CN111183254A - Antifouling fiber structure - Google Patents

Antifouling fiber structure Download PDF

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Publication number
CN111183254A
CN111183254A CN201880064334.1A CN201880064334A CN111183254A CN 111183254 A CN111183254 A CN 111183254A CN 201880064334 A CN201880064334 A CN 201880064334A CN 111183254 A CN111183254 A CN 111183254A
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China
Prior art keywords
fiber structure
stain
fluorine
resin
oil
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竹下将太
竹田惠司
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Toray Industries Inc
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Toray Industries Inc
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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/208—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
    • D03D15/217—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based natural from plants, e.g. cotton
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • D—TEXTILES; PAPER
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • D—TEXTILES; PAPER
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]

Abstract

Provided is a fiber structure having high adhesion inhibition properties for aqueous and oily soils and soil removal properties by washing. A stain-resistant fiber structure characterized by having a resin coating film on at least a part of the fiber surface, the resin coating film comprising a fluorine-based oil-repellent resin containing a hydrophilic component and polyvinyl alcohol, and the stain-resistant fiber structure having a water repellency of grade 2 or less as measured by JIS L-1092 spray test and an oil repellency of grade 2 or more as measured by AATCC 118 method. The fluorine-based oil-repellent resin is preferably a fluorine-based oil-repellent resin containing a polyoxyalkylene group. The polyvinyl alcohol has an average polymerization degree of 200 to 1500.

Description

Antifouling fiber structure
Technical Field
The present invention relates to a fiber structure having high stain resistance.
Background
Conventionally, there has been a high demand for improvement in the stain resistance of a fiber structure of a fabric such as a woven fabric, and various methods for improving the stain resistance have been proposed. In general, as a method for imparting soil resistance to a fiber structure, a processing method in which a hydrophilic resin is imparted to a fiber structure to improve affinity with a washing liquid and thereby to easily cause soil to fall off, and a processing technique in which a water-and oil-repellent resin is imparted to a fiber structure to suppress adhesion of soil to fibers have been studied.
However, when a hydrophilic resin is applied to a fiber structure, there is a problem that when water-based dirt adheres, the water-based dirt tends to spread greatly. Further, when a water-and oil-repellent resin is provided to a fibrous structure, there is a problem that the affinity between a washing liquid and an aqueous soil is lowered due to water repellency, and therefore, once the soil is adhered, the soil is not easily removed by washing, and recontamination is easily caused.
In order to solve such problems, it has been studied to provide a water-and oil-repellent resin containing a hydrophilic group to fibers in order to satisfy both of the performance of difficulty in adhesion of dirt and the performance of easiness in detachment.
Patent documents 1 and 2 propose a water-absorbing, oil-repellent, and stain-proofing method for forming a film of a fluorine-based water repellent having a hydrophilic component.
Patent document 3 proposes a water-repellent, oil-repellent, and stain-proofing method for imparting a fluorine-based water-repellent agent to a fiber fabric using a non-blocked water-dispersible isocyanate crosslinking agent.
Patent document 4 proposes a water-repellent, oil-repellent, and stain-proofing method in which a coating film in which a polymer formed from a triazine ring-containing polymerizable monomer and a fluorine-based water repellent agent having a hydrophilic component are mixed is formed on the surface of a single fiber.
Patent document 5 proposes a weak water-and oil-repellent antifouling method for forming a coating film of a fluorine-based water repellent having a hydrophilic component, in which the mass concentration ratio of oxygen atoms to fluorine atoms is adjusted.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2006-152508
Patent document 2: japanese laid-open patent publication No. 2014-163030
Patent document 3: japanese patent laid-open publication No. 2013-36136
Patent document 4: japanese patent No. 5114946
Patent document 5: international publication No. 2017/006849
Disclosure of Invention
Problems to be solved by the invention
However, the processing methods proposed in patent documents 1 and 2 have a problem that, since they have high hydrophilicity, the scale is easily diffused when the water-based scale adheres.
The processing method proposed in patent document 3 has a problem that, since it exhibits high water repellency, affinity of a washing liquid with an aqueous soil during washing tends to be lowered, and soil removability by washing tends to be lowered, and in particular, soil removability after processing is low. In the processing method proposed in patent document 4, since a polymer formed from a triazine ring-containing polymerizable monomer is used in a large amount, there is a problem that a fluororesin or a hydrophilic component is buried and sufficient antifouling property cannot be exerted.
The processing method proposed in patent document 5 has a problem that although it has high washing durability, it has low antifouling property after processing.
In view of the problems of the prior art described above, an object of the present invention is to provide a fiber structure having both high adhesion-inhibiting properties and stain-removing properties with respect to aqueous and oily stains even after repeated washing after completion of processing.
Means for solving the problems
In order to solve the above problems, the present invention adopts the following means.
(1) A stain-resistant fiber structure characterized by having a coating film on at least a part of the fiber surface, the coating film comprising a fluorine-based oil-repellent resin containing a hydrophilic component and polyvinyl alcohol, and the stain-resistant fiber structure having a water repellency of grade 2 or less as measured by JIS L-1092 spray test and an oil repellency of grade 2 or more as measured by AATCC 118 method.
(2) The stain-proofing fiber structure according to the item (1), wherein the fluorine-based oil-repellent resin having a hydrophilic component is a fluorine-based oil-repellent resin containing a polyoxyalkylene group.
(3) The antifouling fibrous structure according to (1) or (2), wherein the polyvinyl alcohol has an average polymerization degree of 200 to 1500.
(4) The stain-resistant fibrous structure according to any one of (1) to (3), wherein the fluorine-based oil-repellent resin contains a repeating unit derived from a fluorovinyl monomer represented by the following general formula (I), and the fluorine-based oil-repellent resin has a content of perfluorooctanoic acid and perfluorooctane sulfonic acid lower than a detection limit.
CH2＝C(CH3)C(＝O)OCH2CH2(CF2)5CF3(I)
(5) The stain-repellent fiber structure according to any one of (1) to (4), which is characterized in that the fluorine-based oil-repellent resin, polyvinyl alcohol and a triazine ring-containing resin are applied to the surface of the fiber structure.
(6) The stain-proofing fibrous structure according to any one of (1) to (5), wherein the stain removability in the stain removability test for an indentation stain is grade 3-4 or more after 50 industrial washings.
(7) A clothing using the fiber structure according to any one of (1) to (6).
(8) A method for producing a stain-resistant fiber structure, characterized in that a fiber structure is treated with a treatment liquid containing a fluorine-based oil-repellent resin having a hydrophilic component and polyvinyl alcohol (hereinafter, also referred to as "treatment liquid containing a stain-resistant resin").
Effects of the invention
According to the present invention, a fiber structure having high stain resistance can be stably provided.
The antifouling fibrous structure of the present invention has a resin coating film on at least a part of the fiber surface, the resin coating film containing a fluorine-based oil-repellent resin having a hydrophilic component and polyvinyl alcohol, thereby suppressing adhesion of oil stains that are difficult to remove by washing to the fibers and improving affinity with a washing liquid during washing, and therefore, a fibrous structure having both high adhesion suppression property and stain removal property to aqueous and oily stains even after repeated washing after completion of processing can be provided.
Detailed Description
The antifouling fibrous structure of the present invention has a coating film on at least a part of the fiber surface, the coating film comprising a fluorine-based oil-repellent resin containing a hydrophilic component and polyvinyl alcohol, and the antifouling fibrous structure has a water repellency of grade 2 or less as measured by JIS L-1092 spray test and an oil repellency of grade 2 or more as measured by AATCC 118 method.
When the oil repellency is not less than 2 grade, the oil repellency is sufficient, and the dirt is less likely to be adsorbed to the fibers. Further, the number is preferably 5 or more. By setting the water repellency to 2 or less, sufficient hydrophilicity is provided, the affinity between the fibers and the washing liquid can be maintained, and the washing liquid does not fall into the fiber structure and contact dirt during washing, thereby removing the dirt.
That is, in the present invention, a fiber structure having a weak water-and oil-repellency which suppresses the degree of water repellency and has an oil repellency can exhibit a high stain resistance, and further, the degree of water repellency is controlled to a more appropriate weak water-repellent region, whereby the washing durability can be improved.
The oil repellency of the fiber structure is a value evaluated by AATCC 118 method (2013), and the water repellency is a value evaluated by a spraying method defined in JIS L1092 "water repellency test method for fiber products" (2009).
As the fluorine-based oil-repellent resin and polyvinyl alcohol having a hydrophilic component of the present invention, a fluorine-based oil-repellent resin and polyvinyl alcohol having an oil repellency of 2 or more and a water repellency of 2 or less by forming a coating film containing these on the fiber surface are preferably used.
The fluorine-based oil-repellent resin having a hydrophilic component is preferably a fluorine-containing copolymer having a repeating unit derived from a vinyl monomer having a perfluoroalkyl group and a vinyl monomer having a hydrophilic functional group (hydrophilic vinyl monomer).
As the vinyl monomer having a perfluoroalkyl group, a vinyl monomer having a perfluoroalkyl group having 6 or less carbon atoms is preferably used, and a monomer containing CH is more preferably used2＝C(CH3)C(＝O)OCH2CH2(CF2)5CF3A vinyl monomer of a derived repeating unit.
Examples of the hydrophilic vinyl monomer include vinyl monomers containing a hydrophilic functional group such as a sulfonyl group, a sulfonate group, a carboxyl group, a carboxylate group, an ammonium salt group, an oxyalkylene group, or a polyoxyalkylene group, and among them, a vinyl monomer represented by the following general formula (II) is preferable.
CH2＝CR1C(＝O)O-(R2O)n-R3(II)
In the formula, R1Usually H or an alkyl group having 1 to 4 carbon atoms, preferably H or CH3。-(R2O)n-represents an oxyalkylene group or a polyoxyalkylene group. R2An alkylene group having 2 to 5 carbon atoms is generally preferred, and CH is more preferred from the viewpoint of controlling the hydrophilicity to a more preferred range2CH2、CH2CH2CH2Or CH2(CH3)CH2。R3Usually represents H or CH3. n is a polymerization degree and represents 1 to 20.
The fluorine-based oil-repellent resin preferably used in the present invention is preferably a fluorine-based oil-repellent resin having a water absorption of 40 seconds or more, a water repellency of 2 or less and an oil repellency of 2 or more as measured by JIS L1907-dropping method (2010), and is more preferably a fluorine-based oil-repellent resin having a weak water repellency such as a water absorption of 60 seconds or more in view of improving washing durability of soil removability from an indentation soil. Further, the oil repellency is more preferably class 7 or less from the viewpoint of the balance between the difficulty of adhesion of dirt and the affinity with washing water.
The ratio of the vinyl monomer having a perfluoroalkyl group to the hydrophilic vinyl monomer in the above-mentioned fluorine-containing copolymer to be preferably used is not limited as long as it satisfies the range specified in the present invention, and can be controlled so as to have weak water-and oil-repellency and water-and oil-repellency by the following method. This control can be performed by the following method. That is, the water repellency can be suppressed by increasing the ratio of the vinyl monomer having a hydrophilic functional group, and the ratio of the vinyl monomer having a perfluoroalkyl group may be increased to increase the oil repellency.
In addition, even in the same ratio, the hydrophilicity of the vinyl monomer containing a hydrophilic functional group may be increased. As a method for this, the proportion of hydrophilic functional groups may be increased, or the water repellency may be reduced by selecting a functional group with higher hydrophilicity as the hydrophilic functional group. As the hydrophilic functional group, an oxyalkylene group (more preferably an oxyethylene group) or a polyoxyalkylene group (more preferably a polyoxyethylene group) is preferable. In the case of using polyoxyalkylene, hydrophilicity can be further improved when the degree of polymerization is large.
Further, the oil repellency can also be improved by increasing the carbon number of the perfluoroalkyl group in the perfluoroalkyl group-containing vinyl monomer.
The fluorine-based oil-repellent resin having a hydrophilic component satisfying the above conditions is preferably a fluorine-based oil-repellent resin which exhibits properties classified into a water-and oil-repellent type having a water repellency of not more than 2 (preferably not less than 1), an oil repellency of not less than 2 and a water absorbency of less than 40 seconds and a weak oil-and oil-repellent type having a water repellency of not more than 2, an oil repellency of not less than 2 and a water absorbency of not less than 40 seconds when applied to a fiber structure, and among them, a fluorine-based oil-repellent resin classified into a weak oil-and oil-repellent type is preferable. Commercially available products include "Paradin" KFS-100 (manufactured by Kyok Kasei K.K.) which is a weak water-and oil-repellent type and "Paradin" KFS-150 (manufactured by Kyok Kasei K.K.) which is an oil-and water-absorbing type. Note that even a fluorine-based water-repellent resin of the strong water-repellent oil-repellent type may be used as long as it satisfies the range specified in the present invention, and if the water repellency and oil repellency are too strong, it is difficult to control the range specified in the present invention, so that attention is required.
The fluorine-based oil-repellent resin preferably has a content of perfluorooctanoic acid and perfluorooctane sulfonic acid lower than the detection limit. Below the detection limit means: the concentrations of perfluorooctanoic acid and perfluorooctane sulfonic acid, and their precursors and salts measured by a high performance liquid chromatography-mass spectrometer (LC-MS) shown below were each less than 5 ng/g.
The device comprises the following steps: LC-MS/MS tandem mass spectrometer TSQ-7000 (thermal electron)
High performance liquid chromatograph LC-10Avp (Shimadzu institute)
A chromatographic column: capcellpak C8100 mm X2 mmi.d. (5 μm)
Mobile phase: a: 0.5mmol/L ammonium acetate B: acetonitrile
Flow rate: 0.2mL/min
Sample injection amount: 3 μ L
CP temperature: 220 deg.C
Ionization voltage: 4.5kv
Ion multiplication voltage (Japanese: イオンマルチ): 1300v
An ionization method: ESI-Negative
The average polymerization degree of polyvinyl alcohol is usually 100 to 3500, and preferably 200 to 1500.
The polyvinyl alcohol may be polyvinyl alcohol produced by saponifying polyvinyl acetate. The saponification degree of polyvinyl alcohol is preferably 70 to 99%, more preferably 80 to 95%.
The average polymerization degree and the saponification degree are values measured according to items 3.7 and 3.5 of JIS K6726 (1994), respectively.
The ratio of the fluorine-based oil-repellent resin and the polyvinyl alcohol used in the present invention is such that the mass of the polyvinyl alcohol is usually 5 to 60, preferably 10 to 40, relative to 100 mass of the solid content of the fluorine-based oil-repellent resin.
The polyvinyl alcohol used in the present invention may further contain a functional group other than a hydroxyl group or an acetoxy group, and examples thereof include an acetoacetyl group, a sulfonyl group, a sulfonate group, a carboxyl group, a carboxylate group, a quaternary ammonium group, an oxyalkylene group, a polyoxyalkylene group, an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and the like.
The amount of the fluorine oil-repellent resin and polyvinyl alcohol bonded to the fibers in the solid content is 0.2 to 1.0% by mass, preferably 0.4 to 0.8% by mass. Such a preferable range is preferable because the stain removing performance can be sufficiently exhibited and the hand feeling is soft.
In the present invention, other resins, compounds, and other preparations may be used in combination with the hydrophilic component-containing fluorine-based oil-repellent resin and polyvinyl alcohol.
In view of stain resistance and washing durability, it is particularly preferable to use a triazine ring-containing resin as the resin. Examples of the triazine ring-containing resin include melamine resin, guanamine resin, bismaleimide triazine resin, and the like, and melamine resin is particularly preferably used.
The triazine ring-containing resin is a resin containing a triazine ring-containing compound as a polymerization component, and the triazine ring-containing compound is a compound containing a triazine ring and having at least 2 polymerizable functional groups, and examples thereof include a triazine ring-containing compound represented by the following structural formula.
[ chemical formula 1]
Chemical formula 1
Figure BDA0002435245460000071
(in the formula, R4～R6Represents H, OH, C6H5、Cn0H2n0+1(n0＝1～2)、COOCn1H2n1+1(n1＝1～20)、CONR7R8、NR7R8. Wherein R is7And R8Representation H, OCn3H2n3+1(n3＝1～20)、CH2COOCn3H2n3+1(n3＝1～20)、CH2OH、CH2CH2OH、CONH2、CONHCH2-O-(X-O)n4-R9(X＝C2H4、C3H6、C4H8；n4＝1～1500；R9＝H、CH3、C3H7))
In addition to the triazine ring-containing compounds represented by the above general formula, ethylene urea copolymer, dimethylol thiourea copolymer, acid colloid compound, and the like of the above compounds can be used.
The method for forming the triazine ring-containing resin is as follows. After an aqueous liquid containing the triazine ring-containing compound and a catalyst is applied to the fibers, the fibers are subjected to heat treatment to polymerize the fibers.
Examples of the catalyst used include acids such as acetic acid, formic acid, acrylic acid, malic acid, tartaric acid, maleic acid, phthalic acid, sulfuric acid, persulfuric acid, hydrochloric acid, and phosphoric acid, and ammonium salts, sodium salts, potassium salts, and magnesium salts thereof, and one or more of them can be used. Among them, ammonium persulfate and potassium persulfate are preferably used as the catalyst. The amount of the catalyst is preferably 0.1 to 20% by mass based on the amount of the monomer.
The heat treatment for the polymerization is preferably a heat treatment in which dry heat treatment and steaming heat treatment are performed at a temperature of 50 to 200 ℃, preferably 80 to 150 ℃ for 0.1 to 30 minutes. The amount of the triazine ring-containing resin deposited is preferably 10 to 100% by mass, more preferably 20 to 60% by mass, based on the total weight of the hydrophilic component-containing fluorine-based oil-repellent resin and the polyvinyl alcohol.
The soil-resistant fibrous structure of the present invention preferably has a soil removal property of 3 to 4 grades or more, more preferably 4 grades or more, after the completion of processing and 50 industrial washes, when the soil removal property test for "soil removal by press-in soil" according to the C method using a component of lipophilic contaminant-3 specified in JIS L1919 (2006) "soil removal property test" is performed.
The fiber material used for the antifouling fiber structure of the present invention includes: fibers made of polyalkylene terephthalates such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate, aromatic polyester fibers obtained by copolymerizing the third component with these fibers, aliphatic polyester fibers made of aliphatic polyesters such as polylactic acid represented by polylactic acid containing L-lactic acid as a main component, polyamide fibers made of polyamides such as nylon 6 and nylon 66, acrylic fibers containing polyacrylonitrile as a main component, polyolefin fibers made of polyolefins 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, and wool. In the present invention, these fibers may be used alone or in the form of a mixture of 2 or more. Among them, it is preferable to use a mixture of fibers mainly composed of polyester fibers or polyamide fibers or fibers mainly composed of polyester fibers or polyamide fibers and natural fibers such as cotton, silk, and wool. The main component herein refers to the fiber having the largest content among the components contained therein, and is preferably contained in an amount of 50 mass% or more.
The fibers used in the antifouling fiber structure of the present invention may be, in addition to the normal flat yarn, filament yarns such as false twist yarn, twisted yarn, taslon yarn, nanofiber, roving yarn, and hybrid yarn, and fibers of various forms such as chopped fiber, staple fiber (tow), and spun yarn (japanese linear) may be used. Preferably, filament yarns are used.
The cross-sectional shape of the single fibers of the fibers used in the antifouling fibrous structure of the present invention is not particularly limited, and fibers of various forms such as round, triangular, flat, and multilobal fibers can be used. A circular cross-sectional shape is preferably used.
The antifouling fibrous structure of the present invention includes fabric-like materials such as knitted fabrics, woven fabrics, and nonwoven fabrics, and rope-like materials, which are formed using the above fibers. Knitted fabrics, woven fabrics and nonwoven fabrics are preferably used.
In addition, a general processing agent such as a fluorescent dye and a softening agent may be added to the fabric or the rope. As a material of the antifouling fibrous structure, a fiber internally modified with an antibacterial agent or a bacteriostatic agent can be used. As the above-mentioned processing agent, pyridine compounds such as 2-chloro-6-trichloromethylpyridine, 2-chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl-6- (2-furylmethoxy) pyridine, bis (4-chlorophenyl) pyridylmethanol, 2, 3, 5-trichloro-4- (n-propylsulfonyl) pyridine, 2-pyridylthiol-1-zinc oxide and bis (2-pyridylthiol-1-oxide) can be used.
In the fabric or rope, fibers may be used in which a resin other than the fluorine-based oil-repellent resin having a hydrophilic component and polyvinyl alcohol (hereinafter, collectively referred to as "antifouling resin", and a coating film including the "antifouling resin" may be referred to as "antifouling resin layer") is adhered to fibers as a raw material. In this case, a resin layer other than the stain-resistant resin is formed on the fibers so that two resin layers of the resin layer and a stain-resistant resin layer formed later are present on the fibers. Examples of the resin other than the antifouling resin include silicone resin, polyester resin, isocyanate compound, epoxy resin, melamine resin, guanamine resin, bismaleimide triazine resin, and the like.
Further, a fiber modified by crosslinking may be used, and as a crosslinking agent used for the crosslinking modification, a compound capable of reacting with a hydroxyl group in a cellulose molecule constituting a cellulose-based fiber, particularly a hydroxyl group located in an amorphous region which causes wrinkles, deformation, and shrinkage at the time of washing, and forming a crosslinked structure between and within the cellulose molecule is preferably used. Specific examples thereof include cellulose-reactive resins such as formaldehyde, dimethylolethyleneurea, dimethylol triazone, 3, 5-dimethylol dihydrooxadiazin-4-one (dimethyloluron), dimethylol glyoxal monourea, dimethylol propyleneurea, and compounds obtained by methoxylating or ethoxylating a part or all of the methylol groups of these compounds, polycarboxylic acids, and isocyanates.
In the present invention, the adhesion of the resin to the fiber structure can be achieved by treating the fiber structure with a treatment liquid containing the antifouling resin, the triazine ring-containing resin as an optional component, or a raw material such as a polymerizable monomer or a catalyst for obtaining the resin. As a specific processing method, there can be used: a Pad-Dry-Cure (Pad-Dry-Cure) method in which a fiber structure is impregnated in a treatment solution containing an antifouling resin, pressed under a constant pressure in a spread state, and then heat-treated; a Pad Cure (Pad Cure) method in which a fiber structure is immersed in a treatment solution containing an antifouling resin, pressed under a constant pressure in a spread state, and then heat-treated; or a Pad Steam (Pad Steam) method in which the impregnation is performed by the above method and then the steaming treatment is performed; or a bath method in which the fiber structure is heated while being immersed in a treatment liquid containing the antifouling resin. Among them, it is preferable to use: a pad-rolling, drying and baking method comprising impregnating a fiber structure in a treatment liquid containing an antifouling resin, pressing the fiber structure in a spread state at a predetermined pressure, drying the fiber structure at a temperature of preferably 80 to 170 ℃, and then heat-treating the fiber structure at a temperature of preferably 170 to 200 ℃; a padding and baking method of drying the resin at 170 to 200 ℃ in one go; a pad steaming method of steaming at a temperature of 80 to 110 ℃; or a bath method in which the fiber structure is immersed in a treatment liquid containing the antifouling resin and the temperature is raised to preferably 50 to 130 ℃. Further, the padding, drying and baking method is most preferable, which is used for drying at a temperature of 120 to 170 ℃ and then performing heat treatment at 170 to 200 ℃.
The antifouling fibrous structure obtained in this way has a resin coating film containing polyvinyl alcohol, and thus inhibits the adhesion of oil stains, which are difficult to remove by washing, to fibers, and also improves the affinity with a washing liquid during washing, and therefore, even after repeated washing after completion of processing, the antifouling fibrous structure has both high adhesion inhibition and stain removal properties to aqueous and oily stains, and therefore, the antifouling fibrous structure can be applied to general clothing, work uniforms (unifonms), bedding, medical clothing, interior decorations, industrial materials, and the like.
Examples
Next, the antifouling fibrous structure of the present invention will be described based on examples. Various measurement evaluations in the examples are shown below.
(degree of Water repellency)
The water repellency was evaluated by the spray method according to the method specified in JIS L1092 "method for testing water repellency of textile products" (2009) to determine the grade of the water repellency. The rank determination was performed by evaluation n-3 times. The grade of the water repellency is 1 to 5, and the larger the value, the higher the water repellency. The judgment standard was identified by a judgment photograph attached to JIS L1092.
(oil repellency)
The oil repellency was measured by the method defined by AATCC 118 method, and the grade was determined. The grade of oil repellency is 1 to 8, and a larger value indicates higher oil repellency. The criterion was identified by a determination photograph attached to the AATCC 118 method. For the grade determination, the average of the evaluation was taken where n is 3 times.
(Industrial washing conditions in soil removability test)
Industrial washing for washing durability and soil removability in the soil removability test was performed 1 time under the following conditions and sequence.
1. Cleaning (water temperature 60 ℃, bath ratio 1: 10, time 15 minutes)
A detergent: phosphorus-free Dash (manufactured by LION corporation) 2.0g/L
Sodium metasilicate 2.0g/L
Clewat N (Nagase Chemte X, Inc.) 1.0g/L
2. Dehydration (time 1 minute)
3. Rinsing 1 (Water temperature 50 ℃, bath ratio 1: 10, time 3 minutes)
4. Dehydration (time 1 minute)
5. Rinsing 2 (Water temperature 35 ℃, bath ratio 1: 10, time 3 minutes)
6. Dehydration (time 1 minute)
7. Rinsing 3 (normal water temperature, bath ratio 1: 10, time 3 minutes)
8. Dehydration (time 1 minute)
9. Drum drying
(test for removing Press-in dirt)
The fiber structure after the industrial washing was carried out 50 times under the above conditions and the fiber structure before the washing were evaluated for the press-in soil removal performance by the C method according to JIS L1919 "method for testing soil resistance of fiber products" (2006). A contaminant (oil red fraction 0.1%) as a component of lipophilic contaminant-3 specified in method C of JIS L1919 "method for testing antifouling property of textile products" (2006) was prepared, and the test was carried out according to the following procedure.
1. A PET film was placed on a square filter paper, and a fabric cut into 8 cm. times.8 cm was placed thereon. 0.1mL of oily soil was added dropwise from a height of 10cm, and the mixture was left for 30 seconds.
2. A PET film cut to the same size as the cloth was placed on the stained cloth, and 4g/cm was applied from above2The load of (2) for 30 seconds. After removing the load and the membrane, a round filter paper was placed, and the dirt was sucked up by the self weight of the filter paper. Further, the position of the filter paper was moved to suck the dirt again with the uncontaminated portion of the filter paper. This operation was repeated until the filter paper became unable to pick up the dirt. When the filter paper does not contact the contaminated part, the filter paper is brought into contact with the dirt so as to hold both ends of the filter paper and apply as little load as possible, thereby performing suction. Then, the mixture was left at 20 ℃ and 65% relative humidity for 24 hours. After the standing, the contaminated fabric was sewn to a size of about 40cm × 40cm, and washed. If the soiled fabric is insufficient, the disposable fabric is sewn.
3. SR property rating determination was performed by visual determination using JIS L0805 (2005) stain gray scale. The scale is 1 to 5 inclusive, and the larger the value, the higher the antifouling property. The equipment used in the above test is shown in table 1.
[ Table 1]
Figure BDA0002435245460000141
(evaluation of spreading mode of dirt after pushing-in of dirt)
In the soil removability test for the press-in soil, the spread of the soil after 24 hours had passed after the adhesion of the soil was visually evaluated, and the evaluation was performed on a 1 to 5 scale.
Level 1: in the test fabric, the dirt penetrated in more than eighty percent of the area of the other part except the press-in dirt part
And 2, stage: in the test fabric, the dirt penetrated into an area of about five percent of the area of the other portion except the press-in dirt portion.
And 3, level: in the test fabric, dirt penetrated into the area of about three minutes except the press-in dirt portion.
4, level: in a state where dirt slightly penetrates in addition to the pressed-in dirt portion.
And 5, stage: in a state where no dirt penetrates except the press-in dirt portion.
(example 1)
A single yarn of 14 count (Japanese: 14 double hand) formed by 65% of polyethylene terephthalate and 35% of cotton was used for the warp and weft yarns, and a twill woven fabric was woven. The obtained twill woven fabric was refined and washed with hot water at a temperature of 95 ℃ by a continuous refiner according to a conventional method, and then dried at a temperature of 130 ℃. Then, the fabric was dyed to fluorescent white at a temperature of 130 ℃ using a flow dyeing machine, washed by a conventional method, washed with hot water and dried, and heated at a temperature of 170 ℃ to obtain a white fabric having a warp density of 86 pieces/2.54 cm and a weft density of 55 pieces/2.54 cm.
Next, 90g/L, (B)18g/L, (H)4.5g/L, and (I)0.75g/L of (A) described later were dissolved to prepare a treatment liquid, and the white fabric produced as described above was immersed in the treatment liquid in a spread state, and a mangle was used at a mangle ratio (Japanese: )
Figure BDA0002435245460000151
Rate) was 60%, dried at a temperature of 130 ℃, and then subjected to heat treatment at a temperature of 170 ℃ to obtain an antifouling fibrous structure. The dirt-removing press-in property gray scale after the completion of the processing of the resulting antifouling fibrous structure was judged as class 4, and the dirt-removing press-in property gray scale after 50 times of industrial washing was judged as class 4.
(example 2)
An antifouling fibrous structure was obtained in the same manner as in example 1, except that (B) in example 1 was changed to 36 g/L. The dirt-removing press-in property after the completion of the processing of the resulting antifouling fibrous structure was judged to be class 4 on the gray scale, and the dirt-removing press-in property after 50 industrial washings was judged to be class 3 to 4 on the gray scale.
(example 3)
An antifouling fiber structure was obtained in the same manner as in example 1, except that 18g/L of (C) was used as polyvinyl alcohol in example 1. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated as 3-4, and the dirt-removing press-in soil scale after 50 industrial washing was rated as 3-4.
(example 4)
An antifouling fiber structure was obtained in the same manner as in example 1, except that 18g/L of (D) was used as polyvinyl alcohol in example 1. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated 3-4, and the dirt-removing press-in soil scale after 50 industrial washing was rated 3.
(example 5)
48 single yarns formed by 65% of polyethylene terephthalate and 35% of cotton were used for the warp and weft yarns, and a plain woven fabric was woven. The obtained plain woven fabric was scoured at a temperature of 95 ℃ by a continuous scouring machine according to a conventional method and washed with hot water, followed by drying at a temperature of 130 ℃. Then, the fabric was dyed to fluorescent white at a temperature of 130 ℃ using a flow dyeing machine, washed by a conventional method, washed with hot water and dried, and heated at a temperature of 170 ℃ to obtain a white fabric having a warp density of 138 pieces/2.54 cm and a weft density of 72 pieces/2.54 cm.
Subsequently, an antifouling treatment was performed in the same manner as in example 1 to obtain an antifouling fibrous structure. The dirt-removing press-in property after the completion of the processing of the resulting antifouling fibrous structure was judged to be class 4 on the gray scale, and the dirt-removing press-in property after 50 industrial washings was judged to be class 4-5 on the gray scale.
(example 6)
An antifouling fibrous structure was obtained in the same manner as in example 5, except that (B) in example 5 was changed to 36 g/L. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated 4-5, and the dirt-removing press-in soil scale after 50 industrial washing was rated 4.
(example 7)
48 single yarns formed of 55% polyethylene terephthalate and 45% cotton were used for the warp and weft yarns, and plain woven fabrics were woven. The resulting plain woven fabric was refined and washed with hot water at a temperature of 95 ℃ by a continuous refiner in a conventional manner, and then dried at a temperature of 130 ℃. Then, the fabric was dyed to fluorescent white at a temperature of 130 ℃ using a flow dyeing machine, washed by a conventional method, washed with hot water and dried, and heated at a temperature of 170 ℃ to obtain a white fabric having a warp density of 115 pieces/2.54 cm and a weft density of 72 pieces/2.54 cm.
Subsequently, an antifouling treatment was performed in the same manner as in example 1 to obtain an antifouling fibrous structure. The dirt-removing press-in property after the completion of the processing of the resulting antifouling fibrous structure was judged to be class 4 on the gray scale, and the dirt-removing press-in property after 50 industrial washings was judged to be class 4-5 on the gray scale.
(example 8)
An antifouling fibrous structure was obtained in the same manner as in example 7, except that (B) in example 7 was changed to 36 g/L. The dirt-removing press-in property after the completion of the processing of the resulting antifouling fibrous structure was judged to be class 4 on the gray scale, and the dirt-removing press-in property after 50 industrial washings was judged to be class 4-5 on the gray scale.
(example 9)
An antifouling fibrous structure was obtained in the same manner as in example 1, except that the amount of (B) in example 1 was changed to 54 g/L. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated 4-5, and the dirt-removing press-in soil scale after 50 industrial washing was rated 2-3.
(example 10)
A stain-resistant fiber structure was obtained in the same manner as in example 1, except that 90g/L of (E) was used as the fluorine-based oil-repellent resin method in example 1. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated 3-4, and the dirt-removing press-in soil scale after 50 industrial washing was rated 2-3.
Comparative example 1
A fiber structure having poor water-and oil-repellency and stain-proofing properties was obtained in the same manner as in example 1, except that (B) was not used in example 1. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated as 2 to 3, and the dirt-removing press-in soil scale after 50 industrial washing was rated as 3 to 4.
Comparative example 2
A fiber structure was obtained in the same manner as in example 1, except that (a) was not used in example 1. The dirt-removing press-in soil scale after the completion of the processing of the resulting antifouling fibrous structure was rated 1-2, and the dirt-removing press-in soil scale after 50 industrial washings was rated 2.
Comparative example 3
A water-and oil-repellent soil-resistant fibrous structure was obtained in the same manner as in comparative example 1, except that 90g/L of (E) was used as the fluorine-based oil-repellent resin in comparative example 1. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated 3-4, and the dirt-removing press-in soil scale after 50 industrial washing was rated 2-3. As a result, the spread of the dirt after the pressing was large as compared with example 8.
Comparative example 4
The white fabric obtained in example 1 was impregnated with the treatment liquid prepared by dissolving (F)45g/L, (H)15g/L, and (J)3.0g/L, and then extruded with a mangle so that the mangle ratio became 60%, and the treatment was performed for 5 minutes in a saturated steam atmosphere at 105 ℃. Subsequently, the fiber was washed with an aqueous solution of sodium carbonate at 1g/L at 60 ℃ for 1 minute, washed with water, dried at 130 ℃ and then heat-treated at 170 ℃ to obtain a water-and oil-repellent and stain-resistant fiber structure. The dirt-removing press-in property after the completion of the processing of the resulting antifouling fibrous structure was judged to be class 3 on the gray scale, and the dirt-removing press-in property after 50 industrial washings was judged to be class 3 on the gray scale.
Comparative example 5
A water-and oil-absorbent and stain-resistant fibrous structure was obtained in the same manner as in comparative example 1, except that 90G/L (G) was used in place of the fluorine-based oil-repellent resin (A) in comparative example 1. The dirt-removing press-in soil scale of the resulting anti-fouling fiber structure after completion of processing was rated as 2 to 3, and the dirt-removing press-in soil scale after 50 industrial washing was rated as 2 to 3.
(A) "Paradin" KFS-100 (fluorine-based oil-repellent resin of weak water-and oil-repellency type, manufactured by Kyowa Kasei K.K., 10% in solid content, polyoxyethylene-containing fluorine-based oil-repellent resin having water repellency of grade 2, oil repellency of grade 6 and water absorbency of 60 seconds or more)
(B) Polyvinyl alcohol (10% in solid content, average degree of polymerization 500, degree of saponification 90%)
(C) Polyvinyl alcohol (solid content 10%, average degree of polymerization 1500, degree of saponification 90%)
(D) Polyvinyl alcohol (solid content 10%, average degree of polymerization 2000, degree of saponification 90%)
(E) "Paradin" KFS-150 (fluorine-based resin of oil and water repellency type, manufactured by Kyowa Kasei K.K., 10% solid content, polyoxyethylene-containing, water repellency grade 1, oil repellency grade 6, water absorbency 30 seconds)
(F) "Asahi Guard" AG-1100 (fluorine-based resin of strong water and oil repellency type manufactured by Asahi glass Co., Ltd., solid content: 20%, polyoxyethylene group-containing, water and oil repellency grade 3, 6, and water absorbency: 60 seconds or more)
(G) "Brian" SR2100 (manufactured by Songban oil & fat pharmaceutical Co., Ltd., solid content 10%, hydrophilic polyester resin, Water repellency grade 1, oil repellency 0, Water absorbency 1 second or less)
(H) "Amidir" M-3 (triazine ring-containing Compound manufactured by DIC Co., Ltd.: solid content: 80%)
(I) "Catalyst" ACX (Catalyst solid content 35% manufactured by DIC corporation)
(J) Ammonium persulfate
The results of compositions (a) to (J) of the treatment liquids of examples 1 to 8 and comparative examples 1 to 5, the properties of the obtained fiber structures, and the like are shown in table 2.
[ Table 2]
Figure BDA0002435245460000201
As can be seen from Table 2: in examples 1 to 10, which are the fiber structures of the present invention, dirt after press-fitting was easily repelled, and the range of spread of dirt was small, and dirt was not easily adhered. In addition, the fiber structure of the present invention is excellent in the stain removability against the press-in stains, while comparative examples 1 to 5, which are different from the antifouling fiber structure of the present invention, are inferior to examples in the stain removability against the press-in stains. In example 9 in which the amount of polyvinyl alcohol was increased, the washing durability of the stain-proofing property could be improved by optimizing the amount of polyvinyl alcohol to be added. By improving the washing durability, the functionality can be maintained even after repeated washing, and the life of the clothes can be prolonged.
Industrial applicability
The antifouling fibrous structure of the present invention has both high adhesion inhibition properties against aqueous and oily soils and soil removal properties by washing, and is therefore suitable for use as general clothing, work uniforms, bedding, medical clothing, upholstery, industrial materials, and the like. Among them, the resin composition is suitable for use as a work uniform which is required to have antifouling performance and to which oil dirt and the like which are not easily detached by washing are easily attached.

Claims (8)

1. A stain-resistant fiber structure characterized by having a resin coating film on at least a part of the fiber surface, the resin coating film comprising a fluorine-based oil-repellent resin containing a hydrophilic component and polyvinyl alcohol, and the stain-resistant fiber structure having a water repellency of grade 2 or less as measured by JISL-1092 spray test and an oil repellency of grade 2 or more as measured by AATCC 118 method.
2. The soil resistant fiber structure according to claim 1, wherein the fluorine-based oil-repellent resin is a polyoxyalkylene group-containing fluorine-based oil-repellent resin.
3. The antifouling fibrous structure according to claim 1 or 2, wherein the polyvinyl alcohol has an average degree of polymerization of 200 to 1500.
4. The stain-resistant fiber structure according to any one of claims 1 to 3, wherein the fluorine-based oil-repellent resin contains a repeating unit derived from a fluorovinyl monomer represented by the following general formula (I), and the fluorine-based oil-repellent resin has a content of perfluorooctanoic acid and perfluorooctane sulfonic acid lower than a detection limit,
CH2＝C(CH3)C(＝O)OCH2CH2(CF2)5CF3(I)。
5. a stain-resistant fiber structure according to any one of claims 1 to 4, wherein the fluorine-based oil-repellent resin, the polyvinyl alcohol and the triazine ring-containing resin are provided on the surface of the fiber structure.
6. The stain-resistant fibrous structure according to any one of claims 1 to 5 wherein the stain removability of the fibrous structure in a stain removability test for an indentation stain is grade 3-4 or more after 50 industrial washings.
7. A clothing material comprising the fiber structure according to any one of claims 1 to 6.
8. A method for producing a stain-proofing fiber structure, characterized in that a fiber structure is treated with a treatment liquid containing a fluorine-based oil-repellent resin having a hydrophilic component and polyvinyl alcohol.
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