JP2007247096A - Fluorine-based water repellent and fiber structure - Google Patents

Fluorine-based water repellent and fiber structure Download PDF

Info

Publication number
JP2007247096A
JP2007247096A JP2006072159A JP2006072159A JP2007247096A JP 2007247096 A JP2007247096 A JP 2007247096A JP 2006072159 A JP2006072159 A JP 2006072159A JP 2006072159 A JP2006072159 A JP 2006072159A JP 2007247096 A JP2007247096 A JP 2007247096A
Authority
JP
Japan
Prior art keywords
fluorine
water repellent
compound
fiber
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2006072159A
Other languages
Japanese (ja)
Inventor
Masao Seki
昌夫 関
Original Assignee
Toray Ind Inc
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Ind Inc, 東レ株式会社 filed Critical Toray Ind Inc
Priority to JP2006072159A priority Critical patent/JP2007247096A/en
Publication of JP2007247096A publication Critical patent/JP2007247096A/en
Pending legal-status Critical Current

Links

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber structure having excellent durability of a fluorine-based water repellent by using the fluorine-based water repellent considering environmental problems. <P>SOLUTION: The fluorine-based water repellent is characterized as follows. The fluorine-based water repellent is a mixture of a fluorine-based water-repellent compound (A) with a fluorine-based water-repellent compound (B). The concentration of PFOA (perfluorooctanoic acid) and/or PFOS (perfluorooctane sulfonic acid) when measured by an LC-MS (high performance liquid chromatograph-mass spectrometer) is <5 ng/g in the (A), >5 ng/g in the (B) and <5 ng/g in the mixture of the (A) with the (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fiber structure in which the durability of a fluorine-based water repellent that is environmentally friendly is improved.

  In order to impart water repellency to clothing and industrial materials made of textiles, water repellents made of fluorine compounds have been widely used for a long time.

  Recently, such fluorine-based water repellents contain compounds that may affect living environment and living organisms, such as perfluorooctanoic acid (hereinafter PFOA), perfluorooctanesulfonic acid (hereinafter PFOS), and the like. It turns out. There is a demand for a textile product using a fluorine-based water repellent that does not contain the compound or has as little content as possible. Two or three kinds of compounds have been proposed as the environmentally-friendly fluorine-based water repellents. However, when performance is compared with conventional fluorine-based water repellents, the decrease in water repellency after washing is particularly large and durable. Improving sex is an urgent issue.

  In view of the present situation, the present invention uses a fluorine-based water repellent agent that is environmentally friendly and provides a fiber structure having excellent durability.

  In order to solve the above problems, the present invention employs the following means.

    (1) A mixture of a fluorine-based water-repellent compound (A) and a fluorine-based water-repellent compound (B), and perfluorooctanoic acid and / or as measured by a high performance liquid chromatograph-mass spectrometer (LC-MS) The concentration of perfluorooctane sulfonic acid is such that (A) is less than 5 ng / g, (B) is more than 5 ng / g, and the mixture of (A) and (B) is less than 5 ng / g. Fluorine-based water repellent.

    (2) The fluorinated water repellent according to (1) above, wherein the fluorinated water repellent compound (B) is a mixture of a plurality of fluorinated water repellent compounds.

    (3) The fluorine-based water repellent according to the above (1) and (2), wherein the weight mixing ratio of (A) and (B) is 15 or less with respect to (A) 100.

    (4) The fiber surface is coated with a fluorine-based water repellent, and the fluorine-based water repellent is a mixture of a fluorine-based water repellent compound (A) and a fluorine-based water repellent compound (B). The concentration of perfluorooctanoic acid and / or perfluorooctane sulfonic acid as measured by a high performance liquid chromatograph-mass spectrometer (LC-MS) is such that (A) is less than 5 ng / g and (B) is 5 ng A fiber structure characterized in that the mixture of (A) and (B) is less than 5 ng / g.

    (5) The fiber structure according to (4), wherein the fluorine-based water repellent coated on the fiber surface contains a triazine ring-containing compound and / or an isocyanate compound.

  According to the present invention, it is possible to stably supply a fluorine-based water repellent that is environmentally and biologically friendly, and a fiber structure having water repellency excellent in durability using the water repellent. The fiber structure of the present invention can be suitably used for apparel use and industrial material use.

  As a result of intensive studies on the above-mentioned problem, that is, a fiber structure having excellent water repellency using a fluorine-based water repellent that is friendly to the environment and organisms, the amount of PFOA and PFOS is the lower limit of quantification. It was sought to solve this problem at once by mixing a water-repellent compound with a fluorine compound exceeding the lower limit of quantification and mixing the water-repellent agent so that the mixing part does not exceed the lower limit of quantification. It is.

    The fluorine-based compound (A) of the present invention means a fluorine-based water repellent that has taken measures against PFOA and PFOS as an environmental load, and the amount of PFOA and / or PFOS contained in the compound is a high-speed liquid. When measured with a chromatograph-mass spectrometer (LC-MS), the lower limit of quantification is less than 5 ng / g, and preferably the lower limit of detection is less than 1 ng / g. Such a fluorine-based compound uses a new production method that eliminates the generation of the environmental load, or a method that uses various methods to recover the environmental load in the course of the conventional production method. In particular, Asahi Guard E Series AG-E061, which is a fluorine-based water repellent manufactured by Asahi Glass Co., Ltd., and Scotch Guards PM 3622, PM 490, PM 930 manufactured by Sumitomo 3M Co., Ltd. are exemplified.

    The fluorine-based compound (B) of the present invention means a conventionally used fluorine-based water repellent and is an acrylate-based compound containing a perfluoroalkyl group represented by the following general formula. Commercially available water repellents may be used alone or in admixture of two or more.

    The water repellent compound (A) referred to in the present invention does not contain an environmental adduct, so that a water-repellent perfluoroalkyl group having a strong water repellency is not higher than C8 and is used to adjust to C4 or lower. It has a fatal defect that the durability of water is inferior, and also has a defect that the Bundesmann water repellency is greatly reduced especially in the case of heavy rain required for sports applications.

    In the present invention, perfluorooctanoic acid and / or perfluorooctanesulfonic acid when the water repellent compound (B) is measured with a high performance liquid chromatograph-mass spectrometer (LC-MS) is added to the water repellent compound (A). A water repellent is prepared by mixing so that the concentration does not exceed the lower limit of quantification of 5 ng / g, and the durability of water repellency is improved.

    The mixing amount of the water repellent compound (B) varies depending on the type of the compound, but is 15 or less, preferably 9 or less with respect to (A) 100 in weight ratio, so that it does not exceed the lower limit of quantification of 5 ng / g. To mix.

    In the present invention, a water-repellent compound containing no fluorine element can be mixed with the fluorine-based compound. Such compounds include paraffinic compounds, aliphatic amide compounds, alkylethyleneurea compounds, and silicon compounds. Known compounds can be used, and one or more of these compounds can be used as fluorine-based water repellents. Mix in the agent.

    The fiber structure of the present invention is formed by coating the above water-repellent compound on the fiber surface.

    The coated water repellent of the present invention is mixed with at least one of a triazine ring-containing compound and an isocyanate compound. 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 Mention may be made of a polyfunctional block isocyanate urethane resin in which an ester, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam or the like is reacted. 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 dioleate, dibutyltin stearate, stearyl zinc and organic amine compounds are preferred.

    The method for applying the water repellent of the present invention to the fiber is not particularly limited, but after being immersed in an aqueous treatment liquid having a predetermined concentration, after being squeezed with a mangle so as to have a desired adhesion amount, the temperature is 100 to 140 ° C. After drying at a temperature and heat-treating at a temperature of 150 to 200 ° C., or after applying the treatment liquid by spraying, it may be similarly dried and heat-treated. Furthermore, the process in the bath which makes the temperature of a liquid rise to 50-130 degreeC and is made to adsorb | suck to the fiber surface can also be employ | adopted as it is immersed in a process liquid.

    In the present invention, in order to have antistatic properties, a water repellent agent may be fixed in a layer form on the antistatic polymer film. Examples of the antistatic polymer include a polyester resin containing a polyethylene glycol group, a urethane resin containing a polyethylene glycol group, a reaction product of a polycation compound containing a polyethylene glycol group and diglycidyl ether, and the like. In particular, as a monomer having two or more acrylic and / or methacrylic groups as both ends or one end of the main chain mainly composed of a polyalkylene oxide segment or a side chain of the main chain, for example, polyethylene glycol diester Acrylate, polyethylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol diacrylate, ethylene oxide adduct dimethacrylate of bisphenol A A monomer composed of a rate, an ethylene oxide adduct diacrylate of bisphenol A, a propylene oxide adduct dimethacrylate of bisphenol A, a propylene oxide adduct diacrylate of bisphenol A, etc., is used alone or as a mixture of two or more. Coalescence 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.

  An antistatic compound may be mixed in the water repellent of the present invention. Antistatic compounds used in the present invention include anionic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, phosphates, amine salts, quaternary ammonium salts, imidazoline 4 Cationic surfactants such as quaternary salts, nonionic surfactants such as polyethylene glycol type and polyhydric alcohol ester types, amphoteric surfactants such as imidazoline type quaternary salts, alanine type and betaine type, and polymer compound types As the above, at least one of the above-mentioned antistatic polymer and polyalkylamine can be used. Furthermore, an inorganic salt such as lithium chloride and magnesium chloride and an organic salt such as guanidine hydrochloride may be mixed.

  The fiber constituting the fiber structure of the present invention is not particularly limited, but includes polyester fiber, polyethylene fiber, polypropylene fiber, polyamide fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyacrylonitrile fiber, and the like. Synthetic fibers, semi-synthetic fibers such as rayon and acetate, and natural fibers such as cotton, hemp, silk, and wool. These fibers can be used alone or in admixture of two or more, and short fibers, long fibers or these may be mixed.

    Examples of the polyester fiber include a polyester fiber containing an aromatic component and an aliphatic polyester fiber. Examples of the polyester fiber containing an aromatic component include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate or those obtained by copolymerization or blending with a third component such as isophthalic acid, isophthalic acid sulfonate, adipic acid and polyethylene glycol. can do. Examples of the aliphatic polyester fiber include poly L lactic acid, poly D lactic acid and poly D, homopolymer composed of L lactic acid, polylactic acid-glycolic acid copolymer, and the like. The fibers used in the present invention may contain various commonly used additives for improving the productivity and properties in the production process and processing process of the raw yarn. For example, additives such as heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, antistatic agents, colorants, smoothing agents, plasticizers, antibacterial agents, fungicides and deodorants may be included. it can.

    As the fiber structure of the present invention, those in the form of fabrics such as woven fabrics, knitted fabrics and non-woven fabrics can be used, but are not limited thereto.

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
(Water repellent a)
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.

(Water repellency b)
Evaluation was made by the Bundesmann 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 K337 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 10 minutes, then drained and washed with overflow water for 10 minutes × 2 times, and this was repeated 30 times, followed by air drying.

(Examples 1-13, Comparative Examples 1-7)
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 with a liquid dyeing machine, dried at 130 ° C., and pintter set at 170 ° C. to obtain a scarlet woven fabric having a warp / width of 140/88 / 2.54 cm.

The dyed fabric was treated by the following method, and the performance was evaluated.
<Water repellent treatment>
(Water repellent A)
A-1: Asahi Guard AG-E061 (Asahi Glass Co., Ltd., fluorinated water repellent, solid content 20%)
A-2: Scotch guard PM3622 (manufactured by Sumitomo 3M Limited, fluorine-based water repellent, solid content 30%)
(Water repellent B)
B-1: Asahi Guard GS-10 (Asahi Glass Co., Ltd., fluorinated water repellent, solid content 18%)
B-2: Asahi Guard AG-7000 (Asahi Glass Co., Ltd., fluorinated water repellent, solid content 20%)
3 g / L of Sumitres Resin M-3 (manufactured by Sumitomo Chemical Co., Ltd., trimethylol melamine solid content 80%) as a crosslinking agent in the water repellent treatment solution, Sumitex Accelerator ACX (manufactured by Sumitomo Chemical Co., Ltd.) , Solid content 35%) 0.5 g / L, Super Fresh JB-7200 (manufactured by Kyokin Kasei Co., Ltd., polyfunctional block isocyanate-containing urethane resin, active ingredient 40%) was used in a mixture of 7 g / L. .

  A water repellent treatment solution is prepared using the above water repellent and crosslinking agent, a fabric is dipped in the solution, squeezed with a mangle so that the adhesion amount becomes 100%, dried at 120 ° C., and pinned at 170 ° C. Tenter set.

  It can be seen from Table 1 that the durability according to the present invention improves the water repellency.

Claims (5)

  1. Perfluorooctanoic acid and / or perfluorooctane as a mixture of a fluorinated water repellent compound (A) and a fluorinated water repellent compound (B) as measured by a high performance liquid chromatograph-mass spectrometer (LC-MS) The sulfonic acid concentration is such that (A) is less than 5 ng / g, (B) is more than 5 ng / g, and the mixture of (A) and (B) is less than 5 ng / g. Fluorine-based water repellent.
  2. The fluorine-based water repellent according to claim 1, wherein the fluorine-based water repellent compound (B) is a mixture of a plurality of fluorine-based water repellent compounds.
  3. The fluorine-based water repellent according to claim 1 or 2, wherein the weight mixing ratio of (A) and (B) is 15 or less with respect to (A) 100.
  4. The fiber surface is coated with a fluorine-based water repellent, and the fluorine-based water repellent is a mixture of a fluorine-based water repellent compound (A) and a fluorine-based water repellent compound (B). The concentration of perfluorooctanoic acid and / or perfluorooctane sulfonic acid as measured by a chromatograph-mass spectrometer (LC-MS) is such that (A) is less than 5 ng / g and (B) is 5 ng / g. A fiber structure characterized in that the mixture of (A) and (B) is less than 5 ng / g.
  5. The fiber structure according to claim 4, wherein the fluorine-based water repellent coated on the fiber surface contains a triazine ring-containing compound and / or an isocyanate compound.
JP2006072159A 2006-03-16 2006-03-16 Fluorine-based water repellent and fiber structure Pending JP2007247096A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006072159A JP2007247096A (en) 2006-03-16 2006-03-16 Fluorine-based water repellent and fiber structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006072159A JP2007247096A (en) 2006-03-16 2006-03-16 Fluorine-based water repellent and fiber structure

Publications (1)

Publication Number Publication Date
JP2007247096A true JP2007247096A (en) 2007-09-27

Family

ID=38591701

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2006072159A Pending JP2007247096A (en) 2006-03-16 2006-03-16 Fluorine-based water repellent and fiber structure

Country Status (1)

Country Link
JP (1) JP2007247096A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009057744A1 (en) * 2007-10-31 2009-05-07 Daikin Industries, Ltd. Aqueous composition for fluororubber vulcanization and coated article
WO2009081822A1 (en) 2007-12-26 2009-07-02 Asahi Glass Company, Limited Method for analysis of low-molecular-weight organic compound having 20 or less carbon atoms in water- and oil-repellent composition
JP2012122144A (en) * 2010-12-06 2012-06-28 Teijin Fibers Ltd Water-repellent woven fabric and clothing
JP2013083008A (en) * 2011-10-06 2013-05-09 Teijin Frontier Co Ltd Fabric and fiber product
US20130239289A1 (en) * 2010-12-07 2013-09-19 Teijin Frontier Co., Ltd. Water-repellent woven fabric and garment
US20150050438A1 (en) * 2012-12-17 2015-02-19 Teijin Frontier Co., Ltd. Cloth and textile product

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009057744A1 (en) * 2007-10-31 2009-05-07 Daikin Industries, Ltd. Aqueous composition for fluororubber vulcanization and coated article
JPWO2009057744A1 (en) * 2007-10-31 2011-03-10 ダイキン工業株式会社 Aqueous composition for fluororubber vulcanization and coated article
JPWO2009081822A1 (en) * 2007-12-26 2011-05-06 旭硝子株式会社 Method for analyzing low molecular weight organic compound having 20 or less carbon atoms in water / oil repellent composition
WO2009081822A1 (en) 2007-12-26 2009-07-02 Asahi Glass Company, Limited Method for analysis of low-molecular-weight organic compound having 20 or less carbon atoms in water- and oil-repellent composition
JP2012122144A (en) * 2010-12-06 2012-06-28 Teijin Fibers Ltd Water-repellent woven fabric and clothing
US9127380B2 (en) * 2010-12-07 2015-09-08 Teijin Frontier Co., Ltd. Water-repellent woven fabric and garment
TWI593842B (en) * 2010-12-07 2017-08-01 Teijin Frontier Co Ltd Water splashing fabric and clothing
US20130239289A1 (en) * 2010-12-07 2013-09-19 Teijin Frontier Co., Ltd. Water-repellent woven fabric and garment
EP2650430A4 (en) * 2010-12-07 2017-03-08 Teijin Frontier Co., Ltd. Water-repellent woven fabric and garment
EP2650430A1 (en) * 2010-12-07 2013-10-16 Teijin Frontier Co., Ltd. Water-repellent woven fabric and garment
JP2013083008A (en) * 2011-10-06 2013-05-09 Teijin Frontier Co Ltd Fabric and fiber product
KR20150096311A (en) * 2012-12-17 2015-08-24 데이진 프론티아 가부시키가이샤 Fabric and fiber product
US20150050438A1 (en) * 2012-12-17 2015-02-19 Teijin Frontier Co., Ltd. Cloth and textile product
US10161065B2 (en) * 2012-12-17 2018-12-25 Teijin Frontier Co., Ltd. Cloth and textile product
KR102046198B1 (en) * 2012-12-17 2019-11-18 데이진 프론티아 가부시키가이샤 Fabric and fiber product

Similar Documents

Publication Publication Date Title
US7615592B2 (en) Process for producing water- and oil-repellent agent
DE60026043T2 (en) Copolymers and such oil and water repellent compositions
US8796368B2 (en) Water-and oil-repellent
DE60212456T2 (en) Method for the water- and oil-repellent treatment of a weave or foam
AU759506B2 (en) Treated textile fabric
US7427300B2 (en) Hydrophilic finish for fibrous substrates
KR100810942B1 (en) Treated articles and methods of making and using same
AU2003301335B2 (en) Method of treating fibers, carpet yarns and carpets to enhance repellency
CA2777679C (en) Flame resistant textile
US8507580B2 (en) Antifouling composition, process for its production and article treated therewith
US6899923B2 (en) Methods for imparting reversibly adaptable surface energy properties to target surfaces
US20060005317A1 (en) Water and oil repellent aqueous composition
US7485588B2 (en) Method for making textile substrates having layered finish structure for improving liquid repellency and stain release
US20040138083A1 (en) Substrates having reversibly adaptable surface energy properties and method for making the same
US7407899B2 (en) Textile substrates having layered finish structure for improving liquid repellency and stain release
TWI593842B (en) Water splashing fabric and clothing
US7244371B2 (en) Compositions and methods for treating a textile using such compositions
TWI354724B (en) Coated woven or knit airbag fabric
US9091020B2 (en) Flame resistant fabrics and process for making
JP2003529673A (en) Finishing of textile fibers, fabrics and fabrics
KR100233702B1 (en) Treatment agent for fiber product, method of treating fiber product, and fiber product treated thereby
KR20030022265A (en) Textile substrates having improved durable water repellency and soil release and method for producing same
US20060228964A1 (en) Fabric treated with durable stain repel and stain release finish and method of industrial laundering to maintain durability of finish
US20040137814A1 (en) Wash-durable, liquid repellent, and stain releasing polyester fabric substrates
KR101761096B1 (en) Composition for oil- and /or water-repellent finishing of fiber materials