JP5994918B2 - Method for producing water / oil repellent fabric and fabric thereof - Google Patents

Description

  The present invention relates to a method for producing a water- and oil-repellent fabric that maintains the original tactile sensation of the base fabric and has an excellent anti-staining effect on the base fabric, and the fabric.

Many attempts have been made to improve the antifouling function by imparting water repellency and oil repellency to a synthetic fiber or natural fiber fabric.
For example, Patent Document 1 proposes forming a copolymer film comprising a fluorine-containing polymer monomer, a comonomer not containing a fluorine atom, and a crosslinking agent between a fabric and a fluorine-containing polymer. ing.

In Patent Document 2, a coating resin solution made of a synthetic polymer mainly composed of polyurethane resin or polyamino acid urethane resin is applied to a polyester fiber fabric dyed with a disperse dye to form a coating film, and then the coating is formed. A method for producing a coated fabric is disclosed in which an electron beam is irradiated on a film in an atmosphere having an oxygen concentration of 500 ppm or less.
Patent Document 3 discloses an oil repellent / water repellent filter in which an oil repellent / water repellent is fixed to a surface including a porous space of a filter based on a gas permeable material having a continuous porous structure by ultraviolet irradiation. A manufacturing method is disclosed.
In Patent Document 4, at least one surface of a fibrous base material of a fabric is treated with a treatment liquid comprising a fluorine-containing water- and oil-repellent agent containing an organic solvent and an antifoaming agent containing a fluorine compound. There has been proposed a method for producing a fabric having the following.

Patent Document 5 proposes a water- and oil-repellent fabric obtained by adding a fluorine-based water repellent and a non-block type water-dispersed polyisocyanate-based crosslinking agent to a fiber fabric.
Patent Document 6 discloses a method for processing a polyester / cotton fabric, which includes a step of applying an antistatic monomer to a fabric made of polyester and cotton, reacting and fixing, and a step of applying a fluoroalkyl acrylate polymer emulsion to the fabric. Is disclosed.
In Patent Document 7, a polyester-based fabric dipped in a methanol solution of a vinyl monomer containing a fluorine atom in the molecule is sandwiched between films and pressed to remove excess monomer and oxygen, and then irradiated with an electron beam. A method for producing a polyester fabric that is graft-polymerized at a temperature of ˜70 ° C. has been proposed.
Furthermore, Patent Document 8 discloses that a composition containing a complex between an anionic polymer and a cationic polymer is used to make a fabric water repellency, oil repellency, dirt resistance, wrinkle resistance, antistatic property, antifouling property. Disclosed is a method for providing performance enhancing properties selected from the group consisting of properties, hydrophobicity, hydrophilicity, antibacterial properties, flame retardancy, temperature control and UV resistance.

JP 60-39482 A JP-A-7-11586 JP-A-9-103662 Japanese Patent Laid-Open No. 9-302583 JP 2006-207060 A JP 2007-9337 A JP 2008-115492 A JP 2008-508440 A

However, in the above-described method, it has been difficult to suitably improve the anti-contamination effect of the base fabric while maintaining the original feel of the base fabric when manufacturing the water / oil repellent fabric.
Under such circumstances, the present invention provides a water- and oil-repellent coat on a base fabric that is a fabric including a non-woven fabric, and is excellent in anti-pollution effects of the base fabric by repelling liquid contaminants such as dyes and blood. Another object of the present invention is to provide a water and oil repellent fabric that maintains the original feel of the base fabric.

As a result of intensive research in order to solve the above problems, the present inventor applied a specific coating coating solution to a base fabric or dipped the base fabric in the coating coating solution to make a specific surface roughness water repellent. It has been found that the above-mentioned problems can be solved by forming an oil-repellent fabric. The present invention has been completed based on such findings.
That is, the present invention
(1) The above-mentioned water repellency in a water / oil repellent fabric in which a cured film of an ionizing radiation curable resin composition containing at least an ionizing radiation curable resin and a fluorine compound is formed on the surface of a fiber constituting the base fabric. The surface roughness Zb (μm) of the water / oil repellent fabric is 1.5 times or more the surface roughness Za (μm) of the base fabric before the formation of the cured film , and the surface roughness of the water / oil repellent fabric. Zb is 120～600Myuemu, water- and oil-repellency fabric 帛, wherein the total weight of the cured film is 0.2-5 g / m ^2,
[Measurement Method of Surface Roughness Using a non-contact surface shape / roughness measuring device, the distance in the depth direction from the outermost surface of the base fabric or water / oil repellent fabric is measured. The average distance is calculated from the value measured n = 2601 every 10 μm in the range of 500 μm × 500 μm, and the surface roughness Za or Zb is obtained. And (2) An ionizing radiation curable resin composition containing an ionizing radiation curable resin and a fluorine compound and a coating coating solution containing at least a solvent are applied to the base fabric, or the base fabric is immersed in the coating coating solution. Forming a coating film on the surface of the fibers constituting the base fabric;
A method for producing a water- and oil-repellent fabric comprising the step of irradiating the coating film with ionizing radiation to form a cured film on the surface of the fiber, wherein the surface of the water- and oil-repellent fabric has a cured film formed thereon. The roughness Zb (μm) is 1.5 times or more the surface roughness Za (μm) of the base fabric before forming a cured film , and the surface roughness Zb of the water / oil repellent fabric is 120 to 600 μm . A method for producing a water- and oil-repellent fabric , wherein the cured film has a total mass of 0.2 to 5 g / m ² ;
[Measurement Method of Surface Roughness Using a non-contact surface shape / roughness measuring device, the distance in the depth direction from the outermost surface of the base fabric or water / oil repellent fabric is measured. The average distance is calculated from the value measured n = 2601 every 10 μm in the range of 500 μm × 500 μm, and the surface roughness Za or Zb is obtained. ]
Is to provide.

  According to the present invention, it is possible to provide a water- and oil-repellent fabric that is excellent in the effect of preventing contamination of the base fabric by repelling liquid contaminants such as dyes and blood and that maintains the original feel of the base fabric.

The method for producing a water- and oil-repellent fabric of the present invention comprises applying an ionizing radiation curable resin composition containing an ionizing radiation curable resin and a fluorine compound and a coating solution containing at least a solvent to the base fabric, or applying the base fabric to the base fabric. A step of immersing in the coating solution to form a coating film on the surface of the fibers constituting the base fabric (hereinafter sometimes referred to as “first step”), and irradiating the coating film with ionizing radiation A method for producing a water / oil repellent fabric comprising a step of forming a cured film on the surface of the fiber (hereinafter sometimes referred to as “second step”), the surface of the water / oil repellent fabric being The roughness Zb (μm) is 1.5 times or more the surface roughness Za (μm) of the base fabric before coating or dipping.
Here, the measuring method of surface roughness measures the depth direction distance from the fabric outermost surface using a non-contact surface shape / roughness measuring instrument. The average distance is calculated by arithmetic mean from the value measured n = 2601 every 10 μm in the range of 500 μm × 500 μm, and the average distance of the base fabric before coating or dipping is defined as the surface roughness Za (μm). The average distance of the oil fabric is defined as the surface roughness Zb (μm).
If the surface roughness Zb of the water / oil repellent fabric obtained by the production method of the present invention is in the range of 120 to 600 μm, both water repellency and oil repellency are improved.

Hereinafter, the first step and the second step will be described.
[First step]
The first step according to the production method of the present invention is to apply a coating coating solution containing at least an ionizing radiation curable resin composition containing an ionizing radiation curable resin and a fluorine-based compound and a solvent to the base fabric, or apply the base fabric to the base fabric. It is a process to form a coating film on the surface of the fiber that constitutes the base fabric by immersing in the coating liquid. By adjusting the amount of solvent in the coating liquid, the coating film (the solvent is removed and dried) The thickness of the subsequent coating film) will be controlled. From the viewpoint of controlling the surface roughness Zb (μm) of the water / oil repellent fabric to 1.5 times or more of the surface roughness Za (μm) of the base fabric before application or immersion, the mass part of the solvent of the coating coating solution is It is preferably 2 to 150 times the mass part of the ionizing radiation curable resin, more preferably 5 to 100 times, and still more preferably 20 to 50 times.
As an application method for applying the coating liquid to the base fabric, a normal coating method, for example, reverse coating, knife coating, comma coating, gravure coating, gravure reverse coating, bar coating, roll coating, reverse roll coating, or the like is used. . Moreover, as a dipping method for dipping the base fabric in the coating coating solution, for example, dip coating or the like is used.
As a drying method for forming the coating film, a normal drying method, for example, heat treatment, reduced pressure drying treatment, or the like is used. Examples of the heat treatment include leaving in an oven at 60 to 120 ° C. for 1 to 10 minutes.

[Second step]
The second step according to the production method of the present invention is a step of forming a cured film on the fiber surface by irradiating the coating film obtained in the first step with ionizing radiation.
It is easy to dissolve in water with water-based resin coating alone, but by using ionizing radiation curing method, it becomes difficult to dissolve in water after curing, and water and oil and oil repellency can be maintained for a long time even in a humid environment. Become. In addition, oil repellency may not be obtained only with an organic solvent-based resin coating, but by using a method of ionizing radiation curing, oil repellency can be maintained for a long time after curing.
Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as rays and γ rays, and charged particle beams such as α rays and ion rays can also be used. Among these ionizing radiations, an electron beam (EB) is preferable from the viewpoint of environment and health because it is easy to select an appropriate strength for immobilizing the coating film on the entire fiber surface constituting the base fabric. The irradiation condition of the electron beam (EB) is preferably in the range of 50 to 200 kV and 20 to 70 kGy, more preferably in the range of 20 to 40 kGy, from the viewpoint of maintaining both the original touch feeling of the base fabric and enjoying a high antifouling effect. preferable.
The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

[Water and oil repellent fabric]
In the production method of the present invention, the surface roughness Zb (μm) of the obtained water / oil repellent fabric is 1.5 times or more the surface roughness Za (μm) of the base fabric before coating or dipping, The apparent contact angle can be increased by emphasizing the fine structure of the surface of the base fabric and increasing the occupied area of the surface recesses. Thereby, the water and oil repellency more than the effect which the surface free energy fall by the coating of a fluorine compound brings about can be shown.
This Zb / Za is preferably 1.5 to 5 times, more preferably 1.5 to 4 times, and still more preferably 2 to 4 times. By setting it to 1.5 times or more, both water repellency and oil repellency can be suitably imparted.
As a non-contact surface shape / roughness measuring instrument used to measure surface roughness Zb and Za, for example, a measurement microscope that can observe minute steps on a sample surface that cannot be normally seen using light polarization and coherence Are preferably used. As this measuring microscope, Olympus Corporation make and measuring microscope "STM6" (brand name) are mentioned suitably.
Moreover, by making the total amount of the cured film in the range of 0.2 to 50 g / m ^{2 on} the surface of the fibers constituting the base fabric, it is possible to bring it closer to the original feel of the base fabric.
The water and oil repellent fabric of the present invention obtained as described above has a cured film of an ionizing radiation curable resin composition containing at least an ionizing radiation curable resin and a fluorine-based compound on the fiber surface of the base fabric. It is.

[Base fabric]
The base fabric used in the production method of the present invention is not particularly limited, and includes all fiber fabric products such as general woven fabrics, knitted fabrics, and nonwoven fabrics. The fibers constituting the base fabric include polyolefin fibers such as polyethylene, synthetic fibers such as polyester fibers and polyamide fibers, natural fibers such as cotton, wool and silk, regenerated fibers such as rayon, and semisynthetic fibers such as triacetate. Can be mentioned. Moreover, those blends, union, mixed fiber may be sufficient. As described above, the present invention is a highly versatile production method in which all fiber fabric-like products selected from natural, regenerated, and synthetic fibers can be used as a base fabric.
Examples of the nonwoven fabric used as the base fabric include polyethylene-based nonwoven fabrics, cotton nonwoven fabrics, and rayon nonwoven fabrics.
Examples of the bonding process of the nonwoven fabric include a resin bond method, a thermal bond method, a needle punch method, a spun bond method, a melt blown method, a spun lace method, an airlaid method, a wet method, and an air through method. It is preferable to use a nonwoven fabric entangled by a spunlace method or an air-through method in that the surface roughness Za and Zb (μm) can be appropriately controlled.
Here, the spunbond method is a production method in which long fibers called filaments are formed into a sheet and finished as a nonwoven fabric by applying heat and pressure. The spunlace method is a manufacturing method in which a high-pressure jet stream is applied to a web, fibers are entangled and mechanically bonded, and wound after drying. The air-through method is a manufacturing method in which fibers are bonded by a water flow and then dried through high-temperature dry air. The spunbond nonwoven fabric refers to a nonwoven fabric produced by a spunbond method.

[Coating fluid]
The coating coating liquid according to the present invention includes at least an ionizing radiation curable resin composition containing an ionizing radiation curable resin and a fluorine-based compound and a solvent.
(Ionizing radiation curable resin)
As the ionizing radiation curable resin, typically, a (meth) acrylate (monomer or oligomer) having a radical polymerizable unsaturated group in the molecule is suitable, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, as the (meth) acrylate monomer, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) Acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Examples include hexa (meth) acrylate and urethane (meth) acrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  Next, as the (meth) acrylate oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a polyether (meta) ) Acrylate oligomers and the like. Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. A carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. Examples of the polyester (meth) acrylate oligomer include esterification of a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

In addition, (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and aminoplast resins with many reactive groups in small molecules. There are aminoplast resin (meth) acrylate oligomers modified with the above, oligomers having a cationic polymerizable functional group in the molecule such as novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, and aromatic vinyl ether, and acrylic polymers.
As the above-mentioned ionizing radiation curable resin, urethane (meth) acrylate is preferable and urethane acrylate oligomer is particularly preferable from the viewpoint of maintaining both the original feel of the base fabric and enjoying a high antifouling effect.

In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.
The above-mentioned monofunctional (meth) acrylate is also included in the ionizing radiation curable resin.

(Fluorine compounds)
The fluorine-based compound according to the present invention is not particularly limited as long as it is a fluorine-containing compound. However, at least one fluorine-based compound selected from a fluorine-containing polymer and a fluorine-containing nonionic surfactant is preferable. This is because both water repellency and oil repellency can be imparted.
On the other hand, if a silicone compound or water-repellent treated silica is used instead of the fluorine-based compound, both water repellency and oil repellency cannot be imparted and the problem of the present invention cannot be solved.

The fluorine-containing polymer according to the present invention is not particularly limited as long as it is a fluorine-containing polymer that can improve water repellency and oil repellency, but fluorine-containing (meth) acrylate polymer and fluorinated alkyl group-containing alkoxysilane are not particularly limited. It is preferably at least one polymer selected from polymers.
This fluorine-containing polymer is preferably contained in an amount of 0.5 to 5% by mass in the total amount of ionizing radiation curable resin composition (without solvent). If it is 0.5% by mass or more, the water repellency improvement effect of the fabric is further improved, and if it is 5% by mass or less, the improvement of the water repellency effect is not slowed down compared to the increase in the blending amount, and it is economical. This is advantageous.

  The fluorine-containing (meth) acrylate polymer is a copolymer obtained by emulsion polymerization of a (meth) acrylate having a fluoroalkyl group and another monomer copolymerizable therewith. preferable. Here, (meth) acrylate is as described above.

The (meth) acrylate having a fluoroalkyl group described above preferably has 3 to 21 carbon atoms in the fluoroalkyl group, and more preferably 6 to 18 carbon atoms in the fluoroalkyl group. Examples of the (meth) acrylate having such a fluoroalkyl group include compounds represented by the following general formula (1).
^{Rf 1 -XOCOCR 1 = CH 2 ···} (1)
[Wherein Rf ¹ is a fluoroalkyl group. R ¹ is a hydrogen atom or a methyl group. X is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, general formula (2): —SO ₂ NR ³ —R ⁴ — (2)
(Wherein R ³ is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to ⁴ carbon atoms, and R ⁴ is a straight chain having 1 to 10 carbon atoms, preferably 1 to ⁴ carbon atoms. A chain or branched alkylene group), and a general formula (3): —CH ₂ CH (OR ⁵ ) CH ₂ — (3)
(Wherein R ⁵ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms) is a divalent organic group selected from the group consisting of. ]

Examples of the fluoroalkyl group represented by Rf ¹ include CF ₃ (CF ₂ ) ₄ —, CF ₃ (CF ₂ ) ₅ —, CF ₃ (CF ₂ ) ₆ —, CF ₃ (CF ₂ ) ₇ —, _{CF 3 (CF 2) 8 -} , CF 3 (CF 2) 9 -, (CF 3) 2 CFCF 2 -, (CF 3) 2 CF (CF 2) 2 -, (CF 3) 2 CF (CF 2) ₃₋ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ −, (CF ₃ ) ₂ CF (CF ₂ ) ₆ −, (CF ₃ ) ₂ CF (CF ₂ ) ₈ −, (CF ₃ ) ₂ CF (CF _{2) 10 -, H (CF} 2) 10 - and _{CF 2 C1 (CF 2) 10} - and the like.
Among the divalent organic groups represented by X, the alkylene group and the alkylene group represented by R4 are specifically methylene, ethylene, trimethylene, propylene, ethylethylene, tetramethylene, hexa A methylene group, 2-methylpropylene group, etc. are mentioned.
Specific examples of the alkyl group represented by R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, and octyl. Group, nonyl group, decyl group and the like.
Specific examples of R ⁵ in the general formula (3) include a formyl group, an acetyl group, a propionyl group, a butyryl group, and a valeryl group.

Examples of the (meth) acrylate having a fluoroalkyl group represented by the general formula (1) include the following compounds.
CF ₃ (CF ₂ ) ₄ CH ₂ OCOC (CH ₃ ) = CH _{2
CF 3 (CF 2) 7 (} CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 (CF 2) 6 CH} 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₆ CH ₂ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) OCOC (CH ₃ ) = CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH═CH _{2
CF 3 (CF 2) 7 (} CH 2) 2 OCOC (CH 3) = CH 2
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CH ₂ ) ₈ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂
(CF ₃ ) ₂ CF (CH ₂ ) ₈ (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCH═CH ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₉ CONH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ CF (CF ₂ Cl) (CF ₂ ) ₇ CONH (CH ₂ ) ₂ OCOCH═CH ₂
(CF ₃ ) ₂ CF (CF) ₈ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂
(CF ₃ ) ₂ CF (CF) ₈ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOCH═CH ₂
H (CF ₂ ) ₁₀ CH ₂ OCOCH═CH ₂
CF ₂ Cl (CF ₂ ) ₁₀ CH ₂ OCOC (CH ₃ ) = CH ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (CH ₂ ) ₂ OCOCH═CH _{2
CF 3 CF (CF 2 Cl)} (CF 2) 7 CONH (CH 2) 2 OCOC (CH 3) = CH 2
_{CF 3 CF 2 CH 2 CH (} OH) CH 2 OCH 2 CH 2 OCOCH = CH 2

  Examples of other monomers copolymerizable with the (meth) acrylate having a fluoroalkyl group represented by the general formula (1) include lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) ) Acrylate, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, hydroxyalkyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, alkylene diol (meth) acrylate, etc. (meth) acrylic acid esters , (Meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, (meth) acrylamide such as methylolated diacetone (meth) acrylamide, alkyl maleate such as dibutyl maleate, lid Acid alkyl ester, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, styrene, α-methyl styrene, β-methyl styrene, alkyl vinyl ether, halogenated alkyl vinyl ether, alkyl vinyl ketone, cyclohexyl acrylate, cyclohexyl methacrylate, maleic anhydride , Butadiene, isoprene, chloroprene and the like.

  In the fluorine-containing (meth) acrylate polymer according to the present invention, the amount ratio of the (meth) acrylate having a fluoroalkyl group and the other monomer copolymerizable therewith is the total monomer used in the copolymerization. Among them, the total of (meth) acrylates having a fluoroalkyl group is preferably 40% by mass or more, and more preferably 50 to 80% by mass. The (meth) acrylate having a fluoroalkyl group and the other monomer copolymerizable with these usually give a fluorine-containing (meth) acrylate polymer as a copolymer by emulsion polymerization.

The copolymer suitable as the fluorine-containing (meth) acrylate polymer according to the present invention is emulsion polymerization according to a conventional method, that is, (meth) acrylate having the fluoroalkyl group, and other copolymerizable with these. The monomer is emulsified in an aqueous medium using a surfactant (preferably, the monomer mixture is emulsified and dispersed by transmitting ultrasonic waves while stirring), and a polymerization initiator is added and stirred. It can obtain by the method of superposing | polymerizing. As the surfactant, those known as anionic, cationic or nonionic surfactants can be used without particular limitation, and in particular, cationic surfactants and nonionic surfactants can be used. Is preferred. As the polymerization initiator, a known polymerization initiator can be used, for example, a peroxide such as diisopropyl peroxydicarbonate; an azo compound such as azobisisobutylamidine dihydrochloride; and (NH 4) 2 S 2 O 8, Examples thereof include persulfuric acid compounds such as K2S2O8. The reaction temperature during the polymerization is usually 10 to 150 ° C, preferably 40 to 100 ° C. What is necessary is just to determine reaction time suitably according to a manufacturing scale, surfactant, and the kind of polymerization initiator.
The medium for emulsion polymerization is not particularly limited, but an aqueous solvent obtained by adding a water-soluble organic solvent to water is preferably used. When an aqueous solvent obtained by adding a water-soluble organic solvent to water is used, monomers and copolymers are hardly aggregated, and a stable emulsion can be obtained.

［式中、Ｒｆ²は、 The fluorinated alkyl group-containing alkoxysilane polymer suitable as the fluorine-containing polymer according to the present invention includes, for example, a fluorinated alkyl group-containing alkoxysilane compound represented by the following general formula (4) in excess water or a fluorine-containing polymer. It can be obtained by hydrolysis / condensation reaction in a system solvent.

[Wherein Rf ² is

（ｐは１〜２０の整数、ｍは１以上、好ましくは１〜２０、特に好ましくは１〜１０の整数）で表されるエーテル結合を１個以上含んでいても良いポリフルオロアルキル基を示し、Ｘ¹は−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＮＲ⁸−、−ＣＯＯ−、−ＣＯＮＲ⁸−、−Ｓ−、−ＳＯ₃−又はＳＯ₂ＮＲ⁸−（Ｒ⁸ は水素原子又は炭素数１〜８のアルキル基）の１種又は２種以上の結合基を示し、Ｒ⁶ は炭素数１〜４のアルキル基、Ｒ⁷ は炭素数１〜４のアルキル基を示す。ａは０〜３の整数、ｂは１〜３の整数、ｃは０又は１である。］

(P is an integer of 1 to 20, m is 1 or more, preferably 1 to 20, particularly preferably an integer of 1 to 10) and represents a polyfluoroalkyl group which may contain one or more ether bonds. , X ¹ is _{-CH 2 -, - CH 2 O} -, - NR 8 -, - COO -, - CONR 8 -, - S -, - SO 3 - or SO ₂ NR ⁸ - (R ⁸ is a hydrogen atom or represents one or more linking groups alkyl group) having 1 to 8 carbon atoms, R ⁶ is an alkyl group having 1 to 4 carbon atoms, R ⁷ represents an alkyl group having 1 to 4 carbon atoms. a is an integer of 0 to 3, b is an integer of 1 to 3, and c is 0 or 1. ]

In Rf ² in the general formula (4), as the _{C p F 2p + 1, CF} 3 -, C 2 F 5 -, C 3 F 7 -, C 4 F 9 -, C 6 F 13 -, C 8 _{F 17 -, C 10 F 21} -, C 12 F 25 -, C 14 F 29 -, C 16 F 33 -, C 18 F 37 -, C 20 F 41 - , and the like.

Examples of the fluorinated alkyl group-containing alkoxysilane compound represented by the general formula (4) include the following.
Rf ² (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
Rf ² (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
_{^{Rf 2 (CH 2) 2 Si}} (CH 3) 2 (OCH 3),
_{^{Rf 2 (CH 2) 2 Si}} (OCH 2 CH 3) 3,
_{^{Rf 2 (CH 2) 2 SiCH}} 3 (OCH 2 CH 3) 2,
_{^{Rf 2 (CH 2) 2 Si}} (CH 3) 2 (OCH 2 CH 3),
Rf ² (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
Rf ² (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ,
Rf ² (CH ₂ ) ₃ Si (CH ₃ ) ₂ (OCH ₃ ),
_{^{Rf 2 (CH 2) 3 Si}} (OCH 2 CH 3) 3,
_{^{Rf 2 (CH 2) 3 SiCH}} 3 (OCH 2 CH 3) 2,
_{^{Rf 2 (CH 2) 3 Si}} (CH 3) 2 (OCH 2 CH 3),
Rf ² NH (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
Rf ² NH (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
_{^{Rf 2 NH (CH 2) 2}} Si (CH 3) 2 (OCH 3),
_{^{Rf 2 NH (CH 2) 2}} Si (OCH 2 CH 3) 3,
Rf ² NH (CH ₂ ) ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
_{^{Rf 2 NH (CH 2) 2}} Si (CH 3) 2 (OCH 2 CH 3),
_{^{Rf 2 NH (CH 2) 2}} NH (CH 2) 2 Si (OCH 3) 3,
_{^{Rf 2 NH (CH 2) 2}} NH (CH 2) 2 SiCH 3 (OCH 3) 2,
_{^{Rf 2 NH (CH 2) 2}} NH (CH 2) 2 Si (CH 3) 2 (OCH 3),
_{^{Rf 2 NH (CH 2) 2}} NH (CH 2) 2 Si (OCH 2 CH 3) 3,
_{^{Rf 2 NH (CH 2) 2}} NH (CH 2) 2 SiCH 3 (OCH 2 CH 3) 2,
Rf ² NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₂ CH ₃ ),
Rf ² CONH (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
Rf ² CONH (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
Rf ² CONH (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₃ ),
Rf ² CONH (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ,
Rf ² CONH (CH ₂ ) ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
Rf ² CONH (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₂ CH ₃ ),
Rf ² SO ₂ NH (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
Rf ² SO ₂ NH (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
Rf ² SO ₂ NH (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₃ ),
Rf ² SO ₂ NH (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ,
Rf ² SO ₂ NH (CH ₂ ) ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
Rf ² SO ₂ NH (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₂ CH ₃ )

Preferable examples include the following.
CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
CF ₃ (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₃ ),
CF ₃ (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ,
CF ₃ (CH ₂ ) ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₂ CH ₃ ),
C ₈ F ₁₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,
C ₈ F ₁₇ (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
C ₈ F ₁₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₃ ),
C ₈ F ₁₇ (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ,
C ₈ F ₁₇ (CH ₂ ) ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂ ,
C ₈ F ₁₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₂ CH ₃ ),
C ₃ F ₇ (CF (CF ₃ ) CF ₂ O) ₃ CF (CF ₃ ) CH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
These alkoxysilane compounds can be used individually by 1 type or in mixture of 2 or more types.

The above fluorinated alkyl group-containing alkoxysilane polymer is obtained by mixing a mixture of a fluorinated alkyl group-containing alkoxysilane compound represented by the general formula (4) and a silane compound represented by the following general formula (5) with an excess of water. Alternatively, it may be obtained by hydrolysis / condensation reaction in a fluorine-containing solvent.
R ⁹ _d Si (OR ¹⁰ ) _4-d (5)
(In the formula, R ⁹ is an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkenyl group, or an epoxy group, a (meth) acryloyloxy group, a mercapto group, an amino group or a cyano group-substituted alkyl group, an aryl group or an alkenyl group. R ¹⁰ represents an alkyl group having 1 to ¹⁰ carbon atoms, an alkenyl group, an aryl group, an alkoxyalkyl group, or an acyl group, and d is an integer of 0 to 3, preferably an integer of 0 to 2.

Here, R ⁹ is specifically an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a decyl group or a cyclohexyl group, an aryl group such as a phenyl group or a phenethyl group, Vinyl group, allyl group, 9-decenyl group, alkenyl group such as p-vinylbenzyl group, 3-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, 9,10-epoxydecyl group, etc. Epoxy group-containing organic group, (meth) acryloyloxy group-containing organic group such as γ-methacryloyloxypropyl group, γ-acryloyloxypropyl group, mercapto group such as γ-mercaptopropyl group, p-mercaptomethylphenylethyl group An amino group-containing organic group such as an organic group, γ-aminopropyl group, (β-aminoethyl) -γ-aminopropyl group, Examples thereof include cyano group-containing organic groups such as β-cyanoethyl group.
Specific examples of R ¹⁰ include methyl, ethyl, propyl, isopropyl, butyl, hexyl, phenyl, isopropenyl, methoxyethyl, and acetyl groups.

  Specific examples of the silane compound represented by the general formula (5) include methyltrimethoxysilane, methyltriethoxysilane, methyltris (2-methoxyethoxy) silane, methyltriacetoxysilane, methyltripropoxysilane, and methyltriisopropeno. Xysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropenoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycid Cypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloylio Trialkoxy or triacyloxysilanes such as cypropyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi (2-methoxyethoxy) silane , Dimethyldiacetoxysilane, dimethyldipropoxysilane, dimethyldiisopropenoxysilane, dimethyldibutoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldi (2-methoxyethoxy) silane, vinyl Methyldiisopropenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldiacetoxysilane, stiri Trimethoxysilane, styrylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, N- (β-aminoethyl) ) -Γ-aminopropylmethyldimethoxysilane, dialkoxysilane or diacyloxysilane such as β-cyanoethylmethyldimethoxysilane; methyl silicate, ethyl silicate, n- B pills silicate, n- butyl silicate, can be given tetraalkoxysilanes such as sec- butyl silicate and t- butyl silicate.

When the fluorinated alkyl group-containing alkoxysilane polymer is blended in the ionizing radiation curable resin composition, it is preferably a fluorinated alkyl group-containing alkoxysilane- (meth) acryloyl group-containing silane copolymer. That is, as the silane compound represented by the general formula (5), a (meth) acryloyl group-containing silane compound is preferable, and γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloyloxypropyltrimethoxy is preferable. Silane, γ-acryloyloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, etc. Can be mentioned. In addition, you may use what hydrolyzed these silane compounds partially.
Furthermore, these silane compounds or partial hydrolysates can be used alone or as a mixture of two or more.

  The fluorinated alkyl group-containing alkoxysilane polymer suitable as the fluorine-containing polymer according to the present invention is a fluorinated alkyl group-containing alkoxysilane compound represented by the general formula (4) [hereinafter abbreviated as component (M). There is. ] And a silane compound represented by the above general formula (5) [hereinafter sometimes abbreviated as component (N). ], It is preferable that the compounding ratio in the case of obtaining with a mixture with a component (N) is 0-1,000 mass parts with respect to 100 mass parts of components (M). More preferably, a component (N) is 0-300 mass parts. In addition, when mix | blending a component (N), in order to exhibit the effect effectively, it is preferable to mix | blend 5 mass parts or more.

  Conditions for hydrolysis / condensation reaction of the above fluorinated alkyl group-containing alkoxysilane compound alone or a mixture of the fluorinated alkyl group-containing alkoxysilane compound and the silane compound in excess water or a fluorine-containing solvent ( Details of the solvent, catalyst, temperature, time, and the like are described in, for example, JP-A-2002-53805 and JP-A-2007-9216.

Examples of the fluorine-containing nonionic surfactant according to the present invention include nonionic surfactants containing a perfluoroalkyl group or a perfluoroalkenyl group.
Examples of the nonionic surfactant containing a perfluoroalkyl group include AGC Seimi Chemical Co., Ltd., trade names “Surflon S-611”, “Surflon S-651”, “Surflon S-420” and the like. Examples of nonionic surfactants containing a fluoroalkenyl group include those manufactured by Neos Co., Ltd., trade names “Factent 222F”, “Factent 208G”, and the like.
The fluorine-containing nonionic surfactant is preferably contained in an amount of 0.5 to 5% by mass in the total amount of ionizing radiation curable resin composition (not including a solvent), like the fluorine-containing polymer. If it is 0.5% by mass or more, the water repellency improvement effect of the fabric is further improved, and if it is 5% by mass or less, the improvement of the water repellency effect is not slowed down compared to the increase in the blending amount, and it is economical. This is advantageous.

Among the fluorine compounds according to the present invention described above, examples of the reactive fluorine compound include a fluorine-containing (meth) acrylate polymer and a fluoroalkyl group-containing alkoxysilane- (meth) acryloyl group-containing silane copolymer. Examples of non-reactive fluorine compounds include fluorine-containing nonionic surfactants, fluorinated alkyl group-containing alkoxysilane homopolymers, and fluorinated alkyl group-containing alkoxysilanes-other silane compound copolymers.
In order to improve the temporal stability of the water and oil repellency of the fabric of the present invention, a fluorine-containing (meth) acrylate polymer which is a reactive fluorine compound and a fluoroalkyl group-containing alkoxysilane- (meth) acryloyl group-containing silane More preferred is a fluorine-based compound that is at least one selected from copolymers.

(solvent)
As the solvent according to the present invention, ester organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, Examples include alcohol organic solvents such as ethylene glycol and propylene glycol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; water; Ethyl acetate and methyl ethyl ketone are preferable in terms of excellent coating suitability and quick drying. Moreover, water is preferable in terms of being excellent in terms of environment and hygiene.

When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
When the ionizing radiation curable resin is UV-cured, the photopolymerization initiator is added in an amount of about 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of the ionizing radiation curable resin. It is desirable. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, etc. It is done.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

Moreover, various additives can be mix | blended with the ionizing-radiation-curable resin composition used for the coating liquid in this invention as needed. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a coloring agent, etc. are mentioned.
Examples of the ultraviolet absorber include triazine-based UVA, benzotriazole-based UVA, and benzophenone-based UVA. Moreover, as a light stabilizer, a hindered amine light stabilizer (HALS) is mentioned, for example.

  By the production method of the present invention described above, the fabric surface has a cured film of an ionizing radiation curable resin composition containing at least an ionizing radiation curable resin and a fluorine-based compound, and the fabric has a surface roughness Zb. Is a water- and oil-repellent fabric characterized by having a thickness of 120 to 600 μm.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation method)
The water / oil repellent fabrics obtained in the respective examples and comparative examples were evaluated by the following methods.
(1) Tactile sensation Tactile sensation when touched with a hand was evaluated according to the following criteria.
4: Both touch and bending hardness are equivalent to the base fabric before coating.
3: The touch is equivalent to the base fabric before coating, but the bending hardness is firm compared to the base fabric before coating.
2: A rough feel remains in the touch.
1: The touch of the base fabric is not left and is hard.

(2) Surface roughness The depth direction distance from the outermost surface of the fabric was measured using a measuring microscope STM6 manufactured by Olympus Corporation as a non-contact surface shape / roughness measuring device. The average distance is calculated by arithmetic mean from the value measured n = 2601 every 10 μm in the range of 500 μm × 500 μm, and the average distance of the base fabric before coating or dipping is defined as the surface roughness Za (μm). The average distance of the oily fabric was defined as the surface roughness Zb (μm). These ratios Zb / Za were calculated, and those having a value of 1.5 or more were evaluated as “good” and those having a value less than 1.5 were evaluated as “bad”.

(3) Water repellency and oil repellency (3-1) Appearance Tilt the fabric at an angle of 30 degrees from the horizontal, and test solution (pure water for water repellency evaluation, oleic acid for water repellency evaluation) The behavior of the test solution when 50 mL was dropped was evaluated according to the following criteria.
4: The test solution slides on the fabric surface and does not adhere to the fabric surface.
3: Although the test liquid flows down on the fabric surface, a small amount of droplets of the test liquid remains on the fabric surface.
2: The test solution is repelled without soaking into the fabric.
1: The test solution soaks into the fabric.
(3-2) Contact angle 25 mL of a test solution (pure water is used for water repellency evaluation and oleic acid is used for oil repellency evaluation) is directly dropped on the fabric surface, and the contact angle with the fabric surface is measured. . An arithmetic average value of N = 5 was calculated.

Synthesis Example 1 (Synthesis of fluorinated alkyl group-containing alkoxysilane-acryloyl group-containing silane copolymer)
In a 0.5 liter flask equipped with a stirrer, condenser and thermometer,
C ₈ F ₁₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
Heptadecafluorooctylethyltrimethoxysilane 50 g (0.088 mol), γ-acryloxypropyltrimethoxysilane 41.2 g (0.176 mol), m-xylene hexafluoride (MXHF) 30 g and perfluoro- 70 g of 2-butyltetrahydrofuran (PBTF) was added and stirred, and the mixture was added dropwise over 5 minutes using a dropping funnel charged with 7.1 g of a 0.25 N aqueous acetic acid solution. The reaction was allowed to proceed at room temperature for 3 hours, followed by reaction at 80 ° C. for 2 hours. After the reaction, the reaction solution was separated into two layers. This was separated, and the upper layer was dried with bow glass. This was filtered, and MXHF and PBTF were volatilized under reduced pressure to obtain 67 g of a transparent liquid resin. This had a molecular weight of about 2,200 by GPC. The refractive index was 1.3733.

Production Example 1
Silica obtained by classifying Ube Nitto Kasei Co., Ltd. product name “HI-PRECICA TS” to an average particle size of 3 μm is dried at 150 ° C. for 3 hours, so that the amount of adsorbed moisture is 0.23 mass%. Adjusted. 200 g of this fine silica powder after adjustment was charged into a vibrating fluidized bed (vibrating fluidized phase device manufactured by Chuo Kako Co., Ltd.) and n-octyltriethoxy while being vibrated and flowed with air dehumidified to a moisture content of 0.38% by mass. After spraying 12 g of silane, another 15 g of dimethyl silicone oil was sprayed and fluidly mixed for 30 minutes. Thereafter, it was immediately put into a constant temperature and humidity chamber maintained at a temperature of 25 ° C. and a humidity of 90%, and maintained for 72 hours to produce hydrophobized silica.

Examples 1 , 2, 4 to 6 , Reference Example 3 and Comparative Examples 1 to 7
The base fabric described in Table 1 was dipped in the coating coating solution described in Table 1 (dip coating), and then left in a 60 ° C. oven for 2 minutes to dry. Next, an electron beam was irradiated under conditions of 165 kV and 50 kGy to fix the coating film on the fiber surface of the base fabric. In Comparative Examples 1 to 3, no coating treatment was performed. The tactile sensation, surface roughness, water repellency and oil repellency of the 13 kinds of fabrics thus obtained were evaluated by the above methods. The results are shown in Table 1.

(note)
* 1: Polyethylene-based spunbonded nonwoven fabric (Shinwa Co., Ltd., trade name “Hybon”) * 2: Cotton spunlace nonwoven fabric (Marusan Sangyo Co., Ltd., trade name “Serena”)
* 3: Spunlaced non-woven fabric made of rayon (Kuraray Co., Ltd., trade name “Kuraflex”)
* 4: Trifunctional urethane acrylate oligomer (manufactured by DIC Graphics, solid resin content 70% by mass)
* 5: Fluorinated alkyl group-containing alkoxysilane-acryloyl group-containing silane copolymer obtained in Synthesis Example 1 * 6: Nonionic surfactant containing a perfluoroalkyl group (trade name, manufactured by AGC Seimi Chemical Co., Ltd.) "Surflon S-611")
* 7: Water repellent treated silica obtained in Production Example 1 * 8: Silicone compound (trade name “Iupimer UV H5000” manufactured by Mitsubishi Chemical Corporation)
* 9: Ethyl acetate

  As is apparent from Table 1, the fabrics of Examples 1 to 6 had better tactile sensation and were superior in both water repellency and oil repellency compared to the fabrics of Comparative Examples 1 to 7.

  The fabric obtained by the production method of the present invention is used in clothing, diapers, sanitary products, industrial materials, and other wide-ranging fabric products, and is particularly suitable for various members that require improved stain resistance performance. .

Claims (4)

Surface roughness of the water / oil repellent fabric in a water / oil repellent fabric having a cured film of an ionizing radiation curable resin composition containing at least an ionizing radiation curable resin and a fluorine-based compound formed on the surface of a fiber constituting the base fabric. Zb (μm) is 1.5 times or more the surface roughness Za (μm) of the base fabric before forming a cured film, and the surface roughness Zb of the water / oil repellent fabric is 120 to 600 μm, The total mass of the cured film is 0.2-5 g / m ² A water- and oil-repellent fabric characterized in that
[Measurement method of surface roughness
Using a non-contact surface shape / roughness measuring device, the distance in the depth direction from the outermost surface of the base fabric or the water / oil repellent fabric is measured. The average distance is calculated from the value measured n = 2601 every 10 μm in the range of 500 μm × 500 μm, and the surface roughness Za or Zb is obtained. ] The water / oil repellent fabric according to claim 1, wherein the base fabric is a fabric selected from a polyethylene-based nonwoven fabric, a cotton nonwoven fabric, and a rayon nonwoven fabric. The water / oil repellent fabric according to claim 1, wherein the fluorine compound is a reactive fluorine compound. Applying a coating coating liquid containing at least an ionizing radiation curable resin composition and a solvent containing an ionizing radiation curable resin and a fluorine-based compound to the base fabric, or immersing the base fabric in the coating coating solution, Forming a coating film on the surface of the fiber to be formed;
Irradiating the coating film with ionizing radiation to form a cured film on the fiber surface, and a method for producing a water- and oil-repellent fabric,
The surface roughness Zb (μm) of the water- and oil-repellent fabric formed with a cured film is 1.5 times or more the surface roughness Za (μm) of the base fabric before forming the cured film, and the water-repellent property The surface roughness Zb of the oil-repellent fabric is 120 to 600 μm, and the total mass of the cured film is 0.2 to 5 g / m. ² A method for producing a water- and oil-repellent fabric, characterized in that
[Measurement method of surface roughness
Using a non-contact surface shape / roughness measuring device, the distance in the depth direction from the outermost surface of the base fabric or the water / oil repellent fabric is measured. The average distance is calculated from the value measured n = 2601 every 10 μm in the range of 500 μm × 500 μm, and the surface roughness Za or Zb is obtained. ]