JP2007247089A - Fiber structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber structure having antistatic properties and water repellency with excellent durability in combination and multiple functions by using a fluorine-based water and oil repellent considering environmental problems. <P>SOLUTION: The fiber structure is characterized as follows. The fluorine-based water and oil repellent is fixed in a layer form through a film composed of an antistatic polymer or through a film composed of the antistatic polymer and the fluorine-based water and oil repellent and the fluorine-based water and oil repellent is PFOA (perfluorooctanoic acid) and/or PFOS (perfluorooctane sulfonic acid) at <5 ng/g concentration thereof when measured by an LC-MS (high-performance liquid chromatograph-mass spectrometer). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fiber structure having durable antistatic properties, water repellency, and oil repellency using a fluorinated water and oil repellent agent in consideration of environmental problems.

  Water and oil repellents made of fluorine compounds have been widely used for a long time to impart water and oil repellency functions to clothing and industrial materials made of textiles.

  In recent years, such fluorine-based water and oil repellents include compounds that may affect living environment and living organisms, such as perfluorooctanoic acid (hereinafter referred to as PFOA), perfluorooctanesulfonic acid (hereinafter referred to as PFOS), and the like. Thus, there is a demand for a fiber product using a fluorine-based water and oil repellent that does not contain the compound or has as little content as possible.

  In view of the current situation, the present invention uses a fluorine-based water and oil repellent agent that is environmentally friendly, and provides a multifunctional fiber structure that has both antistatic and water repellency with excellent durability. To do.

In order to solve the above problems, the present invention employs the following means.
(1) The fiber-based water / oil repellent is fixed to the fiber surface in a layered manner through a film made of an antistatic polymer or a film made of an antistatic polymer and a fluorine-based water / oil repellent. The concentration of perfluorooctanoic acid and / or perfluorooctanesulfonic acid when the fluorine-based water / oil repellent is measured with a high performance liquid chromatograph-mass spectrometer (LC-MS) is less than 5 ng / g. The fiber structure characterized by being.
(2) The fiber structure according to the above (1), wherein the concentration of perfluorooctanoic acid and / or perfluorooctanesulfonic acid is 1 ng / g or less.
(3) The antistatic polymer is a polymerizable unit having two or more acrylic and / or methacrylic groups as both ends or one end of the main chain mainly composed of polyalkylene oxide segments or side chains of the main chain. The fiber structure according to any one of (1) and (2) above, which is composed of a monomer.
(4) The mixing ratio of the antistatic polymer and the fluorine-based water / oil repellent agent in the film comprising the antistatic polymer and the fluorine-based water / oil repellent agent is 1.0: 0.001 to 1.0: 1.0. The fiber structure according to the above (1) to (3).
(5) The fiber structure according to the above (1) to (4), wherein the film contains inorganic fine particles.
(6) The fiber structure according to (5), wherein the inorganic fine particles are silicon oxide.
(7) The fiber structure according to the above (1) to (6), wherein the film made of the antistatic polymer has a thickness of 5 to 100 nm.
(8) The fiber structure according to any one of (1) to (7), wherein the water / oil repellent contains a triazine ring-containing compound or / and an isocyanate compound.

  ADVANTAGE OF THE INVENTION According to this invention, the fiber structure which has durable water repellency and antistatic property can be provided stably using the fluorine-type water- and oil-repellent agent considered in the environment. The fiber structure of the present invention can be preferably used for a coat, a blouson, a windbreaker, a blouse, a dress shirt, a skirt, slacks, gloves, a hat, a futon side, a futon cover, a curtain, and the like.

  The present invention is a polymer having antistatic properties as a result of intensive studies on the above-mentioned problem, that is, a fiber structure that has both water repellency and antistatic performance by an environment-friendly fluorinated water and oil repellent and has durability. The present inventors have investigated that this problem can be solved at once by fixing a fluorine-based water and oil repellent that does not contain PFOA or PFOS or has a very small content on the film.

  The antistatic polymer of the present invention is a polyester resin containing a polyethylene glycol group, a urethane resin containing a polyethylene glycol group, a reaction between a polycation compound containing a polyethylene glycol group and diglycidyl ether. In particular, as a monomer having two or more acrylic and / or methacrylic groups as both ends or one end of the main chain or a side chain of the main chain mainly composed of a polyalkylene oxide segment, For example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol diacrylate, ethylene oxide addition of bisphenol A Monomers composed of dimethacrylate, ethylene oxide adduct diacrylate of bisphenol A, propylene oxide adduct dimethacrylate of bisphenol A, propylene oxide adduct diacrylate of bisphenol A, etc. are used alone or as a mixture of two or more. A polymer can be preferably used. The polymerizable monomer is preferably polymerized on the fiber surface. As a method for forming a film, an aqueous solution comprising the monomer and a catalyst is applied on the fiber, and then heat treatment is performed. Examples of such catalysts include acetic acid, formic acid, acrylic acid, malic acid, tartaric acid, maleic acid, phthalic acid, sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid and the like, and ammonium salts, sodium salts, potassium salts, magnesium salts thereof and the like. Yes, one or more of these can be used. Of these, ammonium persulfate and potassium persulfate can be preferably used. The amount of the catalyst is preferably 0.1 to 30% by weight based on the amount of the monomer used.

The heat treatment for the polymerization of the monomer is preferably performed at a temperature of 50 to 180 ° C.
The dry heat treatment and / or the wet heat treatment are performed for 30 minutes, but the steam heat treatment is easier to form a uniform film on the surface of the single fiber, and the texture after the film formation is more flexible. In this steaming treatment, saturated steam or superheated steam at 80 to 160 ° C. is preferably used. In the case of more preferable saturated steam, saturated steam at a temperature of 90 to 130 ° C., and in the case of superheated steam, 110 to 160 ° C. These are superheated steam at a temperature of 5 to 10 minutes, and all perform treatment for several seconds to several tens of minutes. After performing such steaming heat treatment, washing with water, washing with hot water or reduction washing can be performed as necessary.

  In the present invention, a fluorine-based water and oil repellent can be mixed with such an antistatic polymer. Such mixing of the fluorine-based water / oil repellent enhances the affinity with the fluorine-based water / oil repellent to be subsequently processed, and improves the durability. As the fluorine-based water and oil repellent agent to be mixed, it is preferable from the environmental viewpoint to mix a processing agent which does not contain PFOA or PFOS which will be described later or has a small content. The mixing ratio of the antistatic polymer and the fluorine-based water / oil repellent in the present invention is 1.0: 0.001 to 1.0: 1.0 by weight mixing ratio. If the fluorine-based water / oil repellent is less than 0.001, the affinity may be insufficient, and if it is more than 1.0, the antistatic polymer film may exhibit a strong water-repellent tendency. On the contrary, the affinity with the water / oil repellent to be coated may decrease.

  In the present invention, it is preferable that the antistatic film contains inorganic fine particles. Inorganic particles include aluminum oxide, silicon oxide, titanium oxide, kaolinite, talc, calcium carbonate, calcium silicate, magnesium oxide, and the like. These can be used alone or in admixture of two or more, but silicon oxide is preferably used. As the particle diameter of the particles, the primary particle diameter is preferably 5 to 400 nm, more preferably 10 to 100 nm, and it is preferably used in the state of an aqueous dispersion. The inorganic fine particles of the present invention can be used by mixing with an aqueous solution of a polymerizable monomer, and the weight mixing ratio with the polymerizable monomer is preferably 0.03 to 1. 0, more preferably 0.05 to 0.7. By mixing the fine particles, the polymer film formation property of the monomer is improved, and a tough film can be formed, so that the durability can be further enhanced.

  The thickness of the coating made of the antistatic polymer of the present invention is preferably 5 to 100 nm, more preferably 5 to 40 nm, giving a high level of antistatic performance and softening the texture. It can be made. The thickness of the film can be observed with a transmission electron microscope (TEM).

  The water / oil repellent mixed with the antistatic polymer of the present invention and the water / oil repellent fixed on the antistatic polymer in a layered manner are fluorine-based water repellent with measures against PFOA and PFOS which are environmentally hazardous substances. Use oil repellent. The amount of PFOA and / or PFOS contained in such a fluorine-based water / oil repellent is preferably less than the lower limit of quantification of 5 ng / g when measured with a high performance liquid chromatograph-mass spectrometer (LC-MS). More preferably, it is less than the detection lower limit of 1 ng / g. Such water- and oil-repellent agents use a new production method that eliminates the generation of PFOA and PFOS, and those that recover PFOA and PFOS using various methods in the course of conventional production methods. In particular, Asahi Guard E Series AG-E061, which is a fluorine-based water and oil repellent manufactured by Asahi Glass Co., Ltd., and Scotch Guards PM3622, PM490, PM930 manufactured by Sumitomo 3M Co., Ltd., can be preferably used. The water / oil repellent is used at a concentration of 0.05 to 10%.

    At least one of a triazine ring-containing compound and an isocyanate compound can be mixed in the fluorine-based water / oil repellent of the present invention. The triazine ring-containing compound of the present invention is a compound containing a triazine ring and containing at least two polymerizable functional groups, and examples thereof include compounds represented by the following formula.

  In the present invention, in addition to the compound represented by the above general formula, a copolymer with an ethylene urea compound, a copolymer with dimethylol urea, an acid colloid compound, and the like can also be used. As the isocyanate compound of the present invention, a polyfunctional isocyanate group-containing urethane resin is preferably used. And dichloromethane diisocyanate. In addition, phenol and diethyl malonate, which are blocking compounds (compounds that regenerate isocyanate groups by heating to 70 to 200 ° C. together with isocyanate adducts) such as trimethylolpropane tolylene diisocyanate adducts and fryserin tolylene diisocyanate adducts Examples thereof include polyfunctional block isocyanate urethane resins obtained by reacting an ester, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam and the like. As the dissociation catalyst used for promoting the improvement of the thermal separation rate of the blocked isocyanate and the reduction of the thermal dissociation temperature, dibutyltin diolate, dibutyltin stearate, stearyl zinc and organic amine compounds are preferred.

  The water / oil repellent may be fixed in a layered manner on at least a part of the antistatic polymer film, but it is more preferable that the water / oil repellent is entirely covered. The fluorine-based water / oil repellent is preferably fixed at 0.01 to 5% by weight with respect to the fiber weight. As a method for applying the resin composition, it is preferable that a treatment liquid in which a triazine ring-containing compound and / or an isocyanate compound is added to a fluorine-based water / oil repellent is attached to the fiber structure and then heat treated. The method of applying the treatment liquid is particularly limited, and a method of applying a predetermined amount by squeezing with a mangle or the like or applying a predetermined amount with a spray or the like after dipping the fiber structure in the aqueous treatment liquid can be adopted. It is not a thing. The heat treatment may be either dry heat treatment or wet heat treatment. Preferably, after applying the aqueous treatment liquid, the heat treatment is performed at a temperature of 100 to 130 ° C., and thereafter, the heat treatment is performed at a temperature of 160 to 190 ° C.

  The water and oil repellent agent of the present invention may or may not contain an antistatic compound, and can be determined according to the target antistatic performance and water repellent performance.

  Other compounds such as a water-absorbing agent, a hygroscopic agent, an ultraviolet absorber, and a light stabilizer as long as the effects of the present invention are not impaired during the formation of the antistatic polymer film of the present invention and the film formation of the fluorine-based water- and oil-repellent agent. , Lubricant, lubricant, inorganic particles, organic particles, antistatic agent, deodorant, antibacterial agent, fungicide, colorant, flame retardant, colorant, deep colorant, water repellent, oil repellent, antifouling You may mix agents.

Examples of fiber materials used in the fiber structure of the present invention include aromatic polyester fibers such as polyethylene terephthalate, polybutylene terephthalate and polypropylene terephthalate, aromatic polyester fibers obtained by copolymerizing aromatic polyester with a third component, L -Aliphatic polyester fiber represented by lactic acid as a main component, polyamide fiber such as nylon 6 and nylon 66, acrylic fiber based on polyacryl with tolyl as main component, polyolefin fiber such as polyethylene and polypropylene And synthetic fibers such as polyvinyl chloride fibers, semi-synthetic fibers such as acetate and rayon, and natural fibers such as cotton, silk, hemp and wool. In the present invention, these fibers can be used singly or as a mixture of two or more kinds, but a fiber mainly composed of a polyester fiber or a polyamide fiber is preferably used.

  The fibers used in the present invention may be false twisted, strongly twisted yarn, Taslan processed yarn, thick and mixed yarn, and various forms such as staple fiber, tow, and spun yarn, in addition to a normal flat yarn. May be used.

    As used in the present invention, in order to improve the productivity and properties in the production process and processing process of the yarn, it is within the range not inhibiting the present invention, for example, a water absorbing agent, a hygroscopic agent, an ultraviolet absorber, a light stabilizer. , Lubricant, lubricant, inorganic particles, organic particles, antistatic agent, deodorant, antibacterial agent, fungicide, colorant, flame retardant, colorant, deep colorant, water repellent, oil repellent, antifouling Additives such as agents can be included.

  The fiber structure of the present invention includes a knitted fabric using the fibers, a fabric-like material such as a woven fabric or a non-woven fabric, or a string-like material.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the performance in an Example was measured with the following method.
(Amount of PFOA and PFOS)
It measured on the following conditions and displayed by ng / g.
Apparatus: LC-MS / MS tandem mass spectrometer TSQ-7000 (Thermo Electron)
High performance liquid chromatograph LC-10Avp (Shimadzu Corporation)
Column: Capcellpak C8 100 mm × 2 mm i.d. (5 μm)
Moving layer: A; 0.5 mmol / L ammonium acetate B; Acetonitrile flow rate: 0.2 mL / min, sample injection amount: 3 μL
CP temperature: 220 ° C., ionization voltage: 4.5 kv, ion multi: 1300 v
Ionization method: ESI-Negative
(Antistatic)
The friction withstand voltage was measured using cotton as a target cloth in an atmosphere of 25 ° C. × 40% RH by the method defined in the JIS L 1094B method (friction band voltage measurement method), and displayed as (V).

(Water repellency)
Evaluation was made by the spray method according to the method specified in JIS L 1092 “Test method for waterproofness of textile products” (1998), and the grade was determined.

(Washing durability)
A weak alkaline synthetic detergent specified in JIS K 337 is dissolved in an automatic inversion swirl electric washing machine to a concentration of 0.2%, a bath ratio of 1:50, and a temperature of 40 ± 2 ° C. under strong conditions. Was washed for 25 minutes, then drained and washed with overflow water for 10 minutes × twice twice and then air-dried. The antistatic property, water repellency and pollen adhesion preventing property after washing were evaluated after washing by the washing method.

(Examples 1-7, Comparative Examples 1-4)
After weaving a plain fabric using 84 dtex, 72 filament false twisted yarn made of polyethylene terephthalate as warp and weft yarns, the fabric is scoured in a conventional method at a temperature of 95 ° C. using a continuous scourer and washed with hot water. Then, it was dried at 130 ° C. and pinter set at 180 ° C. Subsequently, it was dyed pink with a liquid dyeing machine, dried at 130 ° C., and pintter set at 170 ° C. to obtain a warp / width of 140/88 / 2.54 cm. Table 1 shows the results of treating the woven fabric by the following method and evaluating the performance.
<Antistatic treatment>
(1) Polymerizable monomer: Polyethylene glycol dimethacrylate having a polyalkylene oxide segment having a molecular weight of 1000 (solid content: 100%).
(2) Fluorine-based water repellent (A) Asahi Guard AG-E061 (Asahi Glass Co., Ltd., solid content 20%)
(B) Scotch guard PM930 (manufactured by Sumitomo 3M, solid content 30%)
(3) Inorganic fine particles: Snowtex OL (manufactured by Nissan Chemical Industries, Ltd., solid content 20%, particle size 40-50 nm)
(4) Triazine ring-containing material: Sumitex resin M3 (manufactured by Sumitomo Chemical Co., Ltd., methylol melamine, solid content 80%)
The processing condition of the processing agent was changed to prepare an aqueous processing solution, and mixed at a concentration of 2 g / L ammonium persulfate as a polymerization catalyst. The fabric was immersed in the treatment liquid, and the treatment liquid was squeezed with mangles so that the adhesion amount of the treatment liquid was 90% by weight, and the treatment was performed in a saturated steam atmosphere at 105 ° C. for 5 minutes. Subsequently, it was washed with hot water at 60 ° C., washed with water, and dried at 130 ° C.
<Water repellent treatment>
(5) Fluorine-based water repellent: (A) Asahi Guard AG-E061 (Asahi Glass Co., Ltd., solid content 20%)
(C) Scotch guard PM3622 (manufactured by Sumitomo 3M, solid content 30%)
(6) Triazine ring-containing material: Sumitex resin M3 (manufactured by Sumitomo Chemical Co., Ltd., methylolmelamine, solid content 80%)
When using this agent, SMITEX Accelerator ACX (Sumitomo Chemical Co., Ltd.) is used as a catalyst.
Manufactured, 35% solids) was used at a concentration of 0.5 g / L.
(7) Isocyanate compounds: Super Fresh JB-7300 (manufactured by Kyokin Kasei Co., Ltd., 40% active ingredient)
The mixing condition of the processing agent is changed to adjust the aqueous treatment liquid, the fabric is immersed in the treatment liquid, the mangle is squeezed so that the amount of the treatment liquid attached becomes 90% by weight, dried at 130 ° C., 170 The pin tenter was set at ℃.

  From Table 1, it can be seen that the PFOA and PFOS contained in the fluorine-based water repellent are environmentally friendly compounds and have antistatic properties in the fluorinated water repellent. .

Claims (8)

Fluorine-based water- and oil-repellent agent is fixed on the fiber surface in a layered manner through a film made of an antistatic polymer or a film made of an antistatic polymer and a fluorine-based water- and oil-repellent agent. Yes, the concentration of perfluorooctanoic acid and / or perfluorooctanesulfonic acid is less than 5 ng / g when the fluorine-based water / oil repellent is measured by a high performance liquid chromatograph-mass spectrometer (LC-MS). A fiber structure characterized by The fiber structure according to claim 1, wherein the concentration of perfluorooctanoic acid and / or perfluorooctanesulfonic acid is less than 1 ng / g. The antistatic polymer is composed of a polymerizable monomer having two or more acrylic and / or methacrylic groups as both ends of the main chain mainly composed of a polyalkylene oxide segment, one terminal, or a side chain of the main chain. The fiber structure according to claim 1 or 2. The mixing ratio of the antistatic polymer and the fluorine-based water and oil repellent agent in the film comprising the antistatic polymer and the fluorine-based water and oil repellent agent is from 1.0: 0.001 to 1.0: 1.0. Item 3. A fiber structure according to items 1 to 3. The fiber structure according to claim 1, wherein the film contains inorganic fine particles. The fiber structure according to claim 5, wherein the inorganic fine particles are silicon oxide. The fiber structure according to any one of claims 1 to 6, wherein the film made of the antistatic polymer has a thickness of 5 to 100 nm. The fiber structure according to claim 1, wherein the water / oil repellent contains a triazine ring-containing compound or / and an isocyanate compound.