JP2012046840A - Water-repellent fiber sheet and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method for manufacturing, without involving a high temperature condition and the like, a fiber sheet that excels in water repellency and its durability/persistency, as well as a water-repellent fiber sheet formed by the manufacturing method.SOLUTION: The method comprises the steps of: producing a composition (X) for water-repellent treatment in which a polymerizable compound (A) that can be polymerized by irradiation of an energy ray is mixed with a compound (B) that is compatible with the polymerizable compound (A) but incompatible with a polymer (P) polymerized from the polymerizable compound (A), and that is also inert to the energy ray; adhering the composition (X) for water-repellent treatment to a fiber sheet; and removing the compound (B) after polymerizing the polymerizable compound (A) in the composition (X) for water-repellent treatment by irradiation of the energy ray. The compound (B) is in a liquid or solid state. Moreover, the compound (B) is a compound having a molecular weight of 500 or less and a saturated vapor pressure at 25°C of 400 Pa or less.

Description

  The present invention relates to a water-repellent processed fiber sheet and a method for producing the same, and more particularly to a water-repellent processed fiber sheet having a water-repellent structure made of a polymer having a fine concavo-convex structure on the fiber surface and a method for producing the same.

  The fiber sheet is a general term for sheet-like molded products having fibers as constituent components, such as woven fabrics, knitted fabrics, nonwoven fabrics, and composites thereof. At present, the production of a fiber sheet exhibiting water repellency is mainly performed using a water-repellent processed fiber material. In the case of a woven fabric or a knitted fabric, it can be obtained by processing the water-repellent fiber with a loom or knitting machine. Moreover, in the case of a nonwoven fabric, it can be made into a water-repellent fiber sheet by a dry method, a spunbond method, a melt blow method, a flash spinning method, a wet method, or the like.

  As a technology for water-repellent processing of fiber materials, for example, after applying water-repellent resin, emulsion, dispersion, etc. dissolved or dispersed in solvent or water to the fiber material, the solvent or water is vaporized and water-repellent continuous A method for forming a film is known. However, the fibers obtained by these processing treatments and the fiber sheets prepared using them are not always highly durable, and the resin treated with use tends to fall off the surface and lose water repellency. Has the disadvantages.

On the other hand, Patent Documents 1 to 3 propose water-repellent fibers obtained by melt-kneading a fluororesin. In this case, the water repellency itself is highly durable, but in general, fluororesins have a melting point and a decomposition point close to each other. It is difficult to obtain the fiber.
Patent Documents 4 and 5 disclose a technique for adding water-repellent fine particles such as fluorine-based resin fine particles and silicone-based resin fine particles to a spinning dope and kneading the fine particles into the fibers to make water-repellent fibers. Proposed. However, such a method has a problem that only a part of the water repellent particles appears on the fiber surface, and the water repellent particles are scattered on the fiber surface, so that sufficient water repellency cannot be obtained. On the other hand, if a large amount of water-repellent particles is used, a large amount of water-repellent particles are mixed inside the fiber, and the properties of the fiber itself are changed. For example, there are problems that the fiber becomes hard or brittle or that spinning cannot be performed. .

  In order to avoid such a problem, in the method described in Patent Document 6, water-repellent particles heated to a temperature higher than the melting point of the resin are brought into contact with the fiber made of the thermoplastic resin, thereby stably stabilizing the fiber. Water-repellent particles are fixed on the surface, and the fiber is used to successfully produce a fiber sheet excellent in water repellency and durability. In the same patent document, a method for producing a water-repellent fiber sheet by contacting and fixing water-repellent particles heated above the melting point of the resin to a fiber sheet having fibers made of a thermoplastic resin is also proposed. ing. However, these methods are methods that can be performed only on fibers made of a thermoplastic resin, and have the disadvantage of being accompanied by treatment under high temperature conditions.

JP-A-62-238822 JP 09-302523 A JP 09-302524 A JP 2001-146627 A Japanese Patent Laid-Open No. 02-26919 JP 2003-268675 A

  The problem to be solved by the present invention is a simple production method that does not involve high temperature conditions, etc., and is a method for producing a fiber sheet that is excellent in water repellency and has excellent durability and durability, in particular, the water contact angle of the surface. It is in providing the manufacturing method of the fiber sheet which shows super water repellency or high water repellency of 140 degrees or more, and the water-repellent fiber sheet formed by this manufacturing method.

  In addition, another problem to be solved by the present invention is a water-repellent processed fiber sheet by a simple and normal temperature process utilizing a phase separation phenomenon of a polymer caused by a polymerization reaction caused by energy ray irradiation, particularly a water contact angle of 140 °. It is providing the manufacturing method of the fiber sheet which shows the above super water repellency or high water repellency, and the water-repellent processed fiber sheet formed by this manufacturing method.

  As a result of various studies, the present inventors have found on a fiber sheet a composition for water repellent finishing, which is a mixture of a polymerizable compound that can be polymerized by irradiation with energy rays and a soluble additive that is inert to energy rays. It is found that the above problem can be solved by attaching and polymerizing by irradiation with energy rays to induce a phase separation state, and then removing a part of the soluble additive and stably generating a polymer cured product on the fiber. The present invention has been completed.

That is, the present invention comprises a polymerizable compound (A) that can be polymerized by irradiation with energy rays,
A compound (B) that is compatible with the polymerizable compound (A) but is not compatible with the polymer polymer (P _A ) of the polymerizable compound ( _A ) and is inactive with respect to energy rays. A step of producing a water repellent composition (X) mixed with
Attaching the water repellent composition (X) to a fiber sheet;
After polymerizing the polymerizable compound (A) in the water repellent composition (X) by irradiation with energy rays, the method includes a step of removing the compound (B),
Provided is a method for producing a water-repellent fiber sheet, wherein the compound (B) is a liquid or solid, has a molecular weight of 500 or less, and a saturated vapor pressure at 25 ° C. of 400 Pa or less. To do.

  The present invention also provides a water-repellent fiber sheet obtained by the above method.

  Furthermore, the present invention provides a water-repellent processed fiber sheet characterized in that it has a water-repellent structure formed on the fiber surface by a polymer of a polymerizable compound (A) that can be polymerized by irradiation with energy rays. It is.

  According to the production method of the present invention, the water-repellent composition is directly attached to the fiber sheet, and the surface uneven water-repellent cured product made of a polymer is formed by irradiation with energy rays. By a normal temperature process, a highly durable water repellent fiber sheet, particularly a water repellent fiber sheet having a water contact angle of 140 ° or more can be produced.

2 is a scanning electron micrograph of the fiber surface of the water-repellent fiber sheet [H-1] obtained in Example 1. FIG. It is a waterdrop photograph on the surface of the water-repellent fiber sheet [H-7] obtained in Example 7. It is a scanning electron micrograph of the fiber surface of the water repellent fiber sheet [H-7] obtained in Example 7. It is a water droplet photograph on the surface of the water-repellent fiber sheet [H-10] obtained in Example 10. 4 is a scanning electron micrograph of the fiber surface of a water-repellent fiber sheet [H-10] obtained in Example 10. FIG.

  The present invention will be described below.

  In the technical field of water repellent materials, there is no scientific distinction and definition in terms of science, but in general, a surface having a water contact angle of approximately 150 ° or more is referred to as a super water repellent surface, and approximately 120 A surface showing a water contact angle in the range of ˜150 ° is called a highly water-repellent surface, and a surface showing a water contact angle in the range of about 90-120 ° is distinguished from a normal water-repellent surface.

  In the present specification, the above general distinction is adopted, and a surface having a water contact angle of 150 ° or more is defined as a “super-water-repellent” surface, and indicates a water contact angle in a range of 120 ° to less than 150 °. A surface is defined as a “high water repellency” surface, and a surface exhibiting a water contact angle in the range of 90 ° to less than 120 ° is defined as a “normal water repellency” surface. However, the simple description of “water-repellent surface” includes all of “super-water-repellent surface”, “highly water-repellent surface” and “normal water-repellent surface”.

  In the production method of the present invention, the production of fiber sheets having “super water repellency”, “high water repellency” and “normal water repellency” surfaces can be selected by selecting raw materials, adjusting the blending amount, adjusting the film forming conditions, etc. Although it is controllable, it is particularly suitable for the production of fiber sheets having “super water repellency” and “high water repellency” surfaces, and “super water repellency” and “high water repellency” with a water contact angle of 140 ° or more. It is most suitable for the production of fiber sheets having an “aqueous” surface. Therefore, in the following, description will be made mainly on a method for producing a fiber sheet having a super water-repellent surface.

<Basic invention>
The water-repellent processed fiber sheet of the present invention is compatible with the polymerizable compound (A) polymerizable by irradiation with energy rays and the polymerizable compound (A), but the polymer of the polymerizable compound (A). The water repellent composition (X), which is incompatible with the polymer (P _A ) and mixed with the compound (B) that is inactive with respect to the energy rays, is deposited on the fiber sheet and irradiated with energy rays. It can be produced by removing the compound (B) after polymerization.

In this method, the polymer polymer (P _A ) produced by polymerization of the polymerizable compound (A) becomes incompatible with the compound (B), and the phase separation between the polymer polymer (P _A ) and the compound (B) occurs. state occurs, the polymer polymer (P _a) or inside the polymer a polymer (P _a) compounds during (B) is in a state incorporated. By removing this compound (B), the region occupied by the compound (B) becomes pores, and a fine concavo-convex structure is induced on the surface of the polymer cured product to exhibit super water repellency.

  As the polymerizable compound (A), a polymerizable compound (a) that can be polymerized by irradiation with energy rays can be used as a single component or a mixture of two or more thereof. The polymerizable compound (a) is not particularly limited as long as it is a substance that is polymerized by irradiation with energy rays and becomes a polymer, and may be any one such as radical polymerizable, anionic polymerizable, and cationic polymerizable. For example, a polymerizable compound containing a vinyl group is used, and among them, a (meth) acrylic compound having a high polymerization rate by irradiation with energy rays is preferable. Further, since the strength after curing can be increased, the compound is preferably a compound that forms a crosslinked polymer by polymerization, and is particularly preferably a bifunctional or more polymerizable compound having two or more vinyl groups in one molecule. preferable.

  Examples of the (meth) acrylic compound include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di. (Meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, 2- Isocyanato-2-methylpropyl di (meth) acrylate, 2-methacryloyloxyethyl acid phosphate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanedioe Di (meth) acrylate, 2,2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, hydroxydipivalic acid Bifunctional monomers such as neopentyl glycol di (meth) acrylate, dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, trimethylolethane Trifunctional compounds such as tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate Mer; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate.

  Examples of the polymerizable oligomer having a (meth) acryloyl group in the molecular chain include those having a weight average molecular weight of 500 to 50,000. For example, (meth) acrylic acid ester of epoxy resin, ( (Meth) acrylic acid ester, (meth) acrylic acid ester of polyether resin having bisphenol A skeleton, (meth) acrylic acid ester of polybutadiene resin, (meth) acrylic acid ester of polydimethylsiloxane resin, (meth) at the molecular end Examples thereof include a polyurethane resin having an acryloyl group.

  Among the above-mentioned polymerizable compounds and polymerizable oligomers, ethylene glycol di (meth) acrylate is highly hydrophobic and has a high crosslinking density after polymerization and is easy to give a polymer film having a developed surface microstructure. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate is preferably used.

  Moreover, as the polymerizable compound (a), a monofunctional polymerizable compound having one vinyl group, particularly a (meth) acrylic compound having one vinyl group can be used. However, the monofunctional polymerizable compound is preferably used together with a bifunctional or higher polymerizable compound.

  Examples of (meth) acrylic compounds having one vinyl group include methyl (meth) acrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, Phenoxypolyethylene glycol (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol acrylate methacrylate, butanediol mono (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl acrylate, Tylene oxide modified phthalic acid acrylate, ω-carboxycaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloyloxypropyl hexahydrohydrogen phthalate, fluorine-substituted alkyl ( (Meth) acrylate, chlorine-substituted alkyl (meth) acrylate, sulfonic acid sodaethoxy (meth) acrylate, sulfonic acid-2-methylpropane-2-acrylamide, phosphoric ester group-containing (meth) acrylate, glycidyl (meth) acrylate, 2- Isocyanatoethyl (meth) acrylate, (meth) acryloyl chloride, (meth) acrylaldehyde, sulfonate group-containing (meth) acrylate , Silano group-containing (meth) acrylate, ((di) alkyl) amino group-containing (meth) acrylate, quaternary ((di) alkyl) ammonium group-containing (meth) acrylate, (N-alkyl) acrylamide, (N, N -Dialkyl) acrylamide, acryloylmorpholine, polydimethylsiloxane chain-containing (meth) acrylate and the like.

  Among these monofunctional polymerizable compounds, methyl (meth) acrylate, alkyl (meth) acrylate, and isobornyl (meth) acrylate are also used on the film surface after polymerization for the purpose of increasing hydrophobicity and adjusting viscosity. Fluorine-substituted alkyl (meth) acrylate, polydimethylsiloxane chain-containing (meth) acrylate, and the like are preferably used for the purpose of uneven distribution and lowering the free energy of the surface.

As the compound (B), the compound (b) shown below can be used as a single component or a mixture of two or more thereof. In the polymerization process of the polymerizable compound (A), the compound (b) stays on the substrate, and is removed mainly by solvent washing after the polymerization of the polymerizable compound (A). Compound (b) is compatible with the polymerizable compound (A) as a component of the compound (B), but is not compatible with the polymer polymer (P _A ) of the polymerizable compound (A), and There is no particular limitation as long as it is a liquid or solid compound that is inert to energy rays, has a molecular weight of 500 or less, and a saturated vapor pressure at 25 ° C. of 400 Pa or less. However, the molecular weight is more preferably 300 or less. Further, the compound (b) is a highly hydrophobic compound, which is present in the vicinity of the surface when forming a phase separation state with the polymer polymer (P _A ), and after removal, a fine uneven structure is formed on the surface of the polymer cured product. Is preferred, and it is easy to show super water repellency. Therefore, the compound (b) is preferably a compound that does not contain a polar chemical unit such as a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a mercapto group, a cyano group, an amide bond, and a urea bond.

  As a highly hydrophobic compound that satisfies such requirements, the compound (b) is a compound represented by the formula (1), the formula (2), the formula (3), and the formula (4), and An alkane having 10 to 20 carbon atoms which may be branched is exemplified.

（式（１）中、Ｒ_１は炭素数が９〜１９の分岐していてもよいアルキル基又はベンジル基、Ｒ_２はメチル基又はエチル基を表す。）

(In formula (1), R ₁ represents an alkyl group or benzyl group having 9 to 19 carbon atoms, and R ₂ represents a methyl group or an ethyl group.)

（式（２）中、Ｒ_３はメチル基又はエチル基、Ｒ_４は炭素数１０〜２０の分岐していてもよいアルキル基又はベンジル基を表す。）

(In Formula (2), R ₃ represents a methyl group or an ethyl group, and R ₄ represents an alkyl group or a benzyl group having 10 to 20 carbon atoms which may be branched.)

（式（３）中、Ｒ_５〜Ｒ_１０は、それぞれ独立して水素原子又は分岐していてもよいアルキル基を表すが、そのうちの少なくとも２つがエチル基であるか、少なくとも１つが炭素数３〜８の分岐していてもよいアルキル基である。）

(In formula (3), R _{5 to} R ₁₀ each independently represents a hydrogen atom or an optionally branched alkyl group, and at least two of them are ethyl groups, or at least one of them has 3 carbon atoms. -8 alkyl groups which may be branched.)

（式（４）中、Ｒ_１１及びＲ_１２は、それぞれ独立して炭素数２〜８の分岐していてもよいアルキル基を表す。）

(In Formula (4), R ₁₁ and R ₁₂ each independently represents an alkyl group having 2 to 8 carbon atoms which may be branched.)

In Formula (1) and Formula (2), R ₁ and R ₄ are preferably an alkyl group having 7 to 18 carbon atoms, and more preferably an alkyl group having 8 to 16 carbon atoms. In Formula (3), at least one of R _{5 to} R ₁₀ is preferably an alkyl group having 3 to 7 carbon atoms, and more preferably an alkyl group having 3 to 6 carbon atoms. In this case, the remaining other groups are preferably hydrogen atoms. _Further, it is preferable that the total number of carbon atoms in R 5 _{to R 10} is 10 or less. Furthermore, in formula (4), R ₁₁ and R ₁₂ are preferably each independently an alkyl group having 2 to 7 carbon atoms, and more preferably an alkyl group having 2 to 6 carbon atoms. And as an alkane, it is preferable that it is a C12-C20 alkane, and it is more preferable that it is a C12-C18 alkane.

  Among these, when a liquid or solid having a saturated vapor pressure of 150 Pa or less at 25 ° C. is used, a thinner layer can be formed because of its low volatility. When the layer is thin, it is possible to prevent the fibers from becoming hard, and as a result, it is advantageous for maintaining the texture of the fiber sheet. As such compounds, methyl esters of long-chain aliphatic carboxylic acids such as methyl tetradecanoate, methyl hexadecanoate and methyl octadecanoate, and long-chain aliphatic hydrocarbons such as tetradecane, hexadecane and octadecane are preferably used.

  Depending on the contents of the polymerizable compound (A) and the compound (B) contained in the water repellent composition (X), the pore diameter, surface irregularity and strength in the polymer cured product change. As the content of the polymerizable compound (A) increases, the strength of the polymer cured product is improved, but the pore diameter and surface irregularities inside the polymer cured product are reduced, and the water repellency tends to decrease. The preferable content of the polymerizable compound (A) is in the range of 30 to 80% by mass, particularly preferably in the range of 40 to 70% by mass. When the content of the polymerizable compound (A) is 30% by mass or less, the strength of the polymer cured product is lowered, and when the content of the polymerizable compound (A) is 80% by mass or more, the pore diameter inside the polymer cured product is increased. Adjustment of surface irregularities becomes difficult.

Further, in the water repellent composition (X), the coexistence of the highly volatile liquid compound (D) as a constituent component together with the compound (b) reduces the thickness of the polymer cured product to be prepared. It is useful for keeping the texture of the fiber sheet. In this case, after application of the water repellent composition onto the fiber sheet, the compound (b) remains on the fiber through the polymerization process of the polymerizable compound (A), whereas the compound (D) volatilizes. As a result, the thickness of the polymer cured product is reduced. Such a compound (D) is preferably a liquid having a saturated vapor pressure at 25 ° C. of 600 Pa or more. As a highly hydrophobic compound that satisfies such requirements, pentane, hexane, heptane, R ₁₃ COOR ₁₄ (wherein R ₁₃ and R ₁₄ each independently represents an alkyl group having 1 to 5 carbon atoms). The total number of carbon atoms of R ₁₃ and R ₁₄ is 6 or less.), R ₁₅ COR ₁₆ (wherein R ₁₅ and R ₁₆ each independently represents an alkyl group having 1 to 5 carbon atoms). , R ₁₅ and R ₁₆ have a total carbon number of 6 or less.), R ₁₇ OR ₁₈ (wherein R ₁₇ and R ₁₈ each independently represents an alkyl group having 1 to 6 carbon atoms, The total number of carbon atoms of ₁₇ and R ₁₈ is 7 or less.), Benzene, toluene, dichloromethane, chloroform, and carbon tetrachloride are preferably used. Specific examples of R ₁₃ COOR ₁₄ include ethyl acetate, methyl propionate, ethyl propionate, methyl butanoate, ethyl butanoate, methyl pentanoate, ethyl pentanoate, methyl hexanoate and the like. Specific examples of R ₁₅ COR ₁₆ As acetone, methyl ethyl ketone, methyl isobutyl ketone and the like, and specific examples of R ₁₇ OR ₁₈ include diethyl ether. The mixing ratio of the compound (b) and the compound (D) can be appropriately set at an arbitrary ratio depending on the target performance of the water-repellent fiber sheet.

  In the water repellent composition (X), a polymerization initiator, a polymerization inhibitor, a polymerization retarder, or an increaser is used to adjust the polymerization rate and degree of polymerization, the pore size of the polymer cured product, the surface irregularity, and the like. Various additives such as a sticking agent may be added.

  The polymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound (A) by irradiation with energy rays, and includes a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and the like. Can be used. For example, acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, 4,4′-bisdimethylamino Ketones such as benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, hydroxy Benzyl ketals such as cyclohexyl phenyl ketone, and azides such as N-azidosulfonylphenylmaleimide. A polymerizable photopolymerization initiator such as a maleimide compound can also be used. Further, the polymerization initiators listed here are disulfide compounds such as tetraethylthiilam disulfide, nitroxide compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4,4′-di-t- It can also be used as a living radical polymerization initiator in combination with a compound such as butyl-2,2′-bipyridine copper complex-methyl trichloroacetate complex or benzyldiethyldithiocarbamate.

  Examples of the polymerization retarder and polymerization inhibitor include vinyl monomers having a low polymerization rate such as α-methylstyrene and 2,4-diphenyl-4-methyl-1-pentene, and hindant phenols such as tert-butylphenol. .

  For the purpose of improving the coatability and the purpose of controlling the pore diameter inside the polymer cured product and the unevenness of the surface, a thickener can be used as a conventional thickener. When the water repellent composition (X) has a low viscosity, the pore shape is often given as a gap between the granular polymers adhered to each other. Often given as. That is, the higher the viscosity, the better the coatability, but the pore diameter and surface irregularities become finer, and the water repellency tends to decrease. Therefore, it is important to change the viscosity appropriately depending on the combination of materials constituting the water repellent composition (X) and the target performance of the water repellent fiber sheet.

  The fiber constituting the water-repellent fiber sheet of the present invention is not substantially affected by the water-repellent composition (X) or the energy rays used, for example, does not cause dissolution, decomposition, polymerization, and the like. Any material that does not substantially invade the water repellent composition (X) may be used. Examples of such fibers include recycled fibers (eg, rayon fiber, polynosic fiber, cupra fiber, etc.), semi-synthetic fibers (eg, acetate fiber, triacetate fiber, etc.), synthetic fibers (eg, nylon fiber, vinylon fiber, etc.) Vinylidene fiber, polyvinyl chloride fiber, polyester fiber, acrylic fiber, polyethylene fiber, polypropylene fiber, polyurethane fiber, polyacrylonitrile fiber, fluorine fiber, etc.), inorganic fiber (eg, glass fiber, carbon fiber, etc.), plant fiber (eg, Cotton, hemp, etc.), animal fibers (eg, wool, silk, etc.).

  Examples of the structure of the fiber sheet include a woven fabric, a knitted fabric, and a non-woven fabric. In the case of a woven fabric or a knitted fabric, it can be obtained by processing the fiber with a loom or a knitting machine. Moreover, in the case of a nonwoven fabric, it can be made into a fiber sheet by a dry method, a spunbond method, a melt blow method, a flash spinning method, a wet method, or the like. In addition, fiber fibers formed by these manufacturing methods are pre-mixed with adhesive fibers or composite fibers in which two or more types of resins having different melting points are combined, and then heat-treated to join the fibers. It can be a sheet. Moreover, the fiber sheet formed by laminating a plurality of different types of fiber sheets and further integrating them may be used.

  Moreover, the fiber may be surface-treated. The surface treatment is intended to prevent the fiber surface from being dissolved by the water repellent composition (X), to improve the adhesion of the water repellent composition (X) and to improve the adhesion of the water repellent polymer cured product. And so on.

  The surface treatment method of the base material is arbitrary. For example, the polymerizable compound (A) is applied to the surface of the base material and irradiated with energy rays to be cured, corona treatment, plasma treatment, flame treatment, acid or Examples include alkali treatment, sulfonation treatment, fluorination treatment, primer treatment with a silane coupling agent, surface graft polymerization, and application of a surfactant or a release agent. Among these, for example, in the method of treating with a silane coupling agent such as trimethoxysilylpropyl (meth) acrylate or triethoxysilylpropyl (meth) acrylate, the polymer group of these silane coupling agents is used for water repellent processing. The ability to copolymerize with the composition (X) is useful for improving the adhesion of the water-repellent polymer cured product to the fiber.

  The method for applying the water repellent composition (X) to the fiber sheet is not particularly limited, and examples thereof include a dipping method, a roll coating method, a doctor blade method, a spin coating method, a bar coating method, A coating method such as a spray method is preferred.

  Energy rays irradiated in the polymerization process include ultraviolet rays, visible rays, infrared rays, laser rays, radiation rays, etc .; ionizing radiations such as X-rays, gamma rays, radiation rays; electron rays, ion beams, beta rays, heavy particle rays, etc. An example is particle beam. Among these, ultraviolet rays and visible light are preferable from the viewpoint of handleability and curing speed, and ultraviolet rays are particularly preferable. For the purpose of accelerating the curing rate and complete curing, it is preferable to irradiate energy rays in a low oxygen concentration atmosphere. As the low oxygen concentration atmosphere, a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere is preferable.

_A method for removing the compound (B) from the polymer cured product in which the polymer polymer (P _A ) and the compound (B) were phase-separated, produced by polymerization of the water repellent composition (X), used a solvent. This can be done by washing. At that time, the region occupied by the compound (B) is replaced with a solvent, and then the solvent evaporates in the drying process, thereby forming pores in the polymer cured product and a concavo-convex structure on the surface. Is completed. The solvent can be used without limitation as long as it is compatible with the compound (b). However, in order to facilitate the drying operation, it is preferable to use a general-purpose solvent having high volatility such as methanol, ethanol, acetone, hexane, ethyl acetate, diethyl ether and chloroform.

  The water-repellent processed fiber sheet produced by the method of the present invention is a polymer cured product having an aggregated particle structure in which particulate polymers having a diameter of about 0.05 μm to 10 μm are aggregated with each other, and gaps between the particles become pores, A polymer cured product having a three-dimensional network structure in which polymers are aggregated in a network form is provided on the fiber surface.

Moreover, it is advantageous to repeatedly perform the steps of the production method of the present invention in order to obtain a water-repellent processed fiber sheet having excellent durability. In this case, as the process is repeated, the pores of the polymer cured product of the lower layer are partially filled by the penetration of the polymer constituting the polymer cured product of the upper layer, so that the structure is reinforced and, as a result, the water repellent finish The durability of the fiber sheet is improved.
<Invention in which water-repellent composition (X) contains polymer (C)>
The water repellent composition (X) can further contain a polymer (C) that is compatible with the polymerizable compound (A) and the compound (B) and is inert to energy rays. .

In this case, the polymer polymer (P _A ) produced by the polymerization of the polymerizable compound (A) becomes incompatible with the compound (B), and the phase separation state between the polymer polymer (P _A ) and the compound (B) occurs, the polymer polymer (P _a) or inside the polymer a polymer (P _a) compounds during (B) is in a state incorporated. By removing this compound (B), the region occupied by the compound (B) becomes pores, and a fine uneven structure is induced on the surface of the polymer cured product, thereby producing a fiber sheet having super water repellency. The polymer (C) may be completely removed from the cured film of the water repellent composition (X) as long as the effects of the present invention are not impaired, but at least for ensuring the strength of the cured product, It is preferable to leave a part in the cured product. Therefore, in the phase separation state of the polymer polymer (P _A ) and the compound (B), the polymer (C) is preferably distributed to some extent in the polymer polymer (P _A ) phase, and the higher the distribution ratio, the higher The strength of the cured product becomes higher.

  As the polymer (C), a polymer can be used as a single component or a mixture of two or more thereof. As a constituent component of the polymer (C), there is no particular limitation as long as it is compatible with the polymerizable compound (A) and the compound (B) and is inactive with respect to energy rays. From such a point of view, the polymer (C) is preferably a component having a super-water-repellent polymer cured product, and therefore preferably has high hydrophobicity, and is an acrylic (co) polymer or styrene (co) polymer. Coalescence is preferably used. Among them, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyisopropyl (meth) acrylate, polybutyl (meth) acrylate, polyisobutyl (meth) acrylate, poly tert-butyl (meth) acrylate, polyhexyl (meth) acrylate, polydodecyl (Meth) acrylate, polystearyl (meth) acrylate, polyisobornyl (meth) acrylate, polystyrene, and poly α-methylstyrene are particularly preferably used. Further, as one of the roles of the polymer (C), expansion of phase separation conditions by increasing the viscosity of the water repellent composition (X) can be mentioned. That is, the higher the viscosity of the water repellent composition (X), the more types of polymerizable compounds (A) and compounds (B) that can be used in the composition. Moreover, as will be described later, the viscosity of the water repellent composition (X) affects the pore diameter and surface irregularity of the polymer cured product. Therefore, it is important to appropriately set the molecular weight of the polymer according to the target performance of the water-repellent fiber sheet. The molecular weight of the polymer is preferably set in the range of 10,000 to 1,000,000.

  Depending on the relative contents of the polymerizable compound (A), the compound (B) and the polymer (C) contained in the water repellent composition (X), the pore diameter, surface irregularity and strength of the polymer cured product change. As the content of the polymerizable compound (A) is increased, the strength of the cured product is improved, but the pore diameter and surface irregularities inside the cured product are reduced, and the water repellency tends to be lowered. The preferable content of the polymerizable compound (A) is in the range of 30 to 80% by mass, particularly preferably in the range of 40 to 70% by mass. When the content of the polymerizable compound (A) is 30% by mass or less, the strength of the cured product is lowered, and when the content of the polymerizable compound (A) is 80% by mass or more, the pore diameter and surface irregularities inside the cured product are reduced. It becomes difficult to adjust.

  In addition, the viscosity of the water repellent composition (X) affects the pore shape of the polymer cured product. When the water repellent composition (X) has a low viscosity, the pore shape is often given as a gap between the granular polymers adhered to each other. Often given as. That is, the higher the viscosity, the better the coatability and the homogeneity of the thickness of the polymer cured product, but the pore diameter and surface irregularities tend to be finer and the water repellency tends to decrease. Therefore, the relative content of the polymerizable compound (A), the compound (B) and the polymer (C) and the relative content of the polymer (C) with respect to the compound (B) are changed according to the target performance of the water-repellent fiber sheet. It is important to appropriately set the viscosity of the water repellent composition (X).

  In addition, when the polymer (C) is contained in the water repellent composition (X), the compound (B) is composed of a highly volatile liquid compound (D) together with the compound (b). Coexistence as a component is useful for reducing the thickness of the polymer cured product to be prepared and maintaining the texture of the fiber sheet.

  The mixing ratio of the compound (b) and the compound (D) can be appropriately set at an arbitrary ratio depending on the target performance of the water-repellent fiber sheet.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to the range of a following example.

Example 1
[Preparation of water-repellent fiber sheet]
Kyoeisha Chemical Co., Ltd. ethylene glycol dimethacrylate “Light Ester EG” 6.94 g, Kyoeisha Chemical Co., Ltd. tert-butyl methacrylate “Light Ester TB” 1.14 g, Kyoeisha Chemical Co., Ltd. perfluorooctylethyl methacrylate “Light Ester FM” 0.18 g of -108 "and 0.18 g of 1-hydroxycyclohexyl phenyl ketone" Irgacure 184 "manufactured by Ciba Geigy as a photopolymerization initiator were uniformly mixed to prepare a polymerizable composition [A-1]. This was mixed uniformly with 5.23 g of methyl tetradecanoate to prepare a water repellent composition [X-1].

Subsequently, a hydrophilic repellent nonwoven fabric “Nippon Vilene Co., Ltd.“ Mass 18 g / m ² , thickness 0.18 mm ”using a spin coater at 3000 rpm for 10 seconds [X-1 ] Was applied. Using a UE031-353CHC type UV irradiation device made by Eye Graphics Co., Ltd. using a 3000 W metal halide lamp as a light source, the nonwoven fabric was irradiated with ultraviolet rays having an ultraviolet intensity of 40 mW / cm ² at 365 nm for 3 minutes in a nitrogen stream at room temperature. Thus, the water-repellent fiber sheet [H-1] was obtained by polymerizing the water-repellent composition [X-1] and then washing with ethanol and hexane.
[Analysis of water-repellent fiber sheet]
(1) Water contact angle: 144 °
Measuring device: Kyowa Interface Chemical Automatic Contact Angle Meter DM500
Water droplet volume: 4.0 μl
(2) Surface morphology: Evaluated using a scanning electron microscope. A scanning electron micrograph of the fiber sheet surface is shown in FIG.
Measuring device: Keyence Real Surface View Microscope VE-9800
(3) Water contact angle after washing resistance test: 142 °
Test method: 40 liters of water at about 25 ° C. was placed in a household washing machine, 20 g of household laundry detergent was added thereto, and the mixture was stirred well to dissolve the detergent. Three test pieces (10 cm × 10 cm) and an appropriate number of cotton cloths as load cloths were added to the test pieces, which were put into the washing liquid and washed. The washing and stirring operation was performed for 90 minutes, followed by rinsing for 15 minutes and then a dehydration operation for 3 minutes. It was allowed to stand at room temperature and air-dried. After drying, the contact angle was tested.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 2)
[Production of water-repellent fiber sheet]
As the base material, instead of the hydrophilic polyolefin nonwoven fabric, a PET nonwoven fabric “fiber diameter of about 11.6 μm, basis weight 40 g / m ² , thickness 0.32 mm” manufactured by Japan Vilene Co., Ltd. was used in the same manner as in Example 1. Water repellent fiber sheet [H-2] was obtained.
[Analysis of water-repellent fiber sheet]
Water contact angle: 141 ° (water contact angle of untreated PET nonwoven fabric: 118 °)
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 141 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 3)
[Production of water-repellent fiber sheet]
A water-repellent processed fiber was used in the same manner as in Example 1 except that a water-absorbent rayon nonwoven fabric “Non-woven fabric 142 g / m ² , thickness 0.93 mm” manufactured by Japan Vilene Co., Ltd. was used instead of the hydrophilic polyolefin nonwoven fabric. Sheet [H-3] was obtained.
[Analysis of water-repellent fiber sheet]
Water contact angle: 143 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 142 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

Example 4
[Production of water-repellent fiber sheet]
A water-repellent fiber sheet [H-4] was obtained in the same manner as in Example 1 except that a cotton gauze “Sterase S” manufactured by White Cross Co., Ltd. was used in place of the hydrophilic polyolefin nonwoven fabric.
[Analysis of water-repellent fiber sheet]
Water contact angle: 145 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 143 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 5)
[Production of water-repellent fiber sheet]
Kyoeisha Chemical Co., Ltd. 1,6-hexanediol dimethacrylate “Light Ester 1,6HX” 6.87 g, Kyoeisha Chemical Co., Ltd. n-lauryl methacrylate “Light Ester L” 1.27 g, “Light Ester FM-108” 0.16 g and 0.18 g of the above-mentioned “Irgacure 184” as a photopolymerization initiator were uniformly mixed to prepare a polymerizable composition [A-5]. This was mixed uniformly with 9.14 g of tetradecane to prepare a water repellent composition [X-5].
A water repellent fiber sheet [H-5] was obtained in the same manner as in Example 1 except that [X-5] was used instead of the water repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 144 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 140 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 6)
[Production of water-repellent fiber sheet]
Kyoeisha Chemical Co., Ltd. dimethylol tricyclodecane diacrylate “Light acrylate DCP-A” 7.00 g, Osaka Organic Chemical Co., Ltd. isobutyl acrylate “AIB” 1.02 g, Kyoeisha Chemical Co., Ltd. perfluorooctylethyl acrylate “ 0.15 g of light acrylate FA-108 ”and 0.18 g of“ Irgacure 184 ”as a photopolymerization initiator were uniformly mixed to prepare a polymerizable composition [A-6]. This was mixed uniformly with 5.22 g of methyl hexadecanoate to prepare a water repellent composition [X-6].
A water repellent fiber sheet [H-6] was obtained in the same manner as in Example 1 except that [X-6] was used instead of the water repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 145 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 143 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Comparative Example 1)
[Production of non-water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.65 g of methyl hexanoate to prepare a composition [XR-1].
Subsequently, a non-water-repellent fiber sheet [R-1] was obtained in the same manner as in Example 1 except that [XR-1] was used instead of the water-repellent composition [X-1].

[Analysis of non-water-repellent fiber sheet]
Water contact angle: 65 °
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the fiber sheet prepared using the composition containing methyl hexanoate having a saturated vapor pressure at 25 ° C. of 670 Pa as the compound (B) did not show water repellency.

(Comparative Example 2)
[Production of non-water-repellent fiber sheet]
In the same manner as in Example 5, polymerizable compound [A-5] was prepared. This was uniformly mixed with 4.65 g of methyl hexanoate to prepare a composition [XR-2].
Subsequently, a non-water-repellent fiber sheet [R-2] was obtained in the same manner as in Example 1 except that [XR-2] was used instead of the water-repellent composition [X-1].

[Analysis of non-water-repellent fiber sheet]
Water contact angle: 68 °
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the fiber sheet prepared using the composition containing methyl hexanoate having a saturated vapor pressure at 25 ° C. of 670 Pa as the compound (B) did not show water repellency.

(Comparative Example 3)
[Analysis of non-water-repellent fiber sheet]
In the same manner as in Example 6, polymerizable compound [A-6] was prepared. This was uniformly mixed with 4.65 g of methyl hexanoate to prepare a composition [XR-3].
Subsequently, a non-water-repellent fiber sheet [R-3] was obtained in the same manner as in Example 1 except that [XR-3] was used instead of the water-repellent composition [X-1].

[Analysis of non-water-repellent fiber sheet]
Water contact angle: 65 °
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the fiber sheet prepared using the composition containing methyl hexanoate having a saturated vapor pressure at 25 ° C. of 670 Pa as the compound (B) did not show water repellency.

(Example 7)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a water repellent composition [X-7].
A water-repellent fiber sheet [H-7] was obtained in the same manner as in Example 1 except that [X-7] was used instead of the water-repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 152 ° (Water droplet photograph is shown in FIG. 2)
Surface morphology: Evaluated using a scanning electron microscope. A scanning electron micrograph of the fiber sheet surface is shown in FIG.
Water contact angle after washing resistance test: 150 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 8)
[Production of water-repellent fiber sheet]
A water-repellent fiber sheet [H-8] was obtained in the same manner as in Example 7 except that the PET nonwoven fabric was used in place of the hydrophilic polyolefin nonwoven fabric as the substrate.
[Analysis of water-repellent fiber sheet]
Water contact angle: 153 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 150 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

Example 9
[Production of water-repellent fiber sheet]
A water-repellent fiber sheet [H-9] was obtained in the same manner as in Example 7 except that the rayon nonwoven fabric was used instead of the hydrophilic polyolefin nonwoven fabric as a base material.
[Analysis of water-repellent fiber sheet]
Water contact angle: 148 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 146 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 10)
[Production of water-repellent fiber sheet]
A water-repellent fiber sheet [H-10] was obtained in the same manner as in Example 7 except that the cotton gauze “Sterase S” was used in place of the hydrophilic polyolefin nonwoven fabric.
[Analysis of water-repellent fiber sheet]
Water contact angle: 150 ° (water droplet photograph is shown in FIG. 4)
Surface morphology: Evaluated using a scanning electron microscope. A scanning electron micrograph of the fiber sheet surface is shown in FIG.
Water contact angle after washing resistance test: 149 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 11)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.59 g of ethyl phenylacetate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich, to prepare a water repellent composition [X-11].
A water-repellent fiber sheet [H-11] was obtained in the same manner as in Example 1 except that [X-11] was used instead of the water-repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 149 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 146 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 12)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.72 g of tetradecane and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich, to prepare a composition [X-12] for a water-repellent fiber sheet.
A water repellent fiber sheet [H-12] was obtained in the same manner as in Example 1 except that [X-12] was used instead of the water repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 151 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 148 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 13)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.65 g of isobutylbenzene and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a water repellent composition [X-13].
A water repellent fiber sheet [H-13] was obtained in the same manner as in Example 1 except that [X-13] was used instead of the water repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 150 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 149 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 14)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of diethylene glycol dibutyl ether and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a water repellent composition [X-14].
A water-repellent fiber sheet [H-14] was obtained in the same manner as in Example 1 except that [X-14] was used instead of the water-repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 150 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 146 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 15)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyethyl methacrylate (weight average molecular weight 340,000) manufactured by Aldrich, to prepare a water repellent composition [X-15].
A water-repellent fiber sheet [H-15] was obtained in the same manner as in Example 1 except that [X-15] was used instead of the water-repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 149 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 147 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 16)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.50 g of polyisobornyl methacrylate (weight average molecular weight 554,000) manufactured by Aldrich to prepare a water repellent composition [X-16].
A water repellent fiber sheet [H-16] was obtained in the same manner as in Example 1 except that [X-16] was used instead of the water repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 151 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 147 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 17)
[Production of water-repellent fiber sheet]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.48 g of polystyrene (weight average molecular weight 280,000) manufactured by Aldrich to prepare a water repellent composition [X-17].
A water repellent fiber sheet [H-17] was obtained in the same manner as in Example 1 except that [X-17] was used instead of the water repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 148 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 146 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 18)
[Production of water-repellent fiber sheet]
In the same manner as in Example 5, polymerizable compound [A-5] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a water repellent composition [X-18].
A water-repellent fiber sheet [H-18] was obtained in the same manner as in Example 1 except that [X-18] was used instead of the water-repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 149 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 148 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 19)
[Production of water-repellent fiber sheet]
In the same manner as in Example 6, polymerizable compound [A-6] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a water repellent composition [X-19].
A water repellent fiber sheet [H-19] was obtained in the same manner as in Example 1 except that [X-19] was used instead of the water repellent composition [X-1].

[Analysis of water-repellent fiber sheet]
Water contact angle: 151 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 146 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Comparative Example 4)
[Production of non-water-repellent fiber sheet]
A polymerizable compound [A-1] was prepared in the same manner as in Example 7. This was uniformly mixed with 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a composition [XR-4].
Subsequently, a non-water-repellent fiber sheet [R-4] was obtained in the same manner as in Example 7, except that [XR-4] was used instead of the water-repellent composition [X-7].

[Analysis of non-water-repellent fiber sheet]
Water contact angle: 86 °
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the processed fiber sheet prepared using the film-forming composition containing no compound (B) had a lower water contact angle value than the water-repellent processed fiber sheet of Example 7.

(Comparative Example 5)
[Production of non-water-repellent fiber sheet]
A polymerizable compound [A-1] was prepared in the same manner as in Example 7. This was uniformly mixed with 0.52 g of polyethyl methacrylate (weight average molecular weight 340,000) manufactured by Aldrich to prepare a composition [XR-5].
Subsequently, a non-water-repellent fiber sheet [R-5] was obtained in the same manner as in Example 7 except that [XR-5] was used instead of the water-repellent composition [X-7].

[Analysis of non-water-repellent fiber sheet]
Water contact angle: 82 °
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the processed fiber sheet prepared using the film-forming composition containing no compound (B) had a lower water contact angle value than the water-repellent processed fiber sheet of Example 7.

(Comparative Example 6)
[Production of non-water-repellent fiber sheet]
In the same manner as in Example 19, polymerizable compound [A-6] was prepared. This was uniformly mixed with 0.48 g of polystyrene (weight average molecular weight 280,000) manufactured by Aldrich to prepare a composition [XR-6].
Subsequently, a non-water-repellent fiber sheet [R-6] was obtained in the same manner as in Example 7 except that [XR-6] was used instead of the water-repellent composition [X-7].

[Analysis of non-water-repellent fiber sheet]
Water contact angle: 66 °
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the processed fiber sheet prepared using the film-forming composition containing no compound (B) had a lower water contact angle value than the water-repellent processed fiber sheet of Example 7.

(Example 20)
[Production of water-repellent fiber sheet]
A water repellent composition [X-1] was prepared in the same manner as in Example 1. This was uniformly mixed with 51.5 g of ethyl acetate to prepare a water repellent composition [X-20].
In the same manner as in Example 1, the water repellent composition [X-20] was adhered on the hydrophilic polyolefin nonwoven fabric using a spin coater under the conditions of 3000 rpm and 180 seconds. The nonwoven fabric was polymerized in the same manner as in Example 1, followed by washing to obtain a water-repellent fiber sheet [H-20].

[Analysis of water-repellent fiber sheet]
Water contact angle: 140 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 139 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 21)
[Production of water-repellent fiber sheet]
A water repellent composition [X-7] was prepared in the same manner as in Example 7. This was uniformly mixed with 50.5 g of ethyl acetate to prepare a water repellent composition [X-21].
In the same manner as in Example 7, the water repellent composition [X-21] was adhered onto the hydrophilic polyolefin nonwoven fabric using a spin coater under the conditions of 3000 rpm and 180 seconds. The nonwoven fabric was polymerized in the same manner as in Example 7 and then washed to obtain a water-repellent fiber sheet [H-21].

[Analysis of water-repellent fiber sheet]
Water contact angle: 147 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 145 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 22)
[Production of water-repellent fiber sheet]
Using the water repellent composition [X-1] in the same manner as in Example 1, a water repellent polymer cured product was adhered onto the hydrophilic polyolefin nonwoven fabric, and the water repellent fiber sheet [H-1] was prepared. Obtained.
Next, the process of attaching the water-repellent polymer cured product to the water-repellent fiber sheet [H-1] using the water-repellent composition [X-1] in the same manner as in Example 1 is repeated 4 The water-repellent processed fiber sheet [H-22] was obtained.

[Analysis of water-repellent fiber sheet]
Water contact angle: 146 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 145 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

(Example 23)
[Production of water-repellent fiber sheet]
In the same manner as in Example 7, the water-repellent composition [X-7] was used to adhere the water-repellent polymer cured product onto the hydrophilic polyolefin nonwoven fabric, and the water-repellent fiber sheet [H-7] was prepared. Obtained.
Next, the process of attaching a water-repellent polymer cured product on the water-repellent fiber sheet [H-7] using the water-repellent composition [X-7] in the same manner as in Example 7 is repeated 4 The water repellent fiber sheet [H-23] was obtained.

[Analysis of water-repellent fiber sheet]
Water contact angle: 153 °
Surface morphology: Evaluated using a scanning electron microscope.
Water contact angle after washing resistance test: 152 °
The measuring apparatus, test method, etc. are as described in Example 1.
From the above results, it was confirmed that a water-repellent processed fiber sheet having high washing resistance in which a water-repellent polymer cured product having a fine uneven structure was adhered to the fiber surface could be formed.

Claims (10)

A polymerizable compound (A) polymerizable by irradiation with energy rays;
A compound (B) that is compatible with the polymerizable compound (A) but is not compatible with the polymer polymer (P _A ) of the polymerizable compound ( _A ) and is inactive with respect to energy rays. A step of producing a water repellent composition (X) mixed with
Attaching the water repellent composition (X) to a fiber sheet;
After polymerizing the polymerizable compound (A) in the water repellent composition (X) by irradiation with energy rays, the method includes a step of removing the compound (B),
A method for producing a water-repellent fiber sheet, wherein the compound (B) is liquid or solid, has a molecular weight of 500 or less, and a saturated vapor pressure at 25 ° C. of 400 Pa or less. The compound (B) is selected from the group consisting of compounds represented by formula (1), formula (2), formula (3) and formula (4), and optionally branched alkanes having 10 to 20 carbon atoms. The method for producing a water-repellent fiber sheet according to claim 1, which is one or more selected compounds.

(In formula (1), R ₁ represents an alkyl group or benzyl group having 9 to 19 carbon atoms, and R ₂ represents a methyl group or an ethyl group.)

(In Formula (2), R ₃ represents a methyl group or an ethyl group, and R ₄ represents an alkyl group or a benzyl group having 10 to 20 carbon atoms which may be branched.)

(In formula (3), R _{5 to} R ₁₀ each independently represents a hydrogen atom or an optionally branched alkyl group, and at least two of them are ethyl groups, or at least one of them has 3 carbon atoms. It is the alkyl group which may be branched of -8.

(In Formula (4), R ₁₁ and R ₁₂ each independently represents an alkyl group having 2 to 8 carbon atoms which may be branched.)   The water repellent composition (X) further contains a polymer (C) that is compatible with the polymerizable compound (A) and the compound (B) and inert to energy rays. 3. A method for producing a water-repellent fiber sheet according to 1 or 2.   Furthermore, the manufacturing method of the water-repellent processed fiber sheet in any one of Claims 1-3 containing the liquid compound (D) whose saturated vapor pressure in 25 degreeC is 600 Pa or more. The compound (D) is pentane, hexane, heptane, R ₁₃ COOR ₁₄ (wherein R ₁₃ and R ₁₄ each independently represents an alkyl group having 1 to 5 carbon atoms, but carbons of R ₁₃ and R ₁₄ ) The total number is 6 or less.), R ₁₅ COR ₁₆ (wherein R ₁₅ and R ₁₆ each independently represents an alkyl group having 1 to 5 carbon atoms, but the number of carbon atoms of R ₁₅ and R ₁₆ is The total is 6 or less.), R ₁₇ OR ₁₈ (wherein R ₁₇ and R ₁₈ each independently represents an alkyl group having 1 to 6 carbon atoms, but the total number of carbon atoms of R ₁₇ and R ₁₈ is 5. The method for producing a water-repellent fiber sheet according to claim 4, which is at least one compound selected from the group consisting of benzene, toluene, dichloromethane, chloroform and carbon tetrachloride.   The method for producing a water-repellent fiber sheet according to any one of claims 3 to 5, wherein the polymer (C) is an acrylic copolymer or a styrene copolymer.   The method for producing a water repellent fiber sheet according to any one of claims 3 to 6, wherein the molecular weight of the polymer (C) is in the range of 10,000 to 1,000,000.   The method for producing a water-repellent processed fiber sheet according to any one of claims 1 to 7, wherein the surface has a contact angle with water of 150 ° or more and exhibits super water repellency.   A water-repellent fiber sheet obtained by the method according to claim 1.   A water-repellent processed fiber sheet comprising a water-repellent structure formed on a fiber surface, which is formed of a polymer of a polymerizable compound (A) that can be polymerized by irradiation with energy rays.

Images