CN113165010A - Water-repellent treatment product for fiber and method for surface treatment of fiber-made article - Google Patents
Water-repellent treatment product for fiber and method for surface treatment of fiber-made article Download PDFInfo
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- CN113165010A CN113165010A CN201980080263.9A CN201980080263A CN113165010A CN 113165010 A CN113165010 A CN 113165010A CN 201980080263 A CN201980080263 A CN 201980080263A CN 113165010 A CN113165010 A CN 113165010A
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Abstract
The waterproof treated product (1) for fibers of the present invention comprises: a water repellent agent (2) containing a polymer having a predetermined solubility dissolved in a volatile solvent, and a spray type spray container (3) filled with the water repellent agent (2). When the water repellent agent (2) is sprayed onto a fiber product by the spray type spray container (3), the velocity of the liquid droplet (21) obtained by the following method is 400 cm/sec or less when the water repellent agent (2) is sprayed at a position spaced 10cm from the spray type spray container (3). The velocity of the liquid droplet (21) is determined by dividing 5cm, which is the distance from a position 5cm to a position 10cm away from the spray type ejection container (3), by the moving time (seconds) of the liquid droplet (21) from the position 5cm to the position 10cm away from the spray type ejection container (3).
Description
Technical Field
The present invention relates to a water repellent treatment product for fibers and a method for surface treatment of a fiber article using the water repellent treatment product for fibers.
Background
Underwear such as underwear is mainly made of fibers, and is one typical example of a fiber product used by being directly attached to the skin. Absorbent articles of the type which are attached to the inside of a lower body side garment and mainly absorb urine are known. Patent document 1 describes, as one of such absorbent articles, a male incontinence pad provided with a leakage-preventing containment flap which stops a lateral flow of excreted urine so as not to leak out even when a large amount of urine is excreted at one time. The male incontinence pad described in this document can sufficiently satisfy users who have a large amount of excretion.
The present applicant has previously proposed a silicone-based fiber surface treatment agent which is improved in softness, smoothness, and hydrophobicity of fibers and is excellent in color density (see patent document 3). In this document, as a method for adhering a fiber surface treatment agent to the surface of a fiber, an air-blowing method is described.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-188714
Patent document 2: japanese laid-open patent publication No. 2006-249610
Patent document 3: japanese laid-open patent publication No. 4-163374
Disclosure of Invention
The present invention provides a water repellent treatment product for fibers, which comprises: a water repellent agent containing a polymer dissolved in a volatile solvent, and a spray-type spray container filled with the water repellent agent.
In one embodiment, the above-described polymer has a solubility in water at 25 ℃ of less than 50mg/100 g.
In one embodiment, when the water repellent agent is sprayed to a fiber product by the spray type spray container, the velocity of the liquid droplet sprayed at a position spaced apart from the spray type spray container by 10cm is 400 cm/sec or less as determined by the following method.
In one embodiment, the velocity of the liquid droplet is obtained by dividing 5cm, which is a distance from a position 5cm away from the spray container to a position 10cm away from the spray container, by a moving time (sec) of the liquid droplet from the position 5cm away from the spray container to the position 10cm away from the spray container.
Further, the present invention provides a surface treatment method for a fiber article, comprising the steps of: the surface of a fiber-made article is treated with a water repellent treatment agent containing a polymer dissolved in a volatile solvent.
In one embodiment, the above-described polymer has a solubility in water at 25 ℃ of less than 50mg/100 g.
In one embodiment, the water repellent agent is sprayed onto the fiber product using a spray type spray container under the condition that the speed of the droplets of the water repellent agent reaching the fiber product is 400 cm/sec or less.
Drawings
Fig. 1 is a diagram for explaining a method of measuring a velocity of a droplet of a water repellent agent sprayed at a position spaced 10cm from a spray type spray container in a water repellent treatment product for fiber as a preferred embodiment of the present invention.
Fig. 2 is a diagram for explaining a fiber product to which the water repellent treatment product for fiber of the present embodiment is applied.
Detailed Description
Particularly among the elderly men, there are few people who have the following problems: urine is not discharged during urination, and a small amount of urine leaks after urination is completed. In such a user with a small urine leakage, the high water absorption capacity male incontinence pad described in patent document 1 is too exaggerated, and the user may feel impairs self-esteem and feels uncomfortable when the pad is used. In addition, since the male incontinence pad is likely to be bulky due to its high water absorption capacity, there is a concern that the pad may be worn by another person. Further, the disposal of the male incontinence pad after use may be troublesome. Therefore, a technique that can directly use a commonly used lower body underwear or the like without using a large article such as a male incontinence pad and can solve the above-described problems has been strongly desired, and has not yet been provided.
The technique described in patent document 2 is to provide a water repellent to the surface of a knitted fabric to improve the dry feeling of the surface in contact with the skin and reduce the feeling of stuffiness, but the use by a user with a small amount of excretion is not assumed. The method for applying the water repellent agent described in this document is an industrial method, and is not a method in which a user can easily and uniformly apply the water repellent agent.
As for the method of applying the water repellent agent described in patent document 3, a blow-off method is used, and therefore, a user can apply the water repellent agent more easily and uniformly than the application method described in patent document 2. However, the technique described in patent document 3 does not assume the use of a user with a small amount of excretion.
In view of the above, the present invention relates to a water repellent treatment product for fibers which can effectively prevent body fluid excreted from the body from leaking from clothes without impairing the water absorbability of the clothes itself, while using the clothes such as lower body underwear which are commonly used as they are. The present invention also relates to a method for surface treatment of a fiber-made article using the water repellent treatment product for fiber.
The present invention will be described below based on preferred embodiments thereof. The present invention relates to a water repellent treatment product for fibers. As shown in fig. 1, a water repellent treatment product 1 for fiber, which is a preferred embodiment of the water repellent treatment product for fiber of the present invention, includes: a water repellent agent 2 containing a polymer dissolved in a volatile solvent, and a spray type spray container having a container main body 31 filled with the water repellent agent 2. The water repellent treatment product 1 for fibers is used by spraying the water repellent treatment agent 2 filled in the container main body 31 using the spray type spray container 3.
When the water repellent treatment product 1 for fiber is used to spray the water repellent treatment agent 2 onto a fiber product such as underwear for male use by using the spray type spray container 3, the velocity of the sprayed water repellent treatment agent 2 at a position spaced apart from the spray type spray container by 10cm is adjusted so as to be 400 cm/sec or less as determined by the following method. If the speed of the droplets is higher than 400 cm/sec, the water-repellent agent will not travel to the surface of the fiber article on which the water-repellent agent is sprayed, but will also travel over the entire area of the fiber article in the thickness direction to the surface opposite to the surface, and the water absorption and texture of the fiber article itself will be impaired. On the other hand, as shown in fig. 2, when the water repellent agent 2 is sprayed onto the outer surface 41 of the fiber product 4 with a weak force at which the droplet velocity of the water repellent agent 2 is 400 cm/sec or less, the water repellent polymer film 22 is easily formed at the application portion of the outer surface 41. The reason is presumed to be that the water repellent agent 2 is likely to stay at the application site of the fiber product 4 to which the water repellent agent 2 is applied, and the volatile solvent is volatilized at the application site to form the film 22 of the water repellent polymer at the application site. On the other hand, the polymer film 22 is not easily formed on the inner surface 42 side of the fiber article to which the water repellent treatment agent 2 is not applied. Therefore, even if the water repellent agent 2 is applied to, for example, a lower body intimate garment or the like which is in direct contact with the excretory part of the wearer 10, the water absorption property on the inner surface 42 side of the lower body intimate garment or the like is not easily lowered, and therefore, the lower body intimate garment or the like to which the water repellent agent 2 is applied can be worn without giving a feeling of incongruity, and body fluid can be absorbed and held in the fiber product 4. When the film 22 of a waterproof polymer is formed on the outer surface 41 of the lower body coverall or the like, the body fluid excreted by the wearer 10 is less likely to leak to the outer surface 41 of the lower body coverall, and the body fluid is prevented from leaking to the outer garments 5 such as the outer pants. From the viewpoint of easily forming a film of a water repellent polymer only on the outer surface side of the fiber article to which the water repellent agent 2 is sprayed, the velocity of the droplets of the water repellent agent 2 at a position at a distance of 10cm from the spray type discharge vessel is 400 cm/sec or less, preferably 350 cm/sec or less, and more preferably 300 cm/sec or less. The lower limit of the speed of the liquid droplet is not particularly limited as long as the liquid droplet of the water repellent agent 2 reaches the outer surface of the fiber article, and the lower the speed, the better, the 10 cm/sec or more is preferable, and the 100 cm/sec or more is more preferable.
< method for measuring velocity of droplet of water repellent sprayed at distance of 10cm from spray type spraying container >
As shown in fig. 1, the water repellent agent 2 is sprayed in a horizontal direction by a spray type spray container 3. Then, the droplets 21 of the water repellent agent 2 are photographed by a high-speed camera or a high-speed video camera (for example, a high-speed microscope manufactured by KEYENCE: VW-9000). The measurement conditions were 1/750 seconds for the shutter speed, X1(0dB) for the gain, 500fps for the imaging frame rate, and 640 × 240 for the pixels. The velocity of the droplet 21 is determined by dividing a distance L of 5cm, which is a distance L from a position P1 at a distance of 5cm from the spray discharge vessel 3 to a position P2 at a distance of 10cm, specifically, a moving distance of the droplet 21 in the horizontal direction, which is 5cm, by a moving time (sec) of the droplet 21 at a position P2 at a distance of 5cm from the spray discharge vessel 3 to a position P1 at a distance of 10 cm.
Velocity (cm/sec) of droplet 21 is distance L: 5 cm/moving time (seconds)
Examples of the spray-type discharge container 3 include a manual spray container of a direct-pressure or pressure-accumulating type, and an aerosol spray container containing a propellant in a pressure-resistant container. The manual spray container is a spray container provided with a sprayer which does not use a propellant such as a gas, and is a spray container which sprays the water repellent agent 2 in the container by a force of pressing down the sprayer with a finger or pulling the sprayer with a finger. In "an autonomous standard for improving safety of a home aerosol waterproof spray product or the like" made by the japan aerosol association of general financial group jurisdictions, the use of aerosol spray for clothes containing a silicone resin or a fluororesin is limited from the viewpoint of safety. Therefore, when treating clothes indoors, a manual spray container is preferably used for the silicone polymer. On the other hand, both indoor and outdoor, a manual spray container and an aerosol container can be used for the acrylate polymer.
The amount of the water repellent agent 2 to be applied to the fiber article is preferably 15g/m from the viewpoints of shortening the time required for the treatment of the fiber article and simplifying the treatment of the fiber article2Above, more preferably 50g/m2Above, more preferably 80g/m2The above. In addition, from the viewpoint of easily forming a film of a water-repellent polymer only on the application surface side of the fiber article to which the water-repellent agent 2 is applied, it is preferably 300g/m2Hereinafter, more preferably 200g/m2Hereinafter, more preferably 100g/m2The following. The amount of the water repellent agent 2 applied to the fiber article is preferably 15g/m2Above and 300g/m2Hereinafter, more preferably 50g/m2Above and 200g/m2Hereinafter, more preferably 80g/m2Above and 100g/m2The following.
The amount of the polymer soluble in a volatile solvent, which will be described later, when the water repellent treatment agent of the present invention is applied to a fiber article is preferably 0.75g/m from the viewpoint of further improving the water repellency of the fiber article2Above, more preferably 2.5g/m2Above, more preferably 4g/m2The above. Further, it is preferably 15g/m2Hereinafter, more preferably 10g/m2Hereinafter, it is more preferably 5g/m2The following. When the water repellent treatment agent of the present invention is applied to a fiber-made article, the amount of a polymer soluble in a volatile solvent, which will be described later, is preferably 0.75g/m2Above and 15g/m2Hereinafter, more preferably 2.5g/m2Above and 10g/m2Hereinafter, more preferably 4g/m2Above and 5g/m2The following.
When a manual spray container is used as the spray type discharge container 3, the opening diameter K of the discharge port is preferably 0.3mm or more, more preferably 0.35mm or more, and preferably 0.6mm or less, more preferably 0.5mm or less, from the viewpoint of making the velocity of the droplets of the water repellent agent 2 to be sprayed 400 cm/sec or less (hereinafter, also referred to as "optimal velocity of the droplets of the water repellent agent 2"). The opening diameter K of the ejection port is preferably 0.3mm or more and 0.6mm or less, and more preferably 0.35mm or more and 0.5mm or less.
When a manual spray container is used as the spray type discharge container 3, the discharge amount of the water repellent agent 2 per 1 operation is preferably 0.06mL or more, more preferably 0.1mL or more, and preferably 1mL or less, more preferably 0.6mL or less, from the viewpoint of the optimum speed of the droplets of the water repellent agent 2 and the viewpoint of easily forming a film of a water repellent polymer only on the application surface side of the fiber product to which the water repellent agent 2 is applied. The discharge amount of the water repellent agent 2 per 1 operation is preferably 0.06mL or more and 1mL or less, and more preferably 0.1mL or more and 0.6mL or less. From the same viewpoint, the spray angle α of the water repellent agent 2 sprayed from the opening diameter K of the spray port is preferably 30 degrees or more and 90 degrees or less, and more preferably 50 degrees or more and 80 degrees or less, when the amount of spraying is 0.06mL or more and 1mL or less per 1 operation. The spray angle α can be calculated by capturing an image of the spray with a camera and a video camera with the background set to black, and measuring the spray angle of the obtained photograph and moving image with a protractor.
When an aerosol spray container is used as the spray type discharge container 3, it is preferable that a propellant is contained in the spray container in addition to the water repellent agent 2. As the propellant, those conventionally used in aerosol spray containers can be used without particular limitation. Examples of the propellant include LPG, dimethyl ether (DME), carbon dioxide gas, nitrogen gas, and a mixture thereof, and LPG and dimethyl ether (DME) are preferably used from the viewpoint of being easily vaporized and expanded to easily form mist.
In the case of using an aerosol spray container as the spray type discharge container 3, the opening diameter K of the discharge port is preferably 0.3mm or more, more preferably 0.35mm or more, and preferably 0.6mm or less, more preferably 0.5mm or less, from the viewpoint of the optimum velocity of the droplets of the water repellent agent 2. The opening diameter K of the ejection port is preferably 0.3mm or more and 0.6mm or less, and more preferably 0.35mm or more and 0.5mm or less.
When an aerosol spray container is used as the spray type discharge container 3, the discharge amount of the water repellent agent 2 per 1 second when LPG or dimethyl ether (DME) is used as the spray agent is preferably 0.2mL or more, more preferably 0.5mL or more, and preferably 1.5mL or less, more preferably 1mL or less, from the viewpoint of the optimum velocity of the droplets of the water repellent agent 2 and the viewpoint of easily forming a film of a water repellent polymer only on the application surface side of the fiber product to which the water repellent agent 2 is applied. The discharge amount of the water repellent agent 2 per 1 second is preferably 0.2mL or more and 1.5mL or less, and more preferably 0.5mL or more and 1mL or less. From the same viewpoint, the spray angle α of the spray from the opening diameter K of the spray port when the discharge amount of the water repellent agent 2 per 1 second is 0.2mL or more and 1.5mL or less is preferably 10 degrees or more and 80 degrees or less, and more preferably 15 degrees or more and 30 degrees or less. The spray angle α can be calculated by capturing an image of the spray with a camera and a video camera with the background set to black, and measuring the spray angle of the obtained photograph and moving image with a protractor.
When the amount of the water repellent agent 2 ejected per 1 second is adjusted to 0.2mL or more and 1.5mL or less using an aerosol spray container, the amount of the propellant contained in the spray container is such that the mass ratio of the water repellent agent 2 to the propellant is as follows: the propellant is preferably 5: 95-95: 5, more preferably 20: 80-50: 50. the pressure in the spray container is preferably 0.1MPa to 0.8MPa, more preferably 0.2MPa to 0.5MPa, at 25 ℃.
When the viscosity of the water repellent agent 2 increases, the spray angle α at the time of spraying from the spray type spray container 3 tends to become narrow, and the flow of the liquid droplets is concentrated, whereby the speed of the liquid droplets of the water repellent agent 2 tends to become high. Therefore, from the viewpoint of the optimal speed of the droplets of the water repellent agent 2, the viscosity of the water repellent agent 2 filled in the spray type discharge container 3 is preferably 20mPa · s or less, more preferably 15mPa · s or less, and still more preferably 10mPa · s or less at 25 ℃. The lower limit of the viscosity is not particularly limited as long as the droplets of the water repellent agent 2 reach the outer surface of the fibrous article, and is preferably 1mPa · s or more as the lower the viscosity is, the more preferable the viscosity is. The viscosity of the water repellent agent 2 was measured using a B-type viscometer. As the type B viscometer, for example, a type B viscometer (TVB-10 type viscometer) manufactured by Toyobo industries, Ltd can be used. In the measurement conditions in this case, the rotor No. m1 and the rotation speed are measured at an appropriate rotation speed according to the viscosity.
The water repellent agent 2 contains a volatile solvent as one of its constituent components. By containing the volatile solvent, a polymer which can be dissolved in the volatile solvent, which will be described later, can be dispersed over a wide range and sprayed. The volatile solvent is preferably one having a saturated vapor pressure of 3000Pa or more at 25 ℃. Examples of the volatile solvent include water and an organic solvent, and a mixed solvent of water and a water-soluble organic solvent may be used. Examples of the volatile solvent containing an organic solvent include alcohols, esters, nitriles, ethers, hydrocarbons, ketones, and the like. These volatile solvents may be used alone in 1 kind, or may also be used in combination of 2 or more kinds. When 2 or more volatile solvents are used in combination, the saturated vapor pressure refers to the saturated vapor pressure of the volatile solvent having the lowest saturated vapor pressure among the plurality of volatile solvents used. Among these volatile solvents, from the viewpoint of satisfying both the solubility of the polymer described later and the drying time of the water repellent agent, it is preferable to use a combination of 1 or 2 or more selected from water, ethanol, isopropanol, hexane, dimethyl ether, and LPG (a mixture of propane and butane).
When an alcohol is used as the volatile solvent, a monohydric or polyhydric aliphatic alcohol having 1 to 5 carbon atoms is preferably used. In particular, monohydric alcohols having 1 to 3 carbon atoms, such as methanol, ethanol, and isopropanol, are preferably used. When an ester is used as the volatile solvent, it is preferable to use an ester of a monohydric or polyhydric aliphatic alcohol having 1 to 4 carbon atoms and a monohydric or polyhydric fatty acid having 1 to 4 carbon atoms. In particular, esters of monohydric aliphatic alcohols having 1 to 2 carbon atoms and monohydric fatty acids having 1 to 3 carbon atoms, such as ethyl acetate and methyl propionate, are preferably used. When a nitrile is used as the volatile solvent, a nitrile of an alkane having 2 to 3 carbon atoms, for example, acetonitrile or the like is preferably used.
The water repellent agent 2 may contain a nonvolatile solvent in addition to the volatile solvent as described above, as long as the effects of the present invention are not impaired. However, from the viewpoint of reliably obtaining the effects of the present invention, it is preferable that the solvent contained in the water repellent agent 2 is only a volatile solvent.
The water repellent treatment agent 2 contains a polymer soluble in a volatile solvent in addition to the volatile solvent. The water repellent agent 2 is allowed to contain an insoluble polymer in addition to a polymer soluble in a volatile solvent. However, from the viewpoint of reliably obtaining the effects of the present invention, the water repellent agent 2 preferably contains only a polymer that is soluble in a volatile solvent. The polymer soluble in a volatile solvent is a polymer compound having a solubility of 1g or more at 25 ℃ in 100g of a volatile solvent used in the water-repellent treatment agent. When the number of the polymers is 2 or more, it is preferable that all the polymers are polymers soluble in a volatile solvent.
The solubility of the polymer in the volatile solvent was measured by the following method. That is, as the volatile solvent, ethanol is taken as an example, and the limit dissolved amount of the polymer when 100g of ethanol is added and stirred for 24 hours in a closed vessel at 25 ℃ is taken as the solubility (g). The polymer was dissolved in a powder state of less than 16 mesh.
The polymer capable of being dissolved in a volatile solvent has a solubility in water of less than 50mg/100g at 25 ℃. If the surface of the fiber article is treated with a polymer having a solubility in water of less than 50mg/100g at 25 ℃, the body fluid can be effectively prevented from exuding from the clothes. From the viewpoint of effectively preventing body fluid from exuding from clothes, the solubility in water at 25 ℃ is preferably 40mg/100g or less, more preferably 30mg/100g or less, further preferably 20mg/100g or less, and further preferably less than 20mg/100 g. Examples of the polymer include silicone polymers, acrylic resins, and fluorine polymers, but the type of the polymer is not limited as long as the polymer is soluble in a volatile solvent and has a solubility in water at 25 ℃ of less than 50mg/100 g.
In the water repellent agent 2, the content of the polymer soluble in the volatile solvent is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2.5% by mass or more, from the viewpoint of easily forming a film of a water repellent polymer at an application site of the fiber article to which the water repellent agent 2 is applied, and from the viewpoint of washing off the film of the polymer at the time of washing the fiber article and from the viewpoint of ejection property from a nozzle in the case of spraying, is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 7.5% by mass or less. In the water repellent agent 2, the content of the polymer is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less, and further preferably 2.5% by mass or more and 7.5% by mass or less. When 1 polymer is contained in the water repellent agent 2, 1 polymer alone preferably satisfies the above range, and when 2 or more polymers are contained, the whole of all the polymers preferably satisfies the above range.
The present inventors have made various studies and, as a result, have clarified the following: as the polymer that can be dissolved in the volatile solvent, acrylic resins, silicone polymers having a polysiloxane skeleton as a main chain, and fluorine polymers are preferable from the viewpoint of the optimum speed of the droplets of the water repellent agent 2 and the viewpoint of easily forming a film of a water repellent polymer only on the application surface side of the fiber article to which the water repellent agent 2 is applied. The polymer that can be dissolved in the volatile solvent satisfies the above solubility, and from the viewpoint of the optimal speed of the droplets of the water repellent agent 2, the weight average molecular weight is preferably 10000 or more, more preferably 20000 or more and 5000000 or less. When the number of the polymers contained in the water repellent agent 2 is 2 or more, it is preferable that each of the polymers contained satisfies the above range. The weight average molecular weight can be analyzed by a known method, and can be determined as a standard polystyrene value by Gel Permeation Chromatography (GPC) (DP-8020) manufactured by Tosoh, Ltd.
As the acrylic resin, for example, acrylic resins obtained by homopolymerizing or copolymerizing acrylic derivatives such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid esters, or methacrylic acid esters as main components can be used. Specifically, there may be mentioned: (acrylic acid/t-butylacrylamide) copolymer, (alkyl acrylate/t-butylacrylamide) copolymer, (acrylic acid/alkyl acrylate/t-butylacrylamide) copolymer, (alkyl acrylate/octylacrylamide) copolymer, (acrylic acid/acrylamide/ethyl acrylate) copolymer, (methacryloyloxyethylcarboxybetaine/alkyl methacrylate) copolymer, (octylacrylamide/hydroxypropyl acrylate/butylaminoethyl methacrylate) copolymer, (alkylacrylamide/acrylic acid/alkylaminoalkylacrylamide/polyethyleneglycol methacrylate) copolymer, (alkylacrylamide/alkyl acrylate/alkylaminoalkylacrylamide/polyethyleneglycol methacrylate) copolymer, and (meth) acrylic acid/alkyl acrylate/alkylaminoalkylacrylamide/polyethyleneglycol methacrylate) copolymer, (alkylacrylamide/alkylaminoalkylacrylamide/polyethyleneglycol methacrylate) copolymer, alkyl acrylate polymer, (acrylic acid/alkyl acrylate) copolymer, alkyl acrylate/diacetoneacrylamide) copolymer, (acrylic acid/alkyl acrylate (C1-C18) ester/alkyl (C1-C8) acrylamide) copolymer, (methacrylic acid/alkyl acrylate/alkylacrylamide) copolymer, (styrene/acrylic acid) copolymer, (styrene/alkyl acrylate) copolymer, (styrene/acrylamide) copolymer, urethane-acrylic copolymer, (acrylic acid/alkyl methacrylate) copolymer, alkyl methacrylate polymer, (methacrylic acid/alkyl acrylate) copolymer, alkyl acrylate copolymer, and the like, (methacrylic acid/alkyl methacrylate) copolymers, (vinylpyrrolidone/acrylic acid/methacrylic acid) copolymers, (vinylpyrrolidone/alkyl acrylate/methacrylic acid) copolymers, (octylacrylamide/hydroxypropyl acrylate/butylaminoethyl methacrylate) copolymers, (methacryloyloxyethylcarboxybetaine/alkyl methacrylate) copolymers, (acrylic acid/alkyl acrylate/ethylamine methacrylate) copolymers and the like, among these, from the viewpoint of solvent solubility and transparency, it is preferable to use an (acrylic acid/ethyl acrylate/t-butylacrylamide) copolymer (Ultrahold (registered trademark) 8: trade name of BASF corporation) and an (alkyl acrylate/octylacrylamide) copolymer (DERMACRYL 79: trade name of Akzo Nobel Co., Ltd.).
The polysiloxane skeleton refers to a structure containing a bond of-O-Si-, and typically, silicone is used. Among silicones, the use of a silicone graft copolymer is preferable because the above-described effects become more remarkable. The silicone graft copolymer is a polymer compound having a main skeleton based on a siloxane bond, and is a compound containing at least one of N-acylalkyleneimine, acrylic acid, a salt of acrylic acid, an acrylate, acrylamide, methacrylic acid, a salt of methacrylic acid, a methacrylate, and methacrylamide as a copolymerization component in a side chain. Regarding the silicone graft copolymer, the following 2 types are roughly classified: producing a physical cross-linked body of cross-linking points by physical interaction; a covalently bonded chemical cross-linker. In the present invention, a physical crosslinked material is preferably used from the viewpoint of easy dissolution in a volatile solvent.
As the physically crosslinking silicone graft copolymer, (a) a silicone graft copolymer having a contact angle with water of 70 degrees or more and being a solid in air at 25 ℃, or (B) a silicone graft copolymer having an amino group and a liquid having an amine equivalent of 5,000g/mol or less is preferably used. (A) The silicone graft copolymer "solid in air at 25 ℃ of the solid silicone graft copolymer of (1) also includes a silicone graft copolymer which is originally liquid but is polymerized to be solid in an environment of 60% RH at 25 ℃.
The polymer that can be dissolved in the volatile solvent may be only at least one of the solid polymer of the above (a) and the liquid polymer of the above (B), or may be a polymer that can be dissolved, such as the polymer of the above (a), the polymer of the above (B), or the acrylic resin other than these. From the viewpoint of the optimal speed of the liquid droplets of the water repellent agent 2 and the viewpoint of easily forming a film of a water repellent polymer only on the application surface side of the fiber article to which the water repellent agent 2 is applied, it is preferable that only at least one of the polymer (a) and the polymer (B) is used. When the water repellent agent 2 contains both the polymer of (a) and the polymer of (B), the ratio of the solid polymer of (a) to the liquid polymer of (B) is represented by the value of [ (mass of the solid polymer of (a)/(mass of the liquid polymer of (B) ], and is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 1 or more, from the viewpoint of a wide range of selectivity in fiber-made articles. In addition, from the viewpoint of the texture of the fibrous article having the polymer film formed thereon, the value of [ (mass of solid polymer of a/(mass of liquid polymer of B) ] is preferably 100 or less, more preferably 50 or less, and still more preferably 10 or less. The value of [ (mass of solid polymer of a)/(mass of liquid polymer of B) ] is preferably 0.01 to 100, more preferably 0.1 to 50, and still more preferably 1 to 10.
The polymer soluble in the volatile solvent can form a film of a water-repellent polymer not only for a fiber product containing cotton, cuprammonium fiber, rayon, or the like having a cellulose skeleton, but also for a fiber product composed only of synthetic fibers such as polyester fibers. From the viewpoint of easily forming a film of a water repellent polymer only on the treatment surface side of the fiber article to which the water repellent agent 2 is sprayed, the contact angle between the polymer soluble in the volatile solvent and water is preferably 70 degrees or more, more preferably 80 degrees or more, and still more preferably 90 degrees or more. The contact angle is an index of the degree of hydrophobicity of the surface of the fiber-made article treated with the water repellent agent 2, and the larger the value of the contact angle, the stronger the hydrophobicity (the lower the hydrophilicity), and the smaller the value of the contact angle, the weaker the hydrophobicity (the higher the hydrophilicity). When the number of the polymers soluble in the volatile solvent is 2 or more, the whole of the polymers preferably satisfies the above range. The contact angle was measured by the following method.
< method for measuring contact Angle >
The water repellent agent 2 was cast into a tank and left to stand at a temperature of 25 ℃ for 12 hours, thereby forming a film. The film was set as a measurement sample. The measurement environment was set to a temperature of 23. + -. 2 ℃ and a relative humidity of 50. + -. 5% RH. A droplet of 1. mu.L of ion-exchanged water was attached to a surface to be measured for measuring the contact angle of a sample, the droplet was recorded from a side surface where the interface between the droplet and a membrane was visible, and the contact angle was measured based on an image obtained by the recording. As the measuring apparatus, for example, a microscope VHX-1000 manufactured by KEYENCE K.K. was used. Among the recorded images, 10 images with clear droplet outlines were selected, contact angles of the droplets were measured on the basis of the reference surface for each of the 10 images, and the average value of the contact angles was defined as the contact angle between the polymer and water.
Examples of the solid silicone graft copolymer (a) include: poly (N-acylalkyleneimine) modified silicone, poly (N, N-dimethylacrylamide) modified silicone, silicone alkoxy oligomer, silicone resin, acrylic silicone, sugar modified silicone (Japanese patent application laid-open No. 63-139106), polyglycerin modified silicone (Japanese patent application laid-open No. 2004-339244), silicone graft acrylate polymer (Japanese patent application laid-open No. 4-342513), silicone PEG block polymer (Japanese patent application laid-open No. 4-234307), and the like. These silicone graft copolymers may be used alone in 1 kind, or 2 or more kinds may also be used in combination. Among these, poly (N-acylalkyleneimine) -modified silicone and poly (N, N-dimethylacrylamide) -modified silicone are preferably used in terms of high solubility in a volatile solvent.
The poly (N-acylalkyleneimine) modified silicone is preferably a poly (N-acylalkyleneimine) modified silicone having a segment of poly (N-acylalkyleneimine) and a segment of organopolysiloxane in the molecule, and the segment of poly (N-acylalkyleneimine) is bonded to at least 1 of silicon atoms in the terminal or side chain of the segment of organopolysiloxane via an alkylene group. The number of carbon atoms of the alkylene group is preferably 2 to 20. In place of the alkylene group, a group containing a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom between adjacent methylene groups in the alkylene group or at the end of the alkylene group may be used. The number of hetero atoms is preferably 1 to 3.
Specific examples of preferable poly (N-acylalkyleneimine) modified silicones include poly (N-formylethyleneimine) modified silicones, poly (N-acetylethyleneimine) modified silicones, and poly (N-propionylethyleneimine) modified silicones. Among these, poly (N-propionylethyleneimine) modified silicone (INCI: silicone-9) having a weight average molecular weight of about 20,000 to 200,000 and a proportion of poly (N-propionylethyleneimine) segments in the polymer of about 3 to 50 mass% is preferable.
The poly (N, N-dimethylacrylamide) -modified silicone is preferably a poly (N, N-dimethylacrylamide) -modified silicone having, in a molecule, a segment of an organopolysiloxane and a polymer segment derived from an unsaturated monomer, wherein the polymer segment derived from the unsaturated monomer is bonded to at least 1 of silicon atoms at a terminal or a side chain of the segment of the organopolysiloxane via an alkylene group. Specifically, there may be mentioned an organopolysiloxane graft polymer in which repeating units derived from N, N-dimethylacrylamide (DMAAm) are contained in a polymer segment derived from an unsaturated monomer. The number of carbon atoms of the alkylene group is preferably 2 to 20. In place of the alkylene group, a group containing a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom between adjacent methylene groups in the alkylene group or at the end of the alkylene group may be used. The number of hetero atoms is preferably 1 to 3. The portion of the polymer segment derived from an unsaturated monomer other than the repeating unit derived from DMAAm contains repeating units derived from an unsaturated monomer copolymerizable with DMAAm (except DMAAm). Examples of the repeating unit derived from an unsaturated monomer copolymerizable with DMAAm include repeating units derived from an unsaturated monomer such as an olefin, a halogenated olefin, a vinyl ester, (meth) acrylate, or a (meth) acrylamide (excluding DMAAm).
Specific examples of the olefin copolymerizable with DMAAm include ethylene, propylene, and isobutylene. Specific examples of the halogenated olefin include vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride. Specific examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate. Specific examples of the (meth) acrylates include: (meth) acrylic esters having an alkyl group having 1 to 16 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and cyclohexyl (meth) acrylate; a (meth) acrylate having an alkyl group having 1 to 16 carbon atoms substituted with a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate; and polyethylene glycol (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, and the like. Specific examples of (meth) acrylamides other than DMAAm include: (meth) acrylamides such as acrylamide and methacrylamide; n, N-dialkyl (meth) acrylamides such as N, N-diethyl (meth) acrylamide (with the exception of DMAAm); n-alkyl (meth) acrylamides such as N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, and N-tert-octyl (meth) acrylamide; n-monosubstituted (meth) acrylamides having a carbonyl group as a substituent on a nitrogen atom such as diacetone (meth) acrylamide; n-monosubstituted (meth) acrylamides having an amino group as a substituent on a nitrogen atom such as N, N-dimethylaminopropyl (meth) acrylamide; n-monosubstituted (meth) acrylamides having a hydroxyl group as a substituent on a nitrogen atom such as N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.
Specific examples of preferable poly (N, N-dimethylacrylamide) -modified silicones include dimethylacrylamide-grafted organosiloxanes and the like. Among these, a dimethylacrylamide-grafted organosiloxane in which the proportion of a poly (N, N-dimethylacrylamide) segment in the polymer is about 1 to 50% by mass is preferable.
Examples of the liquid silicone graft copolymer (B) include amino-modified silicones. The amino-modified silicone may be used alone in 1 kind, or may also be used in combination of 2 or more kinds. The amino-modified silicone can be used to form a film of a water-repellent polymer only on the treated surface side of a fiber article to which the water-repellent treatment agent 2 is sprayed, since the amino group of the fiber article containing cotton, cuprammonium fiber, rayon, or the like having a cellulose skeleton is easily adsorbed to the hydroxyl group of the cellulose fiber. The amine equivalent of the amino-modified silicone is preferably 5,000g/mol or less, more preferably 4000g/mol or less, and still more preferably 3000g/mol or less, from the viewpoint of easy adsorption to cellulose-based fibers. Here, the amine equivalent refers to the mass of amino-modified silicone per 1 molar equivalent of amino groups, and is a value obtained by dividing the average molecular weight of amino-modified silicone by the number of amino groups present in the molecule of amino-modified silicone 1. The lower the number of amine equivalents, the greater the number of amino groups per unit mass. When the number of the amino-modified silicones contained in the water repellent agent 2 is 2 or more, the whole of all the silicones contained preferably satisfies the above range.
Examples of the fluorine-based polymer used as the polymer soluble in the volatile solvent include a fluorine-based polymer obtained by polymerizing a fluorinated olefin such as polytetrafluoroethylene or polyvinylidene fluoride, and a fluorine-based polymer partially modified.
As the polymer contained in the water repellent agent, other polymers having a solubility in water of less than 50mg/100g may be used in addition to the acrylic resin, silicone polymer, and fluorine polymer. Examples of the other soluble polymer include maleic acid polymers such as a (vinyl methyl ether/maleic acid) copolymer, a (vinyl methyl ether/alkyl maleate) copolymer, and a (vinyl methyl ether/butyl maleate) copolymer.
In the waterproof treatment product 1 for fiber, by applying the waterproof treatment agent 2 to a fiber article such as underwear for men, for example, it is possible to impart waterproofness to the fiber article and is effective for dealing with urine dripping after urination. More specifically, the surface of the fiber article is treated by a method including a step of treating the surface of the fiber article with the water repellent treatment agent 2, and a film of a water repellent polymer is formed only on the application surface side of the fiber article, thereby imparting water repellency to the fiber article. In order to easily form a film of a water-repellent polymer only on the application surface side of a fiber product, the water-repellent agent 2 is sprayed onto the fiber product using the spray type spray container 3 under the condition that the speed at which the droplets 21 of the water-repellent agent 2 reach the fiber product is 400 cm/sec or less. The speed of the droplets 21 when they reach the fiber product is set to the passing speed of the droplets 21 at the position at the same distance as the distance between the fiber product and the spray type discharge vessel 3, and is measured in the same manner as the above-described method of measuring the speed of the droplets of the water repellent agent sprayed at the position at a distance of 10cm from the spray type discharge vessel. Specifically, (1) when the distance between the fiber product and the spray type discharge vessel 3 is 5cm or more, as shown in fig. 1, the water repellent agent 2 is sprayed in the horizontal direction by the spray type discharge vessel 3, and the moving distance in the horizontal direction of the droplet 21 from a position P4 5cm before a position P3 at the same distance as the distance to the position P3, that is, 5cm, is divided by the moving time (sec) of the droplet 21 from the position P4 to the position P3, thereby obtaining the velocity of the droplet 21. (2) When the distance between the fiber product and the spray type discharge container 3 is less than 5cm, as shown in fig. 1, the water repellent agent 2 is sprayed in the horizontal direction by the spray type discharge container 3, and the moving distance of the droplet 21 in the horizontal direction from the position P0 of the spray type discharge container 3 to the position P5 at the same distance as the distance is divided by the moving time (sec) of the droplet 21 from the position P0 to the position P5, thereby determining the velocity of the droplet 21.
When the water repellent agent 2 is sprayed onto the fiber product using the spray type spray container 3, it is preferably sprayed so that the water repellent agent 2 does not reach a non-application surface of the fiber product on the side opposite to the application surface on which the water repellent agent 2 is sprayed. From the viewpoint of spraying so that the water repellent agent 2 does not reach the non-application surface of the water repellent agent 2, the distance between the spray type spray container 3 and the fiber product is preferably 3cm or more, more preferably 5cm or more, preferably 30cm or less, and more preferably 20cm or less. The distance between the spray type discharge vessel 3 and the fiber product is preferably in the range of 3cm to 30cm, and more preferably in the range of 5cm to 20 cm.
As the fiber-made article to which the repellent 2 is applied, underwear such as underwear and body underwear can be cited. Examples of the material include fibers having a cellulose skeleton such as cotton, cuprammonium fibers and rayon, synthetic fibers such as polyester, nylon and acrylic, and a material having air permeability formed of a net-like woven fabric obtained by blending these fibers. The weight per unit area of the woven or knitted fabric is preferably 70g/m2Above and 300g/m2Hereinafter, more preferably 90g/m2Above and 200g/m2The following. The proportion of the fibers having a cellulose skeleton in the fiber-made article is not particularly limited when the polymer soluble in the volatile solvent contained in the water repellent agent 2 is a solid in air at 25 ℃. On the other hand, when the polymer is a liquid in the air, the content of the fiber having a cellulose skeleton in the fiber product is preferably 1 mass% or more, and more preferably 20 mass% or more.
When the water repellent agent 2 is applied to, for example, clothes that are in direct contact with the skin of a user, the water repellent agent can be applied to at least one of the outer surface side of the clothes that is far from the skin of the user and the inner surface side of the clothes that is close to the skin of the user. When the water repellent treatment agent is applied to the outer surface side of the clothes, the amount of body fluid exuded is reduced, and therefore, it is preferable.
According to the surface treatment method of the present invention, a coating film for preventing permeation of a liquid such as urine can be formed only on one surface of a fibrous article having two opposing surfaces (for example, a front surface and a back surface), and the coating film is not formed on the other surface. The advantages of such "single-side coating of a fiber product" include the following: the waterproof property of the fiber product is minimized, and the original physical properties of the fiber product are maintained. When a fiber article is made waterproof by a conventionally known waterproofing treatment method, the waterproofing is excessively advanced, and physical properties such as water absorption, flexibility, and air permeability which are not originally intended to be reduced are greatly reduced, but according to the surface treatment method of the present invention, the fiber article can be easily made into a single-sided film.
An example of the fiber article to which the water repellent agent 2 is applied is a fiber article (hereinafter, also referred to as "water-absorbent fiber article") having a water absorption time of 30 seconds or less, preferably 20 seconds or less, more preferably 15 seconds or less, and further preferably 1 second or less by the dropping method of JIS L-1907. The water-absorbent fibrous article can absorb water and various aqueous liquids, and can absorb sweat, urine, and blood, which are one of body fluids, for example. Typically, the water-absorbent fibrous article is mainly composed of water-absorbent fibers. Examples of the water-absorbent fibers include natural fibers such as wood pulp, cotton, and hemp. The content of the water-absorbent fibers in the water-absorbent fibrous article is preferably 50 mass% or more, and more preferably 70 mass% or more, based on the total mass of the water-absorbent fibrous article. The water-absorbent fibrous article may be, for example, a sheet-like fibrous article having a thickness of about 0.3 to 20mm, and more specifically, may be in a form including 1 or 2 or more kinds of any of woven fabrics (woven fabrics), knitted fabrics, nonwoven fabrics, and papers.
The water repellent agent 2 can be used for barrier treatment of one side of various fiber articles including water-absorbent fiber articles, and is suitable for the following applications (1) to (10), for example. In general, the following (1) to (6) are applications for absorbing a small amount of liquid, specifically, a liquid amount of about 1mL or less, more preferably about 0.5mL or less, and the following (7) to (10) are applications for absorbing a larger amount of liquid than the small amount of liquid, specifically, a liquid amount of about 1 to 100mL, more preferably about 1 to 10 mL.
(1) The sock (water-absorbent fiber article) prevents foot sweat from transferring to the shoe and the insole (deodorization of the shoe) by making the non-skin-facing surface waterproof. The "non-skin-facing surface" herein refers to a surface facing the side opposite to the skin side of the user (the side facing away from the skin of the user) when the water-absorbent fibrous article is used, and the same applies hereinafter unless otherwise specified. The surface of the water-absorbent fibrous article opposite to the non-skin-facing surface (the surface facing the skin of the user during use) is referred to as the "skin-facing surface".
(2) The transfer of excreta (vaginal discharge, menstrual blood, etc.) to the lower body (clothing worn on the lower body) is prevented by the waterproofing of the non-skin-facing surface of the panties (absorbent fibrous article).
(3) The transfer of breast milk to clothes is prevented by making the non-skin-facing surface of a brassiere for women (water-absorbent fiber article) waterproof.
(4) The water-repellent effect of the back surface of the drawing paper (water-absorbent fiber article) prevents the water-based ink from running through.
(5) The concealment is improved by making one surface of the nonwoven fabric (water-absorbent fiber article) waterproof. The nonwoven fabric having improved concealing properties is suitable as a drip pad, for example. The food material is coated with the drip pad containing the non-woven fabric having improved concealment by single-sided blocking, whereby the penetration of drips is prevented by the waterproofed side (the side opposite to the food material side) of the non-woven fabric, and drips oozing from the food material are less likely to be observed from the outside.
(6) The dirt is prevented from transferring to the table by the waterproofing of the back surface of the table cloth.
(7) One surface of a wiper or a cloth (water-absorbing fiber article) is made waterproof to prevent dirt from adhering to the hand. (8) The inner surface (the surface on the body side of the user) of the bib (water-absorbent fiber article) is made waterproof, thereby preventing the transfer of saliva and splashed food to the dirt of clothes.
(9) The waterproof effect of the single surface of the foot pad (water-absorbing fiber product) prevents the ground from being wetted, prevents the ground from slipping, and prevents the propagation of mold and mixed bacteria.
(10) The sheet, the quilt cover, and the pillow cover (the surface on the opposite side to the body side of the user) are made waterproof, thereby preventing sweat from transferring to the mattress, the quilt, and the pillow (moisture prevention).
The water-repellent treatment agent 2 is also suitable for the following uses (11) to (15). The following (11) to (15) may be cases where the opposing both sides of the fiber product are made waterproof without making the above-mentioned one side waterproof.
(11) The outer pants (water-absorbent fiber article) are made waterproof on the skin-facing surface to prevent the adhesion of urine dirt.
(12) The stickiness of sweat is reduced by making shoes, socks, and hats (water-absorbing fiber articles) waterproof to the skin surface.
(13) The stickiness of sweat is reduced by making the surface (the surface on the body side of the user) of the sheet (absorbent fiber article) waterproof.
(14) The stickiness of sweat is reduced by making the skin-facing surface of the underwear (water-absorbent fiber article) waterproof.
(15) Sweat stain is prevented by making the non-skin-facing surface of the underwear (water-absorbent fiber article) waterproof.
The waterproof-treated product 1 for fiber preferably has instructions for use of the waterproof-treated product 1 for fiber described on the wall surface of the spray-type discharge container 3, the package body in which the waterproof-treated product 1 for fiber is packaged, or the like. As an explanation of the use, it is preferable to provide a mark recommended to spray the water repellent agent 2 onto the fiber product from a position spaced apart from the fiber product by about 10cm using the spray type spray container 3.
The water repellent treatment agent of the present invention may contain other components in addition to the above-mentioned volatile solvent and polymer. Examples of such other components include: deodorant, antibacterial agent, or perfume for the purpose of reducing urine odor; a surfactant or plasticizer for the purpose of improving removability by washing; a water-absorbing agent for improving the quick-drying property of excreted urine; dyes, pigments, etc. for the purpose of improving visibility after treatment. These other components are preferably contained in the water repellent treatment agent of the present invention in an amount of 5% by mass or less in total. From the viewpoint of making the effect of the present invention more remarkable, the water repellent treatment agent of the present invention preferably contains only a volatile solvent and a soluble polymer. The volatile solvent becomes a medium that can dissolve the components contained in the repellent treatment agent, and the content of the volatile solvent in the repellent treatment agent can be set as the remaining part of the components.
Examples
The present invention will be described in further detail below with reference to examples. However, the scope of the present invention is not limited by this example.
Examples 1 to 22 and comparative examples 1 to 5
The polymers shown in table 1 below were used. The polymer was dissolved in a volatile solvent shown in table 1 to obtain a water repellent agent having a concentration shown in table 1. The water repellent treatment agent was filled in a manual spray type spray container to produce water repellent treatment products for fibers of examples and comparative examples. As the manual type atomizer, model Z-155-C110-1-290(95-0) (opening diameter: 0.45mm) and model Z-155-C110-1-290(90-0) (opening diameter: 0.3mm) manufactured by Kabushiki Kaisha MITANI VALVE were used. The amount of each of the sprayers discharged per 1 operation was 0.15 mL. The bottle was made of "PH-100 No.2 white" manufactured by bamboo vessel Co.
< method for measuring viscosity of water repellent agent >
The viscosity of each water repellent agent was measured at 25 ℃ using a type B viscometer (type TVB-10 viscometer) manufactured by Toyobo industries Co., Ltd.
< method for measuring solubility in Water >
500g of water was added to a 1L glass beaker, and the mixture was stirred at a rotation speed of 100rpm using a rotor (made of fluororesin (PTFE), 8 mm. phi. times.50 mm) and kept at a temperature of 25 ℃ in a thermostatic bath. 0.1g of each polymer was added, and it was visually confirmed after 10 minutes whether or not the mixture was in a uniform transparent state. Each polymer was added in an amount of 0.1g each time until the mixture became non-uniform and transparent, and the solubility in water was measured.
When the polymer was uniformly transparent even when 50g of the polymer was added, the solubility in 100g of water at 25 ℃ was determined to be 10g or more after the measurement was completed at that time. When the transparency was not uniform when 0.1g of the polymer was added, the solubility in 100g of water at 25 ℃ was judged to be less than 20 mg.
Water: pure water having an electric conductivity of 1. mu.S/cm or less at 25 ℃ manufactured by G-10DSTSET, a pure water apparatus manufactured by Organo corporation.
The details of the polymer shown in table 1 are shown below. Amine equivalents were determined by the method described above. Regarding the ratio of the polysiloxane skeleton in the polymer, the polymer was dissolved in deuterated chloroform, and nuclear magnetic resonance (c) was used1H-NMR) apparatus "Mercury 400" (manufactured by Varian corporation).
OS-88: poly (N-propionylethyleneimine) modified silicone, weight average molecular weight: 11 ten thousand, and the proportion of the polysiloxane skeleton in the polymer was 88 mass%.
OS-71: poly (N-propionylethyleneimine) modified silicone, weight average molecular weight: 7 ten thousand, and the proportion of the polysiloxane skeleton in the polymer was 71 mass%.
DS-75: poly (N, N-dimethylacrylamide) modified silicone, weight average molecular weight: 10 ten thousand, and the proportion of the polysiloxane skeleton in the polymer was 75% by mass.
KF-864: amino-modified silicone (weight average molecular weight: 5 ten thousand, manufactured by shin Etsu chemical Co., Ltd.).
AP-3651: amino-modified silicone (manufactured by Dongliotongning corporation).
KS-7002: alkoxy oligomer (manufactured by shin-Etsu chemical Co., Ltd.).
KR-251: silicone resin (manufactured by shin-Etsu chemical Co., Ltd.).
KP-541: acrylic silicone (manufactured by shin-Etsu chemical Co., Ltd.).
TSPL-30 ID: a silicone coating agent (manufactured by shin-Etsu chemical Co., Ltd.).
Ultrahold (registered trademark) 8: (acrylic ester/t-butylacrylamide) copolymer (manufactured by BASF corporation).
DERMACRYL 79: an alkyl acrylate/octylacrylamide copolymer (manufactured by akzo nobel co., ltd.).
Gentrez ES-435: (vinyl methyl ether/butyl maleate) copolymer (50% isopropyl alcohol solution, manufactured by ISP Japan K.K.).
Amphomer 28-4910: (octylacrylamide/hydroxypropyl acrylate/butylaminoethyl methacrylate) copolymer (manufactured by Akzo Nobel Co., Ltd.).
Yukaforder AMPHOSET: (methacryloyloxyethylcarboxybetaine/alkyl methacrylate) copolymer (50% ethanol solution, manufactured by Mitsubishi chemical corporation).
DIAFORMER Z-651: (acrylic acid ester/lauryl acrylate/stearyl acrylate/ethylamine methacrylate) copolymer (30% ethanol (water 10%) solution, manufactured by Mitsubishi chemical corporation).
UNIDYNE TG-6071: fluorine-based polymer (10-20% n-butyl acetate solution, manufactured by Daikin Industries, Ltd.).
KF-6017: PEG-10 polydimethylsiloxane (manufactured by shin-Etsu chemical Co., Ltd.).
OS-51: poly (N-propionylethyleneimine) modified silicone, weight average molecular weight: 10 ten thousand, and the proportion of the polysiloxane skeleton in the polymer was 51% by mass.
PEG-1000: polyethylene glycol 1,000 (weight average molecular weight: 900 to 1100, manufactured by Fuji film and Wako pure chemical industries, Ltd.).
The details of the fiber product to be sprayed shown in table 1 are shown below.
Cloth 1: the trousers were produced by cutting square shapes of 10cm × 10cm in plan view from SUPIMA COTTON boxer shorts (93% by mass of COTTON and 7% by mass of polyurethane) manufactured by UNIQLO.
Fine white cloth No. 3 manufactured by japan standards association: cotton 100 mass%, size 10cm x 10cm
Cloth 3: square trousers for male use (88% by mass of polyester and 12% by mass of polyurethane) were cut out from alrism male boxer manufactured by UNIQLO, ltd, and produced in a shape of 10cm × 10cm in plan view.
Cloth 4: the trousers were produced by cutting 10cm × 10cm square in plan view from MEN' S boxoms boxer shorts (35 mass% cotton, 65 mass% polyester) manufactured by FREE ADVANCE.
The water repellent treatment products for fibers of examples and comparative examples were evaluated for single-sided barrier properties with respect to the spraying performance shown in table 1. The spray performance spray velocity shown in table 1 is the velocity of the liquid droplets of the water repellent agent when reaching the fiber product, and the velocity of the liquid droplets was measured by the above-described method. Further, the single-sided barrier property was measured by the following method. The results are shown in table 1.
< evaluation of Single-sided Barrier Property 1 >
The fiber-made articles shown in table 1 were placed on a vertical stand, and the water repellent treatment products for fiber of examples and comparative examples were disposed at a distance shown in table 1 from the fiber-made articles so as to face the test cloth. Next, the outer surface of the fiber article was dried by operating the spray type spray container 6 times, spraying the water repellent agent, and then leaving the container to stand for 10 minutes. In this way, a fiber article to which a treatment agent is applied is obtained, the treatment agent being applied to the outer surface side of one surface of the fiber article. Then, another fiber article (fine white cloth No. 3 manufactured by japan standards association) having a square shape in plan view of 10cm × 10cm was placed on a horizontal table, and the fiber article to which the treatment agent was applied was superimposed on the other fiber article so that the surface to which the treatment agent was applied was opposed to the other fiber article. In this state, 0.5mL of colored distilled water was dropped on the surface of the fiber article to which the treating agent had been applied, to which the treating agent had not been applied. The distilled water was colored with 0.01 mass% of a coloring material (blue No. 1). Then, the water absorption time of the distilled water on the surface side to which the treatment agent was not applied was measured for the fiber-made article to which the treatment agent was applied. When the water absorption time is within 5 seconds, it is judged that the water absorption is good. Next, the fiber article to which the treatment agent was applied was removed 1 minute after the dropping of distilled water, and the remaining fiber article was visually observed and evaluated according to the following evaluation criteria. In this test, the fiber article to which the treatment agent was applied was assumed to be an inner-lining garment such as an underwear, and the other fiber article was assumed to be an outer pants of an outer-lining garment. This test evaluates the water absorption of the surface to which no treatment agent is applied in the fiber article to which the treatment agent is applied, and also evaluates the barrier property of the surface to which the treatment agent is applied in the fiber article to which the treatment agent is applied, and evaluates the one-side barrier property. As for the barrier property, the higher the evaluation score, the higher the evaluation.
(evaluation criteria for Barrier Property)
And 5, dividing: the other fiber article had no portion to which distilled water adhered, 3 points: another fiber product has a point-like distilled water adhering portion in plan view having a maximum diameter length of 5mm or less, 0 point: the other fiber product has a point-like distilled water adhering portion having a maximum diameter length of more than 5mm when viewed from above.
< evaluation of Single-sided Barrier Property 2 >
The fiber-made articles shown in table 1 were placed on a vertical stand, and the water repellent treatment products for fiber of examples and comparative examples were disposed opposite to the test cloth and at a distance shown in table 1 from the fiber-made articles. Next, the outer surface of the fiber article was dried by operating the spray type spray container 6 times, spraying the water repellent agent, and then leaving the container to stand for 10 minutes. In this way, a fiber article to which a treatment agent is applied is obtained, the treatment agent being applied to the outer surface of one side of the fiber article. Then, the above-mentioned fiber article to which the treatment agent was applied was superimposed on another fiber article (fine white cloth No. 3 produced by japan standards association) having a square shape in a plan view of 10cm × 10cm and placed on a horizontal glass table so that the surface to which the treatment agent was applied was opposed to the other fiber article. In this state, 2mL of colored distilled water was dropped on the surface of the fiber article to which the treating agent had been applied, to which no treating agent had been applied. The distilled water was colored with 0.01 mass% of a coloring material (blue No. 1). Then, the liquid transfer to another fiber article was visually observed, and the time from the start of dropping of distilled water to the time when distilled water exuded to another fiber article was measured. The number of oozing was > 300 when the measurement was carried out for 300 seconds and the number of oozing was not found at 300 seconds.
[ Table 1]
As is clear from the results shown in table 1, the fiber article to which the treatment agent was applied in each example maintained the water absorbency of the fiber article on the surface side to which the treatment agent was not applied, and had the barrier property on the surface side to which the treatment agent was applied. As is clear from the above, in each example, a film of a water-repellent polymer was formed only on one side of the application site of the fiber article to which the water-repellent treatment agent was applied.
Industrial applicability
According to the present invention, by applying the present invention to clothes such as under-body underwear that directly contacts the excretory part of the wearer, body fluid excreted from the body can be effectively prevented from leaking from the clothes without impairing the water absorbency of the clothes itself. In addition, according to the surface treatment method of the present invention, the fiber article can be effectively surface-treated so that the body fluid excreted from the body can be effectively prevented from leaking from the fiber article without impairing the water absorbency of the fiber article.
Claims (10)
1. A water repellent treatment product for fibers, comprising: a water repellent agent containing a polymer dissolved in a volatile solvent, and a spray-type spray container filled with the water repellent agent,
the polymer has a solubility in water at 25 ℃ of less than 50mg/100g,
when the water repellent agent is sprayed onto a fiber product by the spray type spray container, the velocity of the sprayed water repellent agent at a position spaced apart from the spray type spray container by 10cm is 400 cm/sec or less as determined by the following method,
the velocity of the liquid droplet is obtained by dividing 5cm, which is a distance from a position 5cm away from the spray container to a position 10cm away from the spray container, by a moving time of the liquid droplet from the position 5cm away from the spray container to the position 10cm away from the spray container, and the unit of the moving time is seconds.
2. The water repellent treatment product for fiber according to claim 1, wherein the polymer satisfies the following (a) or (B):
(A) a contact angle with water of 70 degrees or more and a solid in air at 25 ℃,
(B) a liquid having an amino group and an amine equivalent of 5,000g/mol or less.
3. The water repellent treatment product for fiber according to claim 1 or 2, wherein an opening diameter of the ejection port of the spray container is 0.3mm or more and 0.6mm or less.
4. The water repellent treatment product for fiber according to any one of claims 1 to 3, wherein the viscosity of the water repellent treatment agent at 25 ℃ is 20 mPas or less.
5. A surface treatment method for a fiber article, comprising a step of treating the surface of the fiber article with a water repellent treatment agent containing a polymer dissolved in a volatile solvent,
the polymer has a solubility in water at 25 ℃ of less than 50mg/100g,
the water repellent agent is sprayed onto the fiber product under the condition that the speed of the droplets of the water repellent agent reaching the fiber product is 400 cm/sec or less by using a spray type spray container.
6. The surface treatment method for a fiber product according to claim 5, wherein the spray-type discharge vessel has a discharge port with an opening diameter of 0.3mm to 0.6 mm.
7. The surface treatment method for a fiber product according to claim 5 or 6, wherein a water repellent agent having a viscosity of 20 mPas or less at 25 ℃ is used as the water repellent agent.
8. The surface treatment method for a fibrous article according to any one of claims 5 to 7, wherein spraying is performed in a range in which the distance between the spray type spray container and the fibrous article is 3cm or more and 30cm or less.
9. The surface treatment method for a fiber product according to any one of claims 5 to 8, wherein the spraying is performed so that the water repellent agent does not reach a surface of the fiber product opposite to a surface on which the water repellent agent is sprayed.
10. The surface treatment method for a fiber product according to any one of claims 5 to 9, wherein the fiber product is a lower body underwear for men.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018230135 | 2018-12-07 | ||
| JP2018-230135 | 2018-12-07 | ||
| JP2019158438A JP2020094317A (en) | 2018-12-07 | 2019-08-30 | Fiber waterproofed product and surface processing method of fiber product |
| JP2019-158438 | 2019-08-30 | ||
| PCT/JP2019/047741 WO2020116597A1 (en) | 2018-12-07 | 2019-12-06 | Fiber waterproofing product and surface treatment method for fiber article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113165010A true CN113165010A (en) | 2021-07-23 |
Family
ID=71084607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980080263.9A Pending CN113165010A (en) | 2018-12-07 | 2019-12-06 | Water-repellent treatment product for fiber and method for surface treatment of fiber-made article |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2020094317A (en) |
| CN (1) | CN113165010A (en) |
| TW (1) | TW202039961A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102311742B1 (en) * | 2021-07-28 | 2021-10-12 | 강인종 | A manufacturing method for waterproof mask non-woven fabric, mask fabric and mask thereby |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2020094317A (en) | 2020-06-18 |
| TW202039961A (en) | 2020-11-01 |
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