic group.)

  It is preferable that the polymerizable component further contains a monomer (B) represented by the following general formula (2).

(In Formula (2), R ⁶ is a hydrogen atom or a methyl group. AO is an oxyalkylene group having 2 to 3 carbon atoms. M is an integer of 1 to 100. R ⁷ is a hydrogen atom or carbon number. 1 to 3 alkoxy groups.)

  The proportion of the monomer (A) in the polymerizable component is preferably 40 to 99 mol%, and the proportion of the monomer (B) is preferably 1 to 60 mol%.

The molar ratio (A / B) between the monomer (A) and the monomer (B) is preferably 99/1 to 40/60.
M of the monomer (B) is preferably 4 to 90.

The manufacturing method of the antistatic processed fiber of this invention includes the process of providing said antistatic processing agent for fibers with respect to a fiber material.
It is preferable that the manufacturing method of the antistatic processed fiber of this invention further includes the process of providing a crosslinking agent with respect to fiber material.

  The crosslinking agent is preferably at least one selected from diisocyanate crosslinking agents, triisocyanate crosslinking agents, aldehyde crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, and ethyleneimine crosslinking agents.

The antistatic finishing agent for fibers of the present invention can impart excellent antistatic properties to the fiber material and has excellent washing durability.
According to the method for producing an antistatic processed fiber of the present invention, an antistatic processed fiber having excellent antistatic properties and excellent washing durability can be obtained.

  The antistatic processing agent for fibers of the present invention contains a polymer obtained by polymerizing a specific polymerizable component and water. Details will be described below.

[Polymer]
The polymer used in the present invention (hereinafter sometimes simply referred to as a polymer) is obtained by polymerizing a polymerizable component containing a specific amount of the monomer (A) represented by the general formula (1). It is. By containing such a polymer as an essential component, excellent antistatic properties can be imparted to the fiber material, and the washing durability is excellent.

In general formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an alkylene group having 1 to 3 carbon atoms. The alkylene group preferably has 2 to 3 carbon atoms. R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

X ⁻ is a halide ion, a hydroxide ion, R ^a SO ₃ ⁻ , R ^b OSO ₃ ^— or R ^c COO ^— . Examples of halide ions include Cl ⁻ , Br ⁻ , I ^{− and the} like, Cl ⁻ and Br ⁻ are preferable, and Cl ⁻ is more preferable. R ^a , R ^b and R ^c are each independently an organic group. R ^a , R ^b and R ^c are preferably an alkyl group having 1 to 4 carbon atoms, an aryl group or an alkylaryl group, and more preferably an alkyl group having 1 to 3 carbon atoms. X ⁻ is particularly preferably a halide ion.

  The proportion of the monomer (A) in the polymerizable component is 40 mol% or more, preferably 50 to 99 mol%, more preferably 60 to 98.5 mol%, and even more preferably 70 to 98 mol%. When the proportion is less than 40 mol%, the washing durability becomes poor.

  The polymerizable component preferably further contains the monomer (B) represented by the general formula (2). That is, the polymer is preferably a copolymer obtained by polymerizing a polymerizable component containing a specific amount of the monomer (A) and further containing the monomer (B). By using the monomer (B), excellent antistatic properties and washing durability can be imparted to the fiber material, and the temporal stability of the polymer in the processing agent is dramatically improved. .

In general formula (2), R ⁶ is a hydrogen atom or a methyl group. R ⁷ is a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms. 1-2 are preferable and, as for carbon number of an alkoxy group, 1 is more preferable. AO is an oxyalkylene group having 2 to 3 carbon atoms. 2 is preferable. 1 type (s) or 2 or more types may be sufficient as AO. In the case of two or more types, any of a block adduct, an alternating adduct, or a random adduct may be configured.

  m is an integer of 1 to 100, preferably 4 to 90, more preferably 5 to 90, still more preferably 6 to 70, and particularly preferably 7 to 50. When m is less than 1, the antistatic performance may be poor. On the other hand, when m is more than 100, the temporal stability of the polymer becomes poor.

  The proportion of the monomer (B) in the polymerizable component is 1 to 60 mol%, preferably 1 to 50 mol%, more preferably 1.5 to 40 mol%, and further preferably 2 to 30 mol%. When the proportion is more than 60 mol%, gelation may occur when preparing the polymer, and washing durability may be poor.

  Moreover, 50 mol% or more is preferable, as for the ratio of the sum total of the monomer (A) and monomer (B) which occupies for a polymeric component, 60 mol% or more is more preferable, and 70 mol% or more is further more preferable.

  The molar ratio (A / B) of the monomer (A) to the monomer (B) is 99/1 to 40/60, preferably 99/1 to 60/40, and 99/1 to 70 / 30 is more preferable, and 99/1 to 80/20 is more preferable. If the molar ratio is less than 40/60, washing durability may be poor. On the other hand, when the molar ratio exceeds 99/1, the temporal stability of the polymer may be poor.

  The polymerizable component may contain other monomers other than the monomer (A) and monomer (B) as long as the effects of the present invention are not impaired. That is, the polymer contains a specific amount of the monomer (A), optionally contains the monomer (B), and further is a copolymer obtained by polymerizing a polymerizable component containing other monomers. It may be a polymer. Examples of other monomers include (meth) acrylic acid, (meth) acrylic acid ester monomers, and styrene monomers. In addition, in this application, (meth) acryl shall mean acryl and / or methacryl. Therefore, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and (meth) acrylic acid ester monomer means an acrylic acid ester monomer and / or methacrylic acid ester single monomer. Means the body.

  Examples of (meth) acrylate monomers include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, and nonyl acrylate. Decyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, tert-butyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate , Octadecyl acrylate, nonadecyl acrylate, arachidyl acrylate, behenyl acrylate, lignoselenyl acrylate, cerothinyl acrylate, merlicinyl acrylate, palmitoly acrylate Acrylate, oleyl acrylate, linoleyl acrylate, linolenyl acrylate, phenyl acrylate, isobornyl acrylate, cyclohexyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate , Pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, Undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, hept methacrylate Decyl, octadecyl methacrylate, nonadecyl methacrylate, arachidyl methacrylate, behenyl methacrylate, lignoselenyl methacrylate, serotinyl methacrylate, melicinyl methacrylate, palmitoleyl methacrylate, oleyl methacrylate, linoleyl methacrylate, linolenyl methacrylate, methacrylic acid And methacrylic acid ester monomers such as phenyl, isobornyl methacrylate and cyclohexyl methacrylate.

  Examples of the styrenic monomer include styrene, vinyl toluene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn- Hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, α-methyl styrene, dimethyl styrene, n-methoxy styrene, p-phenyl styrene, p -Chlorstyrene, 3, 4- dichlorostyrene, etc. are mentioned.

  When the other monomer is contained, the proportion of the other monomer in the polymerizable component is preferably 1 to 50% by weight, more preferably 1.5 to 40% by weight, and further preferably 2 to 30% by weight.

  The polymer is obtained through a polymerization step for polymerizing the polymerizable component. In the polymerization step, water, a polymerization initiator, and the like are used in addition to the polymerizable component, but the polymerization method is not particularly limited as long as it is known. That is, methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization can be used. Of these methods, solution polymerization using a radical polymerization initiator is preferred.

  Examples of the solution used for solution polymerization include alcohols such as methanol, ethanol and isopropanol, glycol ethers such as ethyl cellosolve and butyl cellosolve; propylene glycol ethers such as propylene glycol monomethyl ether; tetrahydrofuran, 1,4- Ethers such as dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; hydrocarbons such as toluene, xylene, hexane and heptane; esters such as ethyl acetate and butyl acetate; water and the like can be used. These solvents may be used alone or in admixture of two or more depending on the type of monomer to be polymerized and the mixing ratio in the case of copolymerization. The usage-amount of a solvent is 70-99 weight part with respect to 100 weight part of polymeric components, Preferably it is 80-95 weight part.

  The radical polymerization initiator is not particularly limited, but azo compound catalysts such as azobisisobutyronitrile, azobisvaleronitrile, 2,2-azobis- (2-amidinopropane dihydrochloride), benzoyl par Peroxide catalysts such as oxide and hydrogen peroxide, and persulfate catalysts such as ammonium persulfate, sodium persulfate, and potassium persulfate can be used. The usage-amount of a polymerization initiator is 0.05-5 weight part with respect to 100 weight part of polymeric components, Preferably it is 0.2-3 weight part.

  1000-80000 are preferable and, as for the weight average molecular weight of a polymer, 3000-50000 are more preferable. When the weight average molecular weight is less than 1000, washing durability may be poor. On the other hand, when the weight average molecular weight exceeds 80,000, the solubility in water may decrease due to gelation or the like. The weight average molecular weight was measured by gel permeation chromatography (GPC) using a calibration curve with a standard material polystyrene (Tosoh Corp.).

  Although it does not specifically limit in a superposition | polymerization process, It can carry out with the superposition | polymerization temperature and superposition | polymerization time which were adapted by methods, such as emulsion polymerization, solution polymerization, suspension polymerization, and block polymerization. Examples of the polymerization step include solution polymerization using water as a solvent. A polymer can be prepared by adding a polymerizable component and water to a four-necked flask and raising the temperature, and then dropping an aqueous solution containing an initiator.

  The viscosity (20 ° C.) of the aqueous solution when the concentration of the polymer is 8% by weight is preferably 100 to 4000 mPa · s, more preferably 200 to 3000 mPa · s, and further preferably 300 to 2000 mPa · s.

[Antistatic finishing agent for textiles]
The antistatic processing agent for fibers of the present invention is used for imparting excellent antistatic properties to a fiber material. The antistatic processing agent for fibers of the present invention contains the above polymer and water. In addition, the antistatic processing agent of this invention contains the processing liquid which diluted this processing agent with water etc. when it provides to a fiber material not only the chemical | medical agent manufactured with the manufacturing method mentioned later.

  The proportion of the polymer in the antistatic processing agent of the present invention is preferably from 0.1 to 25% by weight, more preferably from 0.5 to 20% by weight, and even more preferably from 1 to 15% by weight.

  The water used in the present invention may be pure water, distilled water, purified water, soft water, ion exchange water, or tap water.

  The viscosity (20 ° C.) of the antistatic processing agent of the present invention is preferably 100 to 10000 mPa · s, more preferably 150 to 8000 mPa · s, and further preferably 200 to 5000 mPa · s.

  The antistatic processing agent of the present invention may contain a crosslinking agent to be described later from the viewpoint of further exerting the effects of antistatic properties and washing durability. In this case, the weight ratio of the polymer and the crosslinking agent (polymer / crosslinking agent) is preferably 99/1 to 60/40, more preferably 95/5 to 65/35, and further preferably 90/10 to 70/30. preferable.

  The antistatic processing agent of this invention may contain other components other than the above in the range which does not impair the effect of this invention. Examples of other components include oil agents, nonionic surfactants, cationic surfactants, anionic surfactants, inorganic substances, preservatives, pH adjusters, antifoaming agents, solvents, fatty acids (salts), and the like.

  The antistatic processing agent of the present invention may contain a processing agent that can be processed simultaneously with the antistatic processing as long as the effects of the present invention are not impaired. Processing agents include discoloration inhibitors, discoloration inhibitors, insecticides, antifungal agents, acaricides, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, and deep colors. Examples thereof include an agent, a smoothing agent, a softening agent, and a water absorbing agent. A plurality of these drugs may be included. About each chemical | medical agent, a well-known thing is employable.

  A method for preparing the antistatic processing agent of the present invention is not particularly limited, and a known method can be employed. For example, a polymer can be prepared as described above, and water and other components can be mixed and stirred as necessary.

[Method for producing antistatic processed fiber]
The manufacturing method of the antistatic processing fiber of this invention includes the process (I) which provides the antistatic processing agent of this invention with respect to a fiber material. That is, the manufacturing method of this invention includes the process of providing an antistatic processing agent to a fiber material by post-processing. Post-processing means processing after the fiber material is manufactured. According to this production method, it is possible to obtain an antistatically processed fiber having excellent antistatic properties and excellent washing durability.

  The fiber material may be either natural fiber or chemical fiber. Examples of natural fibers include plant fibers such as cotton, cannabis, flax, palm, and rush; animal fibers such as wool, goat wool, mohair, cashmere, camel, and silk; and mineral fibers such as asbestos. Examples of the chemical fiber include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulosic fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fiber; melt-spun cellulose fiber; Protein fibers such as milk protein and soybean protein; Regenerated and semi-synthetic fibers such as regenerated silk and alginate fiber; Polyamide fiber, Polyester fiber, Cationic dyeable polyester fiber, Polyvinyl fiber, Polyacrylic alcohol fiber, Polyurethane fiber, Acrylic fiber, Examples thereof include synthetic fibers such as polyethylene fibers, polyvinylidene fibers, and polystyrene fibers. Two or more of these fibers may be combined (mixed spinning, mixed fiber, union, union, etc.).

  Examples of the form of the fiber material include forms such as a woven fabric, a knitted fabric, a fabric, a thread shape, and a non-woven fabric. Applications of the fiber material include objects that impart antistatic properties and washing resistance, such as underwear, work clothes, sports clothing, bedding, and covers.

  The method for applying the antistatic finish to the fiber material is not particularly limited, and a known method can be employed. Among these, at least one method selected from the exhaust method, the pad dry method, the spray method, and the coating method is preferable from the viewpoint that the antistatic finish can be reliably fixed to the fiber material, and the pad dry method is preferable. Further preferred.

  Known methods can be employed as the exhaust method, pad dry method, spray method, and coating method. The exhaustion method is a method in which a diluted solution of a drug is used, conditions such as temperature, immersion time, number of times of liquid circulation, etc. are set, and the drug is selectively adsorbed on a fiber to be exhausted and adhered. Thereafter, washing is usually carried out, followed by centrifugal dehydration and drying. The pad dry method is a method in which fibers are immersed in a drug solution for a short time and immediately attached by squeezing with a dehydrated mangle or the like. Then, drying is performed and curing is performed as necessary. The spray method is a method in which fibers are placed on a conveyor at a constant speed and adhered by spraying a predetermined amount of a solution of the drug from the fiber. Then, drying is performed and curing is performed as necessary. The coating method is a method in which a drug solution is usually applied by applying from one side with a mangle. Then, the excess drug is scraped off with a doctor, dried, and cured if necessary.

  5-40 degreeC is suitable for the temperature at the time of providing the antistatic processing agent of this invention to a fiber material. When the application temperature is lower than 5 ° C., it may be difficult to maintain the constant temperature, and thus it may not be possible to perform constant application to the fiber material. On the other hand, when the application temperature is higher than 40 ° C., the elution of dyes and the like contained in the fiber material may increase.

  The weight ratio of the polymer in the antistatic processing agent (processing solution) when applied to the fiber material is preferably 0.01 to 25% by weight, more preferably 0.05 to 20% by weight, 15% by weight is more preferred. The predetermined weight ratio can be prepared by diluting with water or the like.

  The amount of polymer applied to the fiber material is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.03 to 15% by weight, and 0.05 to 10% by weight based on the fiber material. Is more preferable. If it is less than 0.01% by weight, the fiber treated in the antistatic finish may not exhibit antistatic properties. If it exceeds 20% by weight, no further improvement in antistatic property and washing durability is observed, which may be economically disadvantageous.

  The production method of the present invention preferably further includes a step (II) of imparting a crosslinking agent to the fiber material from the viewpoint of further exerting the effects of antistatic properties and washing durability. The method for applying the crosslinking agent to the fiber material is the same as that for the antistatic processing agent. Process (II) may be performed simultaneously with said process (I), and may be performed separately. At the same time, the antistatic processing agent (processing solution) further contains a crosslinking agent. From the viewpoint of productivity and economy, it is preferable to perform step (I) and step (II) simultaneously.

  99 / 1-60 / 40 is preferable, as for the weight ratio (polymer / crosslinking agent) of said polymer at the time of providing a crosslinking agent, and a crosslinking agent, 95 / 5-65 / 35 is more preferable, 90/10 -70/30 is more preferable.

  The crosslinking agent is not particularly limited as long as it crosslinks fibers, antistatic processing agents, or fibers and antistatic processing agents. What is marketed can be used as a crosslinking agent. Examples of the crosslinking agent include at least one selected from diisocyanate crosslinking agents, triisocyanate crosslinking agents, aldehyde crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, and ethyleneimine crosslinking agents. Specifically, for example, diisocyanate crosslinking agents such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane isocyanate, isophorone diisocyanate, hexamethylene diisocyanate; Triisocyanate-based crosslinking agent obtained by reacting styrene with trimethylolpropane or glycerin; aldehyde-based crosslinking agents such as formaldehyde, acetaldehyde, glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, phthaldialdehyde; 2-iso Propenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline, 2,2'-o-phenylenebis (2-oxazoline), 2,2 ' m-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline), 2,2′-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-m -Phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4,4'- Dimethyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2-oxazoline), 2, Oxazoly such as 2'-octamethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-diphenylenebis (2-oxazoline) N, N'-di-o-triylcarbodiimide, N, N'-dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide N-triyl-N′-phenylcarbodiimide, N, N′-di-p-nitrophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N '-Di-cyclohexylcarbodiimide, N, N'-di-p-triylcarbodiimide, p-phenylene-bis-di-o-triylcarbodiimide, 4,4'-dicyclohexylmethanecarbodiimide, tetramethylxylylenecarbodiimide N, N′-dimethylphenylcarbodiimide, N, N′-di Examples include carbodiimide-based crosslinking agents such as -2,6-diisopropylphenylcarbodiimide; ethyleneimine-based crosslinking agents. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types. As the crosslinking agent, a carbodiimide-based crosslinking agent is preferable.

  About a bridge | crosslinking process, after processing an antistatic processing agent to a fiber, you may carry out simultaneously with a drying process, and you may provide a bridge | crosslinking process separately after drying. The crosslinking temperature is not particularly limited, but is preferably 100 ° C. or higher and more preferably 110 ° C. or higher in order to crosslink the antistatic processing agent on the fiber. If the crosslinking temperature is lower than 100 ° C., the crosslinking reaction may not proceed.

  The manufacturing method of the present invention may include a process that can be processed simultaneously with the antistatic processing as long as the effects of the present invention are not impaired. Processes that can be processed at the same time include discoloration inhibitors, discoloration inhibitors, insecticides, antifungal agents, acaricides, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, and antifouling agents. , A step of imparting a color deepening agent, a smoothing agent, a softening agent or a water absorbing agent. A plurality of these steps can be performed simultaneously. About each chemical | medical agent, a well-known thing is employable.

  EXAMPLES Examples of the present invention will be described below, and the present invention will be described in more detail. However, the present invention is not limited to these examples. In the examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified.

Example 1
To a 1 liter four-necked flask equipped with a thermometer, stirrer, nitrogen flow, and dropping funnel, 79 g of polymerizable component dimethylaminopropylacrylamide methyl chloride quaternary salt and 246 g of soft water were added, and nitrogen flowed to 70 ° C. The temperature rose. While maintaining the liquid temperature at 70 ° C., 5.4 g of soft water containing 0.4 g of 2,2-azobis (2-methylpropionamidine) dihydrochloride as a polymerization initiator was dropped, and the mixture was heated and stirred for 1 hour to obtain a polymer. An aqueous solution containing was obtained. About the obtained aqueous solution, the viscosity was measured by the following method. Thereafter, 669.6 g of soft water was added to obtain an antistatic processing agent a for fibers in which the proportion of the polymer in the processing agent was 8% by weight. The stability of the obtained antistatic processing agent a for fibers was measured by the following method. The results are shown in Table 1.

<Viscosity>
Soft water was added to the aqueous solution, and the viscosity was measured at a polymer concentration of 8% by weight. The viscosity was measured using a B-type rotational viscometer (manufactured by BROOK FIELD), rotor No. Measured at 20 ° C. with 60 revolutions at 62.

<Evaluation of stability of antistatic finishing agent for fiber>
100 mL of the antistatic finishing agent for fibers was put into a screw tube and sealed. This was left for 1 week in an incubator adjusted to a temperature of 70 ° C., and the stability was judged in the following three stages.
○: Colorless and no turbidity is observed.
X: Obvious turbidity or precipitate is observed.
(Triangle | delta): It is coloring and turbidity about the middle of (circle) and x.

Next, water was added to the antistatic processing agent a obtained above to prepare a processing solution with a polymer weight ratio of 0.5% by weight. Acrylic knit was immersed in this processing solution and squeezed with mangle. At this time, the adhesion amount of the processing solution to the fiber was 80% by weight. In the examples, the adhesion amount of the treatment liquid to the fiber was calculated by the following formula.
Amount of treatment solution attached to fiber (% by weight) = [(Y−X) / X] × 100
X: Weight of raw acrylic knit Y: Weight of acrylic knit containing processing solution

  Next, the acrylic knit was dried with a pintender at 110 ° C. for 3 minutes to obtain a test cloth which is an antistatic processed fiber (a processed finish was obtained. About the friction withstand voltage, half-life and washing durability of the obtained test cloth, The evaluation was performed by the following method, and the results are shown in Table 1.

<Friction band voltage>
Using the test cloth obtained above, which was conditioned for 2 hours in a constant temperature room at 20 ° C. and 45% RH, the frictional voltage was measured using a rotary static tester according to the JIS L-1094 B method.

<Half life>
Using a static Honest meter under the same atmosphere as when the frictional voltage was measured, a voltage of 10 kV was applied to the test cloth obtained above, and the time when the applied charge decayed in half was determined as the half-life. Since the half-life represents the time during which the applied charge is reduced by half, the shorter the half-life, the less the charge is.

<Evaluation of washing durability>
The test cloth obtained above was washed 10 times according to JIS L-0217 103 method, and the frictional band voltage and half-life were measured in the same manner as in the above method. If the half-life is within 30 seconds and the frictional voltage is 3000 V or less, the antistatic property is good, and if the above conditions are satisfied before and after washing, it can be said that the washing durability is good.

(Examples 2 to 13, Comparative Examples 1 to 4)
Evaluation was performed in the same manner as in Example 1 except that the antistatic processing agents bo were obtained by changing the polymerizable component, the polymerization initiator, water, and the ratio thereof shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

(Comparative Example 5)
Example except that water was added to di (stearoyloxyethyl) dimethyl quaternary ammonium chloride to prepare a processing solution in which the weight ratio of di (stearoyloxyethyl) dimethyl quaternary ammonium chloride was 0.5% by weight. Evaluation was conducted in the same manner as in 1. The results are shown in Table 2.

(Comparative Example 6)
Evaluation was performed in the same manner as in Example 1 except that water was added to calcium chloride to prepare a processing solution in which the weight ratio of calcium chloride was 0.5% by weight. The results are shown in Table 2.

(Comparative Example 7)
Evaluation was performed in the same manner as in Example 1 except that water was used instead of the processing solution as a blank (BL). The results are shown in Table 2.

(Example 14)
Crosslinking agent I and water were added to antistatic processing agent d obtained in Example 4 above, and the weight ratio of polymer to crosslinking agent (polymer / crosslinking agent) was 70/30. A processing solution having a total weight ratio of the agent of 0.5% by weight was prepared. Acrylic knit was immersed in this processing solution and squeezed with mangle. At this time, the adhesion amount of the processing solution to the fiber was 80% by weight. The adhesion amount was calculated in the same manner as described above.
Next, the acrylic knit was dried with a pintender at 110 ° C. for 3 minutes and then cured at 180 ° C. for 2 minutes to obtain a test cloth (processed up) as an antistatic processed fiber. The obtained test cloth was evaluated in the same manner as in Example 4 with respect to the friction withstand voltage, half-life and washing durability. The results are shown in Table 3.

In addition, the crosslinking agents I-III in Tables 3 and 4 are as follows.
Crosslinking agent I: Carbodilite V-02-L2 (Nisshinbo Chemical Co., Ltd.)
Crosslinking agent II: Epocross WS-700 (manufactured by Nippon Shokubai Co., Ltd.)
Crosslinking agent III: Carbodilite E-02 (Nisshinbo Chemical Co., Ltd.)

(Examples 15 to 25, comparison 8 to 10)
Evaluation was performed in the same manner as in Example 14 except that the weight ratio of the antistatic processing agent, the crosslinking agent, and the polymer to the crosslinking agent shown in Tables 3 and 4 was changed. The results are shown in Tables 3 and 4.

(Example 26)
An antistatic processing agent for fibers was obtained in the same manner as in Example 1 except that the polymerizable component, polymerization initiator, water, and ratio thereof shown in Table 5 were changed. Next, the crosslinking agent I and water are added to the prepared processing agent, the weight ratio of the polymer and the crosslinking agent (polymer / crosslinking agent) is 80/20, and the total weight ratio of the polymer and the crosslinking agent is A processing solution of 0.5% by weight was prepared. Acrylic knit was immersed in this processing solution and squeezed with mangle. At this time, the adhesion amount of the processing solution to the fiber was 80% by weight. The adhesion amount was calculated in the same manner as described above.
Next, the acrylic knit was dried with a pintender at 110 ° C. for 3 minutes and then cured at 180 ° C. for 2 minutes to obtain a test cloth (processed up) as an antistatic processed fiber. The friction resistance voltage, half-life and washing durability of the obtained test cloth were evaluated in the same manner as in Example 1. The results are shown in Table 5.

(Examples 27 and 28)
Evaluation was performed in the same manner as in Example 25 except that the polymerizable component, polymerization initiator, water, cross-linking agent, and ratio thereof shown in Table 5 were changed. The results are shown in Table 5.

  From Tables 1 to 5, the antistatic processing agent for fibers of the present invention can impart excellent antistatic properties to the fiber material as compared with the comparative example, and has excellent washing durability. You can see that Moreover, since Example 4-13 uses the monomer (B) together as a polymeric component, it turns out that it is excellent in stability of a processing agent. Furthermore, since Examples 14-28 used the crosslinking agent together, it turns out that antistatic property and washing durability are further excellent.

  The antistatic processing agent for fibers of the present invention can be suitably used when imparting antistatic properties to a fiber material.

Claims (8)

A polymer obtained by polymerizing a polymerizable component containing the monomer (A) represented by the following general formula (1) and water, and the proportion of the monomer (A) in the polymerizable component is The antistatic processing agent for textiles which is 40 mol% or more.

(In Formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an alkylene group having 1 to 3 carbon atoms. R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, X ⁻ is a halide ion, a hydroxide ion, R ^a SO ₃ ⁻ , R ^b OSO ₃ ^— or R ^c COO ^— R ^a , R ^b and R ^c is each independently an organic group.) The antistatic processing agent for fibers according to claim 1, wherein the polymerizable component further contains a monomer (B) represented by the following general formula (2).

(In Formula (2), R ⁶ is a hydrogen atom or a methyl group. AO is an oxyalkylene group having 2 to 3 carbon atoms. M is an integer of 1 to 100. R ⁷ is a hydrogen atom or carbon number. 1 to 3 alkoxy groups.)   The ratio for the monomer (A) in the polymerizable component is 40 to 99 mol%, and the ratio for the monomer (B) is 1 to 60 mol%, according to claim 2. Antistatic processing agent.   The antistatic processing agent for textiles according to claim 2 or 3 whose molar ratio (A / B) of said monomer (A) and said monomer (B) is 99/1-40/60. .   The antistatic processing agent for fibers according to any one of claims 2 to 4, wherein m of the monomer (B) is 4 to 90.   The manufacturing method of the antistatic processed fiber including the process of providing the antistatic processing agent for fibers of Claims 1-5 with respect to a fiber material.   The method for producing an antistatic processed fiber according to claim 6, further comprising a step of applying a crosslinking agent to the fiber material.   The said crosslinking agent is at least 1 sort (s) chosen from a diisocyanate type crosslinking agent, a triisocyanate type crosslinking agent, an aldehyde type crosslinking agent, an oxazoline type crosslinking agent, a carbodiimide type crosslinking agent, and an ethyleneimine type crosslinking agent. Manufacturing method of antistatic processed fiber.