JP7222853B2 - Fiber treatment agents and fiber surface treatment products containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fiber treatment agent and a fiber surface treatment article containing the same.

BACKGROUND ART Absorbent articles of the type that are attached to the inner side of a textile article such as underwear and absorb mainly urine are known. Patent Document 1 discloses, as one type of such absorbent article, a leakage-preventing cuff that blocks the lateral flow of excreted urine for the purpose of preventing leakage even if a large amount of urine is excreted at once. A male incontinence pad is described. The male incontinence pad described in the document is sufficiently satisfactory for users who excrete a lot.

Apart from this technology, the present applicant has previously developed a silicone-based fiber surface treatment agent as a fiber surface treatment agent that improves the flexibility, smoothness, and water repellency of fibers and is excellent in deepening the color. proposed (see Patent Document 2). The document describes a spraying method as a method for attaching the fiber surface treatment agent to the surface of the fiber.

JP 2015-188714 A JP-A-4-163374

Among elderly men, not a few people have a problem that they cannot drain all the urine at the time of urination, and a small amount of urine leaks after the completion of urination, in other words, dripping of urine after urination occurs, and urine seeps into the clothes. Since the male incontinence pad described in Patent Document 1 has a high absorption capacity, it is not a direct countermeasure against a small amount of urine leakage. It is not impossible to wear a high absorbent capacity pad, but in that case the high absorbent capacity makes the pad bulky, which makes it difficult for others to notice that you are wearing the pad. There are many people who have anxiety that they will not be able to Moreover, some users feel reluctance to use the pad itself. Therefore, there is a high demand for a technology that can solve the above problems without using bulky items such as male incontinence pads, and the technology has not yet been provided while using everyday clothing such as undergarments. do not have.

Regarding the coating method of the treatment agent described in Patent Document 2, since the spraying method is adopted, the user can easily and uniformly apply the water repellent agent. However, the technology described in Patent Literature 2 is not intended for use by the above-described user with a small amount of excretion.

When the user sprays the fiber treatment agent onto the fiber product by spraying, not all the sprayed droplets of the treatment agent adhere to the fiber product, and some of the droplets scatter. Some of the scattered fiber treatment agents may adhere to the floor, for example. Depending on the type of treatment agent, the floor may become slippery, especially if the floor is a flooring floor.

Therefore, an object of the present invention is to effectively prevent body fluids excreted from the body from oozing out of the clothes while using the clothes such as undergarments that are usually used as they are, and to unintentionally adhere to the floor. To provide a fiber treatment agent which prevents the floor from slipping even when it is wetted.

The present invention comprises a volatile solvent and a polymer or a mixture of two or more polymers soluble in the volatile solvent,
one of said polymers or two or more of said polymers has a solubility in water at 25° C. of less than 50 mg/100 g;
The content of one polymer or a mixture of two or more polymers is 3% by mass or more and 15% by mass or less,
One of the polymers or a mixture of two or more of the polymers has a yield stress at 25° C. of 0.6 MPa or more,
One kind of said polymer or a mixture of two or more kinds of said polymers provides a fiber treatment agent having a contact angle with water of 90 degrees or more.

The present invention also provides a fiber surface treatment article comprising the above fiber treatment agent and a manually operated mist spray container filled with the fiber treatment agent.

The present invention also provides a fiber surface treatment article containing the above fiber treatment agent in a spray container or coating container.

According to the present invention, it is possible to effectively prevent bodily fluids excreted from the body from oozing out of the clothes while using the clothes such as undergarments that are usually used as they are. Provided is a fiber treatment agent that prevents the floor from slipping even in such cases.

The present invention will be described below based on its preferred embodiments. The fiber treatment agent of the present invention is generally liquid in its state of use. The fiber treatment agent of the present invention is contained, for example, in a manually operated mist spray container, and is sprayed onto the fibers from the spray container.

The fiber treatment agent of the present invention contains a volatile solvent as one of its constituent components. The volatile solvent is preferably a substance having a saturated vapor pressure of 3000 Pa or higher at the temperature at which the fiber treatment agent is used. Volatile solvents include water and organic solvents. A mixed solvent of water and a water-soluble organic solvent may be used as the volatile solvent. Examples of volatile organic solvents include alcohols, esters, nitriles, ethers, hydrocarbons, ketones, amines, acetic acid, and the like. One of these volatile solvents can be used alone, or two or more of them can be used in combination. When two or more volatile solvents are used in combination, the saturated vapor pressure is the saturated vapor pressure of the volatile solvent having the lowest saturated vapor pressure among the volatile solvents used. Among these volatile solvents, water and alcohol are preferable from the viewpoint of achieving both the solubility of the polymer described later and the drying time of the fiber treatment agent, and one or two selected from the group consisting of water, ethanol, and propanol. It is more preferable to use a combination of the above.

When alcohol is used as the volatile solvent, it is preferable to use a monohydric or polyhydric aliphatic alcohol having 1 to 5 carbon atoms, and a monohydric alcohol having 2 to 4 carbon atoms, such as , ethanol, propanol and butanol are more preferably used. When an ester is used as the volatile solvent, 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 is preferably used, and an ester of a monovalent aliphatic alcohol having 1 to 2 carbon atoms and a monovalent fatty acid having 1 to 4 carbon atoms, such as ethyl acetate, methyl propionate and butyl acetate etc. is more preferable. When nitrile is used as the volatile solvent, it is preferable to use an alkane nitrile having 2 or more and 3 or less carbon atoms, such as acetonitrile. In addition, from the viewpoint of preventing ignition and ignition, it is preferable to use water and other volatile solvents in combination. It is more preferably contained in an amount of 1 part or more, preferably 50 parts by mass or less, and more preferably 20 parts by mass or less.

The fiber treatment agent of the present invention may contain a non-volatile solvent in addition to the volatile solvent described above as long as the effects of the present invention are not impaired. However, it is preferable that the solvent contained in the fiber treatment agent of the present invention is only a volatile solvent, from the viewpoint of ensuring the effects of the present invention.

The fiber treatment agent of the present invention contains a polymer soluble in the volatile solvent in addition to the volatile solvent. A polymer soluble in a volatile solvent is a polymer compound having a solubility of 1 g or more in 100 g of the volatile solvent used in the present fiber treatment agent at 25°C. The fiber treatment agent of the present invention contains only one kind of polymer that is soluble in the volatile solvent contained therein, or contains two or more kinds of polymers in the form of a mixture. As long as the effects of the present invention are not impaired, the fiber treatment agent of the present invention may contain a polymer that is insoluble in the volatile solvent contained therein. However, the fiber treatment agent of the present invention preferably contains only a polymer soluble in the volatile solvent contained therein, from the viewpoint of ensuring the effects of the present invention. In the following description, a polymer that can be dissolved in a volatile solvent is also referred to as "soluble polymer". Since the fiber treatment agent of the present invention contains a soluble polymer, the fibers treated with the fiber treatment agent of the present invention have good water repellency.

The solubility of a soluble polymer in a volatile solvent is measured, for example, by the following method. That is, 100 g of a volatile solvent is stirred in a closed vessel at 25° C. while a soluble polymer is added and stirred for 24 hours to dissolve. As the amount of the soluble polymer added to the volatile solvent is increased, it is visually confirmed that the soluble polymer cannot be completely dissolved and remains in the liquid. ). When the soluble polymer is solid, it is dissolved in the form of powder under 16 mesh.

The soluble polymer contained in the fiber treatment agent of the present invention has a solubility in water at 25°C of less than 50 mg/100 g. Treating the surface of a textile article with a polymer having a water solubility of less than 50 mg/100 g at 25° C. can effectively prevent bodily fluids from oozing out of clothing. The solubility in water at 25° C. is preferably 40 mg/100 g or less, more preferably 30 mg/100 g or less, still more preferably 20 mg/100 g or less, from the viewpoint of easily imparting water repellency to the fiber surface. Preferably less than 20 mg/100 g.

In the fiber treatment agent of the present invention, the content of the soluble polymer is preferably 3% by mass or more, more preferably 4% by mass or more, from the viewpoint of enhancing the water repellency of the fiber or textile article to be treated. 4.5% by mass or more is more preferable. In the fiber treatment agent of the present invention, the content of the soluble polymer is preferably 15% by mass or less, more preferably 10% by mass or less, and 7% by mass, from the viewpoint of the processing efficiency and sprayability of the fiber treatment agent. More preferred are: In the fiber treatment agent of the present invention, the content of the soluble polymer is preferably 3% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 10% by mass or less, and 4.5% by mass or more and 7% by mass or less. More preferred. The above-mentioned content is the content of the soluble polymer when the fiber treatment agent of the present invention contains only one kind of soluble polymer, and when it contains two or more kinds of soluble polymers, all is the total content of soluble polymers in

The soluble polymer contained in the fiber treatment agent of the present invention has a yield stress of preferably 0.6 MPa or more, more preferably 1 MPa or more, more preferably 1.5 MPa at 25° C., from the viewpoint of ensuring the effects of the present invention. The above is more preferable. Although the upper limit of the yield stress of the soluble polymer is not particularly limited, the yield stress at 25° C. is preferably 20 MPa or less, more preferably 10 MPa or less, and 5 MPa or less from the viewpoint of good sprayability. It is even more preferable to have Since the yield stress of the soluble polymer is at least the above value, when the fiber treatment agent of the present invention unintentionally adheres to an article other than the object to be treated, for example, when it adheres to a floor, the floor becomes slippery. is effectively prevented from becoming The reason for this is that when the fiber treatment agent of the present invention contains a soluble polymer having a yield stress of the above value or more, the film formed from the fiber treatment agent becomes hard. The reason why the yield stress is measured at 25° C. is that the fiber treatment agent of the present invention is usually used at room temperature.

The yield stress of the soluble polymer is the yield stress of the soluble polymer when the fiber treatment agent of the present invention contains only one soluble polymer. When the fiber treatment agent of the present invention contains a mixture of two or more soluble polymers, it means the yield stress of the soluble polymer mixture. When the fiber treatment agent of the present invention contains two or more soluble polymers in the form of a mixture, as long as the yield stress of the soluble polymer mixture is at least the above value, The yield stress of the soluble polymer does not need to be above the above values. Specifically, as long as the yield stress of the mixture of soluble polymers is at least the above value, (i) the yield stress of a portion of the soluble polymer constituting the mixture of soluble polymers is at least the above value, and The yield stress of the remainder of the soluble polymer may be less than said value, and (ii) the yield stress of all soluble polymers making up the mixture of soluble polymers may be greater than or equal to said value, or (iii) the yield stress of all soluble polymers making up the mixture of soluble polymers may be less than said value;

The yield stress of a soluble polymer is measured by the method described below. That is, the fiber treatment agent of the present invention is allowed to stand for 5 hours, and after sufficiently removing air bubbles, it is cast on a vat, dried at 25 ° C. and 50% RH for 48 hours, and further heated at 80 ° C. in a vacuum dryer. and dried for 48 hours to form a 1 mm thick film. Rectangular specimens with a width of 2 mm and a length of more than 10 mm are cut from this membrane. Set each longitudinal end of the test piece in each chuck of the tensile tester. As a tensile tester, for example, Tensilon "RTC series" manufactured by A&D Co., Ltd. is used. The chuck-to-chuck distance is 10 mm. The test piece is pulled at a tensile speed of 1000 mm/min, and the stress at which plastic deformation begins beyond the elastic limit of the test piece is measured. The measurement is performed 5 times, and the average value is taken as the yield stress (unit: MPa).

The soluble polymer contained in the fiber treatment agent of the present invention has a contact angle with water of preferably 90 degrees or more, more preferably 100 degrees or more. The contact angle is an index of the hydrophobicity of the fiber surface treated with the fiber treatment agent. The larger the contact angle value, the stronger the hydrophobicity of the fiber treatment agent, and the smaller the contact angle value, the weaker the hydrophobicity of the fiber treatment agent. The upper limit of the contact angle is not particularly limited, but if the upper limit is as high as about 150 degrees, the effects of the present invention are sufficiently exhibited.

When the fiber treatment agent of the present invention contains only one type of soluble polymer, the contact angle is the contact angle between the soluble polymer and water. When the fiber treatment agent of the present invention contains a mixture of two or more soluble polymers, the contact angle is the contact angle between the soluble polymer mixture and water. When the fiber treatment agent of the present invention contains a mixture of two or more soluble polymers, as long as the contact angle of the mixture of soluble polymers is 90 degrees or more, It is not necessary that the contact angle of the polymer is 90 degrees or more. Specifically, as long as the contact angle of the mixture of soluble polymers is 90 degrees or more, (i) some of the soluble polymers constituting the mixture of soluble polymers have a contact angle of 90 degrees or more, and the remaining The soluble polymer may have a contact angle of less than 90 degrees, (ii) all of the soluble polymers making up the mixture of soluble polymers may have a contact angle of 90 degrees or greater, or (iii) the dissolution The contact angle of all soluble polymers that make up the mixture of soluble polymers may be less than 90 degrees.

A contact angle is measured by the method described below. A measurement sample film is formed in the same manner as for the yield stress described above. That is, the fiber treatment agent of the present invention is allowed to stand for 5 hours, and after sufficiently removing air bubbles, it is cast on a vat, dried at 25° C. and 50% RH for 48 hours, and further heated at 80° C. in a vacuum dryer. Dry for 48 hours to form a film. This film is used as a measurement sample. The measurement environment shall be a temperature of 23±2° C. and a relative humidity of 50±5% RH. A droplet of 1 μL of ion-exchanged water is attached to the surface of the sample to be measured for the contact angle, and the state of the contact surface between the droplet and the membrane is recorded from the side. The contact angle is measured based on multiple images obtained by recording. As a measuring device, for example, a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd. is used. Among the plurality of images, 10 images with a clear outline of the droplet are selected, and the contact angle of the droplet with respect to the reference surface is measured for each of the 10 images. The average value of these contact angles is taken as the contact angle between the soluble polymer and water.

The advantages of imparting water repellency to fibers with the fiber treatment agent of the present invention are as follows. By imparting water repellency to the outer surface of underpants, which are textile articles such as briefs and trunks, with the fiber treatment agent of the present invention, the fibers present on the inner surface of the underpants absorb a small amount of urine instead of a pad, and Since it suppresses the seepage of absorbed urine to the outer surface, it is extremely effective as a measure against leakage of a small amount of urine, in other words, as a measure against dripping of urine after urination without wearing an article such as an incontinence pad.

When the fiber treatment agent of the present invention contains two or more soluble polymers in the form of a mixture, at least one of the soluble polymers constituting the mixture of soluble polymers (A1) yields at 25°C a soluble polymer having a stress of 0.6 MPa or more and a contact angle with water of less than 90 degrees; A soluble polymer having a contact angle with water of less than 6 MPa and 90 degrees or more is preferable from the viewpoint of slip prevention. From the viewpoint of making this effect more pronounced, the soluble polymer (A1) more preferably has a yield stress of 0.6 MPa or more, more preferably 1.5 MPa or more. The contact angle of the soluble polymer (A1) is more preferably 70 degrees or less, more preferably 50 degrees or less. On the other hand, the soluble polymer (A2) more preferably has a yield stress of 0.4 MPa or less. Further, the soluble polymer (A2) preferably has a contact angle of 90 degrees or more, more preferably 100 degrees or more. The soluble polymer (A1) can be used alone or in combination of two or more. Similarly, the soluble polymer (A2) can be used alone or in combination of two or more.

When the fiber treatment agent of the present invention contains two or more soluble polymers in the form of a mixture, the soluble polymers constituting the mixture of soluble polymers are the soluble polymers of (A1) and (A2) It may be the polymer alone, or the soluble polymers (A1) and (A2) and other soluble polymers. From the viewpoint of further enhancing the anti-slip effect, it is preferable that the soluble polymers constituting the mixture of soluble polymers are only the soluble polymers (A1) and (A2).

The yield stress and contact angle with water of the soluble polymer (A1) are measured by the methods described above. In this case, a solution is prepared by dissolving the soluble polymer (A1) in a volatile solvent, the solution is used to form a film for measurement according to the method described above, and the yield stress and contact angle are measured using the film. Just measure. The same applies to the soluble polymer (A2).

When the fiber treatment agent of the present invention contains the soluble polymers (A1) and (A2), the ratio of the soluble polymer (A1) to the total amount of the soluble polymer is 20 from the viewpoint of slip prevention. % by mass or more is preferable, 30% by mass or more is more preferable, and 40% by mass or more is even more preferable. Further, from the viewpoint of imparting water repellency to the fiber surface, the ratio of the soluble polymer (A1) to the total amount of the soluble polymer is preferably 90% by mass or less, more preferably 70% by mass or less, and further 50% by mass or less. preferable. The ratio of the soluble polymer (A1) to the total amount of the soluble polymer is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and further 40% by mass or more and 50% by mass or less. preferable.

On the other hand, from the viewpoint of imparting water repellency to the fiber surface, the ratio of the soluble polymer (A2) to the total amount of the soluble polymer is preferably 10% by mass or more, more preferably 30% by mass or more, and further 50% by mass or more. preferable. From the viewpoint of slip prevention, the ratio of the soluble polymer (A2) to the total amount of the soluble polymer is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. The ratio of the soluble polymer (A2) to the total amount of the soluble polymer is preferably 10% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and further 50% by mass or more and 60% by mass or less. preferable.

When the fiber treatment agent of the present invention contains the soluble polymers (A1) and (A2), the ratio of the soluble polymer (A1) to the soluble polymer (A2) is [(A1 ) of the soluble polymer / (A2) of the soluble polymer], from the viewpoint of slip prevention, preferably 0.25 or more, more preferably 0.43 or more, 0.7 or more More preferred. In addition, the value of [mass of soluble polymer (A1)/mass of soluble polymer (A2)] is preferably 9 or less, more preferably 2.5 or less, from the viewpoint of imparting water repellency to the fiber surface. , 1 or less is more preferable. The value of [mass of soluble polymer (A1)/mass of soluble polymer (A2)] is preferably 0.25 or more and 9 or less, more preferably 0.43 or more and 2.5 or less, and 0.7 or more. 1 or less is more preferable.

The soluble polymer contained in the fiber treatment agent of the present invention is preferably a silicone-based polymer from the viewpoint of slip prevention and imparting water repellency to the fiber surface. Examples of silicone-based polymers include silicone resins, (acrylic acid/dimethicone) copolymers, silicone graft copolymers, etc. Among them, silicone graft copolymers are more preferred. From the viewpoint of making these advantages more conspicuous, the weight average molecular weight of the graft chain in the silicone graft copolymer is preferably 800 or more, more preferably 900 or more and 10000 or less, and 1000 or more and 5200 or less. is more preferred. When the fiber treatment agent of the present invention contains only one type of soluble polymer, the weight average molecular weight of the grafted chain of the soluble polymer is preferably at least the above value. When the fiber treatment agent of the present invention contains a mixture of two or more soluble polymers, (i) the weight of the grafted chain of at least one soluble polymer constituting the mixture of soluble polymers The average molecular weight is preferably at least the above value, and (ii) it is more preferable that the weight average molecular weight of the grafted chains of all the soluble polymers constituting the mixture of soluble polymers is at least the above value. The weight average molecular weight can be determined as a standard polystyrene conversion value by gel permeation chromatography (GPC) (DP-8020) manufactured by Tosoh Corporation, for example.

The type of the soluble polymer contained in the fiber treatment agent of the present invention is not particularly limited as long as it has the above solubility and the above yield stress. Examples of the polymer include silicone-based polymers, acrylic resins, and fluorine-based polymers. Examples of silicone-based polymers include silicone resins, (acrylic acid/dimethicone) copolymers, silicone graft copolymers, and the like. It has been found that very satisfactory results are obtained with the silicone graft copolymers described below. A polysiloxane skeleton is a structure composed of --O--Si--O--Si-- bonds, and typically includes silicone. As the silicone, it is preferable to use various modified silicones from the viewpoint of further slip prevention. Examples of modified silicones include, but are not limited to, fatty acid-modified silicones and acrylic silicones. Of the modified silicones, it is preferable to use a silicone graft copolymer, since the effects of the present invention are more pronounced. When the fiber treatment agent of the present invention contains only one type of soluble polymer, the soluble polymer is preferably a silicone graft copolymer. When the fiber treatment agent of the present invention contains two or more soluble polymers in the form of a mixture, (i) at least one soluble polymer constituting the mixture of soluble polymers is a silicone-grafted copolymer. Preferably, (ii) all soluble polymers that make up the mixture of soluble polymers are silicone graft copolymers.

As the silicone graft copolymer, it is possible to use those having a polysiloxane skeleton as a main chain and groups derived from N-acylalkyleneimine, acrylic acid, acrylate, acrylic ester or acrylamide in side chains, It is preferable from the viewpoint of anti-slip properties and the viewpoint of imparting water repellency to fibers. Silicone graft copolymers are roughly classified into two types: physically crosslinked products in which crosslink points are formed by physical interaction, and chemical crosslinked products in which crosslinks are linked by covalent bonds. From the viewpoint of being easily dissolved in a volatile solvent, it is preferable to use a physically crosslinked product in the present invention.

Physically crosslinked silicone graft copolymers include, for example, poly(N-acylalkyleneimine)-modified silicone, poly(N,N-dimethylacrylamide)-modified silicone, fatty acid-modified silicone, acrylic silicone, sugar-modified silicone 63-139106), polyglycerin-modified silicone (JP-A-2004-339244), polyamino acid-modified silicone (JP-A-2002-145724), silicone graft acrylate polymer (JP-A-4-342513), silicone PEG block polymer (JP-A-4-234307) is exemplified. Among these, poly(N-acylalkyleneimine)-modified silicone and poly(N,N-dimethylacrylamide)-modified silicone are preferably used because of their high solubility in volatile solvents.

Examples of the above-mentioned poly(N-acylalkyleneimine)-modified silicone include, for example, a poly(N-acylalkyleneimine) segment and an organopolysiloxane segment in the molecule, and the end of the organopolysiloxane segment or Preferably, the poly(N-acylalkyleneimine) segment is bonded to at least one silicon atom of the side chain via an alkylene group. The alkylene group preferably has 2 to 20 carbon atoms. Instead of this alkylene group, a group containing a heteroatom 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 heteroatoms is preferably 1-3.

Specific examples of preferred poly(N-acylalkyleneimine)-modified silicones include poly(N-formylethyleneimine)-modified silicone, poly(N-acetylethyleneimine)-modified silicone, poly(N-propionylethyleneimine)-modified silicone and the like. Among them, poly(N-propionylethyleneimine)-modified silicone ( The INCI name: Polysilicone-9) is preferred.

As the above-mentioned poly(N,N-dimethylacrylamide)-modified silicone, for example, it has an organopolysiloxane segment and a polymer segment derived from an unsaturated monomer in the molecule, and the end of the organopolysiloxane segment Alternatively, a polymer segment derived from the unsaturated monomer is preferably bonded to at least one silicon atom of the side chain via an alkylene group. Specific examples include organopolysiloxane graft polymers containing repeating units derived from N,N-dimethylacrylamide (DMAAm) in polymer segments derived from unsaturated monomers. The alkylene group preferably has 2 to 20 carbon atoms. Instead of this alkylene group, a group containing a heteroatom 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 heteroatoms is preferably 1-3. In the polymer segment derived from the unsaturated monomer, the portion other than the repeating unit derived from DMAAm consists of repeating units derived from unsaturated monomers copolymerizable with DMAAm (excluding DMAAm). Repeating units derived from unsaturated monomers copolymerizable with DMAAm include olefins, halogenated olefins, vinyl esters, (meth)acrylates, or (meth)acrylamides (excluding DMAAm). Examples include repeating units derived from unsaturated monomers.

Specific examples of olefins copolymerizable with DMAAm include ethylene, propylene, and isobutylene. Specific examples of halogenated olefins include vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride. Specific examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate. Specific examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylic (Meth)acrylic acid ester having an alkyl group having 1 to 16 carbon atoms such as cyclohexyl acid; ) acrylic acid ester; 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; excluding); N-alkyl (meth)acrylamides such as N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-tert-octyl (meth)acrylamide; diacetone N-monosubstituted (meth)acrylamides having a carbonyl group as a substituent on the nitrogen atom such as (meth)acrylamide; N,N-dimethylaminopropyl (meth)acrylamide having an amino group as a substituent on the nitrogen atom N-monosubstituted (meth)acrylamides having; N-monosubstituted (meth)acrylamides having a hydroxyl group as a substituent on the nitrogen atom such as N-methylol (meth)acrylamide and N-hydroxyethyl (meth)acrylamide be done.

A specific example of a preferred poly(N,N-dimethylacrylamide)-modified silicone is an N,N-dimethyl Acrylamide-modified silicones can be mentioned.

Although it is not entirely clear why the use of the silicone graft copolymer described above as the soluble polymer contained in the fiber treatment agent of the present invention further improves the anti-slip properties, the present inventors have made the following points. thinking. When the volatile solvent evaporates from the fiber treatment agent and the soluble polymer solidifies to form a film, the polysiloxane skeleton of the main chain, which is the water-repellent part, gathers on the surface of the film, and the side that is the hydrophilic part The chains become clustered inside the membrane. As a result, a hard film is likely to be formed, which is thought to be the reason for the improved anti-slip properties of the film. However, the scope of the present invention is not bound by this theory.

In particular, when the fiber treatment agent of the present invention contains a mixture of two or more soluble polymers, and the mixture contains the soluble polymer (A1) and the soluble polymer (A2), these (A1) and The soluble polymer (A2) is preferably a silicone having a polysiloxane skeleton as a main chain. In this case, the proportion of the polysiloxane skeleton in the soluble polymer (A1) is preferably 40% by mass or more and less than 70% by mass, more preferably 50% by mass or more and less than 70% by mass. When the ratio of the polysiloxane skeleton in the soluble polymer (A1) is within this range, the physical properties of the graft chain rather than the silicone main chain become dominant, resulting in an advantageous effect of increasing the yield stress. be.

On the other hand, the proportion of the polysiloxane skeleton in the soluble polymer (A2) is preferably 70% by mass or more. The proportion of the polysiloxane skeleton in the soluble polymer (A2) is preferably 99% by mass or less, more preferably 90% by mass or less. In particular, the proportion of the polysiloxane skeleton in the soluble polymer (A2) is preferably 70% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 90% by mass or less. When the ratio of the polysiloxane skeleton in the soluble polymer (A2) is within this range, the advantageous effect of exhibiting the hydrophobic properties of silicone is exhibited.

The ratio of the polysiloxane skeleton in the soluble polymers (A1) and (A2) can be determined, for example, by dissolving the soluble polymers in deuterated chloroform and analyzing them with a nuclear magnetic resonance ( ¹ H-NMR) apparatus "Mercury 400" (manufactured by Varian). ) can be measured using

Examples of the acrylic resin include acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid esters, and acrylic acid derivatives such as methacrylic acid esters as main components, and those obtained by homopolymerization or copolymerization are used. be able to. Specifically, (acrylic acid / acrylamide) copolymer such as (acrylic acid / t-butyl acrylamide) copolymer, (acrylic acid / acrylamide / acrylic acid alkyl ester) copolymer, (alkylacrylamide/acrylic acid/alkylaminoalkylacrylamide/polyethylene glycol methacrylate) copolymer, acrylic acid alkyl ester polymer, methacrylic acid alkyl ester copolymer, (acrylic acid/acrylic acid alkyl ester) copolymer, (acrylic acid/methacrylic acid alkyl ester) copolymer, (methacrylic acid/acrylic acid alkyl ester) copolymer, (methacrylic acid/methacrylic acid alkyl ester) copolymer, (acrylic acid (alkyl acrylate/t-butyl acrylamide) copolymer, (alkyl acrylate/octyl acrylamide) copolymer, (acrylic acid/alkyl acrylate/t-butyl (acrylic acid/acrylic acid alkyl ester/alkyl acrylamide) copolymer such as acrylamide) copolymer, (methacrylic acid/acrylic acid alkyl ester/alkyl acrylamide) copolymer, (methacryloyloxyethyl carboxybetaine/methacrylic acid alkyl ester) ) copolymer, (alkylacrylamide/alkylaminoalkylacrylamide/polyethylene glycol methacrylate) copolymer, (octylacrylamide/hydroxypropyl acrylate/butylaminoethyl methacrylate) copolymer, (alkylacrylamide/alkyl acrylate/ Alkylaminoalkylacrylamide/polyethylene glycol methacrylate) copolymer, (alkyl acrylate/diacetone acrylamide) copolymer, (styrene/acrylic acid) copolymer, (styrene/alkyl acrylate) copolymer, ( styrene/acrylamide) copolymer, urethane-acrylic copolymer, (vinylpyrrolidone/acrylic acid/methacrylic acid) copolymer, (vinylpyrrolidone/acrylic acid alkyl ester/methacrylic acid) copolymer, (octylacrylamide/ Hydroxypropyl acrylate/butylaminoethyl methacrylate) polymer, (methacryloyloxyethyl carboxybetaine/methacrylate) acrylic acid alkyl ester) polymer, (acrylic acid/acrylic acid alkyl ester/methacrylic acid ethylamine oxide) copolymer, and the like.

Examples of the fluorine-based polymer include those obtained by polymerizing fluorinated olefins such as polytetrafluoroethylene and polyvinylidene fluoride, as well as those obtained by partially modifying them.

As the polymer contained in the water repellent treatment agent, other polymers having the above-described solubility and yield stress can be used in addition to silicone-based polymers, acrylic resins, and fluorine-based polymers. Examples of other soluble polymers include (vinyl methyl ether/maleic acid) copolymers, (vinyl methyl ether/maleic acid alkyl ester) copolymers, (vinyl methyl ether/butyl maleate) copolymers, and the like. A maleic acid-based polymer can be mentioned.

The fiber treatment agent of the present invention has a solubility in water at 25°C of less than 50 mg/100 g, a yield stress at 25°C of 0.6 MPa or more, and a contact angle with water of 90 degrees or more. In addition to the soluble polymer, (B) a polymer having a solubility in water at 25° C. of 50 mg/100 g or more may be included. The content of the polymer (B) in the fiber treatment agent of the present invention is preferably 0.01% by mass or more and 7.5% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and 0.4% by mass. Above 3.5% by mass or less is more preferable.

Examples of the polymer (B) include nonionic resins that do not ionize when dissolved in a volatile solvent, water-soluble polymers with a high content of water-soluble monomers such as the acrylic resins, and water-soluble polymers that form salts. . Nonionic resins include (vinylpyrrolidone/methacrylamide/vinylimidazole) copolymers, polyvinylcaprolactam, and the like.

The fiber treatment agent of the present invention may contain other components in addition to the volatile solvent and soluble polymer described above. Such other ingredients include, for example, deodorants/antibacterial agents/fragrance agents for the purpose of reducing urine odor, surfactants/plasticizers for the purpose of improving removability by washing, and excreted urine. Examples include a water-absorbing agent for improving dryness, and dyes and pigments for improving visibility after treatment. The total amount of these other components in the fiber treatment agent of the present invention is preferably 5% by mass or less. From the viewpoint of making the effect of the invention more remarkable, the fiber treatment agent of the invention preferably contains only a volatile solvent and a soluble polymer. The volatile solvent serves as a medium capable of dissolving the components contained in the fiber treatment agent, and the content of the volatile solvent in the fiber treatment agent can be the balance of the components.

The fiber treatment agent of the present invention has a viscosity at 25° C. of preferably 20 mPa·s or less, more preferably 15 mPa·s or less, still more preferably 10 mPa·s or less, from the viewpoint of mist uniformity when sprayed. s or less. The lower limit of the viscosity is not particularly limited, and the lower the better, but the effect of the present invention can be fully exhibited if the viscosity is as low as 5 mPa·s. The viscosity of the fiber treatment agent is measured using a Brookfield viscometer. As the B-type viscometer, for example, a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. can be used. The measurement conditions are spindle No. M1 and the number of revolutions are appropriately selected according to the viscosity.

The fiber treatment agent of the present invention can be applied, for example, by directly spraying the treatment agent on the fibers themselves and textile articles such as clothing (hereinafter collectively referred to as "fibers and the like"). When the fiber treatment agent of the present invention is applied to fibers by spraying, a fiber surface treatment article containing the fiber treatment agent in a manually operated mist spray container may be used. When using this fiber surface treatment product, the fiber treatment agent may be sprayed onto the fibers or the like from a mist spray container. A manual mist spray container is one with a manual sprayer. Instead of the mist spray container, the fiber surface treatment product uses a spray container such as an aerosol spray container, or a coating container such as a stick container or roll-on container, and the fiber treatment agent of the present invention is placed in the spray container or coating container. may be filled with

A manual sprayer is a sprayer that does not use a propellant such as gas, and a specific example thereof is a finger spray trigger. The mist spray container may be of an accumulator type equipped with a compressing means, from the viewpoint of the fineness of the mist particle size and the uniformity of the mist size.

From the viewpoint of improving the water repellency of the fibers, etc., the amount of the fiber treatment agent of the present invention applied to the fibers is preferably 2 g/m ² or more, more preferably 6 g/m ² or more, and more preferably 20 g. /m ² or more is more preferable. Also, it is preferably 160 g/m ² or less, more preferably 100 g/m ² or less, and even more preferably 60 g/m ² or less. The amount of the fiber treatment agent of the present invention applied to fibers is preferably 2 g/m ² or more and 160 g/m ² or less, more preferably 6 g/m ² or more and 100 g/m ² or less, and 20 g/m 2 or more. More preferably, it is m ² or more and 60 g/m ² or less.

When the fiber treatment agent of the present invention is applied to, for example, underwear that is in direct contact with the user's skin, the surface of the underwear that is farther from the user's skin and the surface that is closer to the user's skin can be applied to at least one side of Since the textile treatment agent of the present invention can impart water repellency to underwear, it is preferable to apply the textile treatment agent to the side far from the user's skin, as it can effectively prevent liquid from seeping out. . In particular, if the outer surface of underwear such as briefs and trunks is given water repellency by the fiber treatment agent of the present invention, the underwear will absorb a small amount of urine instead of a pad and the absorbed urine will not seep out to the outer surface. Therefore, it is extremely effective as a countermeasure against leakage of a small amount of urine, in other words, as a countermeasure against dripping of urine after urination without wearing an article such as an incontinence pad.

According to the textile treatment agent of the present invention, a textile product having two opposite surfaces (for example, a front surface and a back surface) is coated with a film that prevents permeation of body fluids such as urine on only one surface, and the other surface of the textile product has two surfaces. It is possible to prevent the formation of the film during the process. Advantages of such "one-sided water repellency of the textile product" include the point that the water repellency of the textile product is suppressed to the necessary minimum, and various physical properties inherent in the textile product are maintained. If a textile product is made water repellent according to a conventionally known water repellent treatment method, the water repellency progresses more than necessary, and physical properties such as water absorbency, flexibility, and breathability, which are originally not desired to be reduced, may be greatly reduced. However, according to the textile treatment agent of the present invention, it is possible to easily impart water repellency to one side of textile articles. Moreover, the fiber treatment agent of the present invention can effectively prevent the floor from becoming slippery even if it unintentionally adheres to other than the object to be treated, for example, the floor.

As an example of a textile article to be made water repellent on one side, the water absorption time by the dropping method of JIS L-1907 is 30 seconds or less, preferably 20 seconds or less, more preferably 15 seconds or less, and still more preferably 1 second or less. Those having water absorption (hereinafter also referred to as "water-absorbing fiber products") can be mentioned. A water-absorbent fiber product can absorb water and various aqueous liquids, for example, sweat, urine, and blood, which are types of body fluids. A water-absorbing fiber product is typically composed mainly of water-absorbing fibers. Natural fibers such as wood pulp, cotton and hemp are used as the water absorbent fibers. The content of water-absorbent fibers in the water-absorbent fiber product is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total mass of the water-absorbent fiber product. The water-absorbing fiber product is, for example, a sheet-like fiber product having a thickness of about 0.3 to 20 mm, more specifically, any one or more of textile (woven fabric), knitted fabric, non-woven fabric, and paper. It can be a form containing

The textile treatment agent of the present invention can be used to impart water repellency to one side of various textile products including absorbent textile products, and is suitable for the following applications (1) to (10), for example. In general, the following (1) to (6) are applications for absorbing a relatively small amount of liquid, specifically preferably about 1 mL or less, more preferably about 0.5 mL or less. ) to (10) are applications for absorbing a larger amount of liquid, specifically preferably about 1 to 100 mL, more preferably about 1 to 10 mL.

(1) Prevention of transfer of foot perspiration to shoes and insoles (deodorization of shoes) by making the non-skin-facing surface of socks (water-absorbent textile products) water-repellent. The term "non-skin-facing surface" as used herein refers to the surface facing away from the user's skin when using the absorbent fiber product (the side relatively far from the user's skin). The same is true unless otherwise stated. The surface opposite to the non-skin-facing surface of the absorbent fiber product (the surface facing the user's skin during use) is the "skin-facing surface."
(2) Prevention of transfer of excrement (discharge, menstrual blood, etc.) to the bottom (clothes worn on the lower half of the body) by making the non-skin-facing surface of women's underwear (water-absorbing fiber product) water-repellent.
(3) Prevention of transfer of mother's milk to clothing by making the non-skin-facing surface of a women's brassiere (water-absorbing fiber product) water-repellent.
(4) Prevention of set-off of water-based ink by rendering the back surface of drawing paper (water-absorbing fiber product) water-repellent.
(5) Improving concealability by making one side of the nonwoven fabric (water-absorbing fiber product) water-repellent. Nonwoven fabrics with improved hiding properties are suitable for drip sheets, for example. A drip sheet is a sheet-like material that absorbs and retains drips (blood, etc.) that seep out of ingredients such as meat and fish, and is used to maintain the freshness of ingredients. By covering the food with a drip sheet made of a nonwoven fabric, the one side of the nonwoven fabric that is made water repellent (the side opposite to the side of the food) prevents the penetration of the drip and prevents blood from seeping out of the food. It becomes difficult to see the drip such as from the outside.
(6) Prevention of stain transfer to the table by making the back surface of the tablecloth water-repellent.

(7) Preventing dirt from sticking to hands by making one side of the rag/bed wipe (water-absorbent fiber product) water-repellent.
(8) The inner surface (the surface facing the user's body) of the bib (water-absorbing fiber product) is made water-repellent to prevent drool and spilled food stains from transferring to clothes.
(9) By making one side of the foot-wiping mat (water-absorbing fiber product) water-repellent, the floor is prevented from getting wet, is prevented from slipping, and is prevented from growing mold and germs.
(10) Prevention of transfer of sweat to mattresses, comforters, and pillows by making the back of sheets, futon covers, and pillowcases (water-absorbing fiber products) water-repellent (the side opposite to the user's body) ( moisture-proof).

The fiber treatment agent of the present invention is also suitable for the following uses (11) to (15). The following (11) to (15) need not be made water repellent on one side as described above, and there may be cases where both opposing surfaces of the textile product may be made water repellent.

(11) Prevention of adhesion of urine stains by making the skin-facing surface of trousers (water-absorbing fiber product) water-repellent.
(12) Reduction of stickiness due to perspiration by making the surface facing the skin of shoes, socks, and hats (water-absorbing fiber products) water-repellent.
(13) The surface of the sheet (water-absorbing fiber product) (the surface facing the user's body) is made water-repellent to reduce the stickiness of sweat.
(14) The stickiness of sweat is reduced by making the surface facing the skin of the underwear (water-absorbing fiber product) water-repellent.
(15) Prevention of sweat stains by making the non-skin facing surface of the underwear (water-absorbing fiber product) water-repellent.

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the scope of the invention is not limited to such examples.

[Examples 1 to 6 and Comparative Examples 1 to 7]
The silicone graft copolymers shown in Table 1 below were used as soluble polymers. Ethanol was used as the volatile solvent. The concentration of each soluble polymer in ethanol was 5% by mass. A fiber treatment agent was prepared using these soluble polymers and ethanol. The ratio of each soluble polymer in the fiber treatment agent is shown in the same table.
A fiber surface treatment product was produced by filling a manual mist spray container with the fiber treatment agent. As the sprayer, product number Z-155-C110-1-290 (95-0) manufactured by Mitani Valve Co., Ltd. was used. The sprayer had a discharge volume of 0.15 mL per push. As the bottle, PH-100 No. 2 white manufactured by Takemoto Yoki Co., Ltd. was used.

[Examples 7 to 22]
The polymers and polymer mixtures shown in Table 3 below were used as soluble polymers. Volatile solvents and polymer contents were blended as shown in Table 3 to prepare fiber treatment agents. A fiber surface treatment product was produced by filling a manual mist spray container with the fiber treatment agent. As the sprayer, product number Z-155-C110-1-290 (95-0) manufactured by Mitani Valve Co., Ltd. was used. The sprayer had a discharge volume of 0.15 mL per push. As the bottle, PH-100 No. 2 white manufactured by Takemoto Yoki Co., Ltd. was used.

Details of the polymers used in Examples and Comparative Examples are as shown in Table 2. Table 2 shows the yield stress of each polymer at 25°C and the contact angle with water.
・Polymer A: Poly(N-propionylethyleneimine)-modified silicone (INCI name: Polysilicone-9), weight average molecular weight: about 110,000, weight average molecular weight of graft chain: about 5000, ratio of polysiloxane skeleton: 88 mass %, solubility 50 g in 100 g ethanol at 25°C.
・Polymer B: Poly(N-propionylethyleneimine)-modified silicone (INCI name: Polysilicone-9), weight average molecular weight: about 70,000, weight average molecular weight of graft chain: about 1000, ratio of polysiloxane skeleton: 71 mass %, solubility 67 g in 100 g ethanol at 25°C.
・Polymer C: poly(N-propionylethyleneimine)-modified silicone (INCI name: Polysilicone-9), weight average molecular weight: about 100,000, weight average molecular weight of graft chain: about 3000, ratio of polysiloxane skeleton: 51 mass %, solubility 50 g in 100 g ethanol at 25°C.
Polymer D: poly (N, N-dimethylacrylamide) modified silicone, weight average molecular weight: about 70,000, weight average molecular weight of graft chain: about 1000, ratio of polysiloxane skeleton: 75% by mass, to 100 g of ethanol at 25 ° C. solubility 50 g.
Polymer E: poly(acrylic acid)-modified silicone, weight average molecular weight: about 60,000, weight average molecular weight of graft chain: about 2000, ratio of polysiloxane skeleton: 80% by mass, solubility in 100 g of ethanol at 25°C: 50 g. Polymer E was produced by the production method described below.
-Polymer F: (Acrylates/lauryl acrylate/stearyl acrylate/ethyl amine oxide methacrylate) copolymer (Diaformer Z-631, manufactured by Mitsubishi Chemical Corporation, active ingredient 30% by mass, ethanol 63% by mass, water 7% by mass ).
-Polymer G: (Acrylates/lauryl acrylate/stearyl acrylate/ethyl amine oxide methacrylate) copolymer (Diaformer Z-632, manufactured by Mitsubishi Chemical Corporation, active ingredient 30% by mass, ethanol 54% by mass, water 16% by mass ).
-Polymer H: (Acrylates/lauryl acrylate/stearyl acrylate/ethyl amine oxide methacrylate) copolymer (Diaformer Z-651, manufactured by Mitsubishi Chemical Corporation, active ingredient 30% by mass, ethanol 60% by mass, water 10% by mass ).
Polymer I: Silicone resin (KR-251, manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 20% by mass, toluene 80% by mass).
Polymer J: (Acrylates/Dimethicone) copolymer (KP-541, manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 60% by mass, isopropanol 40% by mass).
Polymer K: tri(trimethylsiloxy)silylpropylcarbamate pullulan (TSPL-30-ID, manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 30% by mass, isododecane 70% by mass).
Polymer L: (vinyl methyl ether/isopropyl maleate) copolymer (Gantrez ES-335I, manufactured by ISP Japan Co., Ltd., active ingredient 50% by mass, isopropanol 50% by mass).
Polymer M: (vinyl methyl ether/butyl maleate) copolymer (Gauntlets ES-435, manufactured by ISP Japan, 50% by mass of active ingredient, 50% by mass of isopropanol).
Polymer N: (Acrylates/t-butylacrylamide) copolymer (Ultrahold Strong, manufactured by BASF).
Polymer O: (octylacrylamide/hydroxypropyl acrylate/butylaminoethyl methacrylate) copolymer (Amphomer 28-4910, manufactured by Akzo Nobel Co., Ltd.).
- Polymer P: (methacryloyloxyethyl carboxybetaine/alkyl methacrylate) copolymer (Yukaformer 202, manufactured by Mitsubishi Chemical Corporation, 30% by mass of active ingredient, 70% by mass of ethanol).
Polymer Q: Vinyl acetate/vinylpyrrolidone copolymer (Lubiskol VA37E, manufactured by BASF, 50% by mass of active ingredient, 50% by mass of ethanol).
Polymer R: (vinylpyrrolidone/methacrylamide/vinylimidazole) copolymer (Lubiset Clear AT2, manufactured by BASF, weight average molecular weight: 270,000, active ingredient 25% by mass, water 75% by mass).
Polymer S: Polyvinylcaprolactam (Lubiskol Plus, manufactured by BASF, weight average molecular weight: 80,000, active ingredient 40% by mass, ethanol 60% by mass).
Polymer T: Fluoroalkyl acrylate copolymer (F-Tone GMW-605, manufactured by Daikin Industries, Ltd., 20-30% by weight of active ingredient, 70-80% by weight of water, less than 5% by weight of acetic acid).

<Method for producing polymer E>
First, a radical-reactive organopolysiloxane was synthesized, and using this, a poly(acrylic acid)-modified silicone of polymer E was synthesized.
<Synthesis of Radical Reactive Organopolysiloxane>
In a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device, side chain primary aminopropyl-modified organopolysiloxane (weight average molecular weight: 50,000, per unit mass) was added as an organopolysiloxane having a reactive functional group. Mole number of amino group; Under a nitrogen atmosphere, the temperature was raised to 100° C. and the mixture was stirred for 3 hours to synthesize a radical-reactive organopolysiloxane having sulfanyl groups.
<Synthesis of polymer E>
A separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirring device was charged with 17 g of ethanol. While stirring under reflux at 80° C. under a nitrogen atmosphere, the following solution (a) and solution (b) were placed in separate dropping funnels and added dropwise over 3 hours. Then, after stirring for 1 hour while refluxing ethanol, the following solution (c) was added dropwise over 1 hour.
Solution (a): A solution obtained by mixing 7.5 g of acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 110 g of ethanol.
・Solution (b): 30 g of the radical-reactive organopolysiloxane synthesized in the above synthesis example, 2,2′-azobis(2,4-dimethylvaleronitrile) “V-65B” (Fujifilm Wako Pure Chemical Industries, Ltd.) A solution in which 0.4 g of an azo polymerization initiator) and 30 g of ethanol were mixed.
- Solution (c): 2,2'-azobis (2,4-dimethylvaleronitrile) "V-65B" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., azo polymerization initiator) 0.4 g, ethanol 20 g mixed solution.
After completion of dropping, the mixture was stirred for 1 hour while refluxing ethanol. Ethanol was removed from the reaction mixture at room temperature (25° C.) under reduced pressure (20 kPa) over 4 hours to obtain a mixture containing polymer E as a white solid.

<Method for measuring solubility in water>
500 g of water is added to a 1 L glass beaker, and the mixture is kept in a constant temperature bath at 25° C. while stirring at 100 rpm using a rotor (fluororesin (PTFE), φ8 mm×50 mm). 0.1 g of each polymer is added, and after 10 minutes, it is visually confirmed whether or not the mixture is in a uniform and transparent state. Additional 0.1 g of each polymer is added until the solution is no longer uniform and transparent, and the solubility in water is measured. When various polymers were obtained as a solution dissolved in a solvent, the measurement was performed after removing the solvent.
When 50 g of the polymer is added and it remains homogeneously transparent, the measurement is terminated at that point, and the solubility in 100 g of water at 25° C. is determined to be 10 g or more. The solubility in 100 g of water at 25° C. is judged to be less than 20 mg if the addition of 0.1 g of polymer is not uniform and clear.
- Water: Pure water having a conductivity of 1 μS/cm or less at 25° C. produced by a water purifier G-10DSTSET manufactured by Organo Corporation.

<Appearance of fiber treatment agent>
10 g of each of the fiber treatment agents in Tables 1 and 3 was individually placed in a transparent glass container (capacity: 20 mL), kept at 25° C., and the appearance was visually observed. The results are shown in Tables 1 and 3.

〔evaluation〕
Textile articles were treated using the textile surface treatment products obtained in Examples and Comparative Examples, and the anti-slip properties of the textile treatment agents and the liquid barrier properties of the textile treatment agents were evaluated by the following methods. The results are shown in Tables 1 and 3.

[Anti-slip property of fiber treatment agent]
A flooring finishing material 148-W281 type manufactured by Osaka Gas Co., Ltd. was prepared. The flooring finish was of rectangular shape, 909 mm long by 151.5 mm wide. The floor surface of the flooring finishing material was treated with floor wax (Rinreiol manufactured by Rinrei Co., Ltd.) three times under standard usage conditions to obtain a floor surface for evaluation. As a standard use condition, floor wax was treated at a rate of 5 mL/m ² to 15 mL/m ² per unit area of floor. Divide the floor surface for evaluation into two halves in the vertical direction. On the other hand, the mist spray container was pushed several times to uniformly spray the fiber treatment agent so that 150 mg/m ² of the fiber treatment agent was adhered, and then left to stand for 5 minutes to dry. The other half of the floor area was not sprayed with fabric treatment. In this way, a floor surface for evaluation of anti-slip property was prepared, in which one of the bisected areas was the treated surface on which the film of the treating agent was formed, and the other bisected area was the untreated surface. Five panelists wearing socks made of 85% by weight polyester, 10% by weight cotton and 5% by weight polyurethane were allowed to walk in the longitudinal direction of the floor surface for slip resistance evaluation from the untreated surface toward the treated surface. . Then, the degree of slippage when making a U-turn on the treated surface was evaluated. The average of the panelists' evaluations was taken as the evaluation result of anti-slip properties. The higher the score, the higher the evaluation.
(Evaluation Criteria for Risk of Slipping)
1 point: Extremely slippery compared to the untreated surface.
2 points: Much slippery compared to the untreated surface.
3 points: Slippery compared to the untreated surface.
4 points: Slightly slippery compared to the untreated surface.
5 points: Not as slippery as the untreated surface.

[Barrier property of artificial urine by fiber treatment agent]
A first textile product (Kanakin No. 3 manufactured by the Japanese Standards Association) made of cloth of 10 cm × 10 cm is placed on a vertical stand, and the upper surface of the textile product is measured from a position 10 cm above the textile product. After spraying the fiber treatment agent by pushing the mist spray container 6 times over the entire area, it was allowed to stand for 10 minutes to dry. Thus, a treating agent-applied textile article was obtained in which the treating agent was applied to the entire one side of the textile article. Next, another second textile product (Kanakin No. 3 manufactured by the Japanese Standards Association) made of cloth of 10 cm × 10 cm is placed on a horizontal table, and the treatment is performed on the second textile product. The treated fibrous articles were superimposed such that the side to which the treatment was applied faced the second fibrous article. The first textile product is assumed to be an undergarment, and the second textile product is assumed to be trousers of outer clothing. Under this condition, 0.5 mL of artificial urine was dripped toward the surface of the treating agent-applied fiber product to which the treating agent was not applied. Immediately after dropping, an acrylic plate having a bottom area larger than that of the first and second textile articles was placed thereon, and a pressure of 1 g/cm ² was applied for 60 seconds. This pressure assumes the mounting pressure applied to the underpants. Next, the acrylic plate was removed, and the mass of the first fiber product before and after the artificial urine was dropped was measured to determine the change in mass. Let this value be the mass change amount (W1) of the first textile product. Similarly, the mass of the second textile product was measured before and after the artificial urine was dropped, and the change in mass was obtained. This value is defined as the bleeding amount (W2) of the artificial urine. The ratio of the mass change amount (W1) of the first textile product to the total value of the mass change amount (W1) and the bleeding amount (W2) of the first textile product was calculated as the barrier property (%). . The closer the value is to 100%, the lower the amount of bleeding and the higher the barrier properties can be evaluated. In this evaluation, "A" was given when the barrier property was 90% or more, and "B" was given when it was less than 90%.

The composition of artificial urine is 1.940% by mass of urea, 0.795% by mass of sodium chloride, 0.110% by mass of magnesium sulfate, 0.062% by mass of calcium chloride, 0.197% by mass of potassium sulfate, and polyoxyethylene lauryl ether. (approximately 0.07% by mass) and water (balance), and the surface tension was adjusted to 53±1 dyne/cm at 23°C.

Regarding Example 1, physiological saline (Otsuka Saline Injection, manufactured by Otsuka Pharmaceutical Factory Co., Ltd.) was used instead of artificial urine, and the barrier properties of the physiological saline due to the fiber treatment agent were similarly evaluated.

As is clear from the results shown in Tables 1 and 3, the condition (I) that the yield stress of the polymer is 0.6 MPa or more and the condition (II) that the contact angle with water is greater than 90 degrees is satisfied. It can be seen that the fiber products treated with the fiber treatment agent of each example that satisfies the above conditions have high barrier properties against artificial urine, and the floor on which the film of the fiber treatment agent of each example is formed is not slippery. In contrast, the fiber products of Comparative Examples 3 and 5 to 7, which satisfy only condition (I), have low barrier properties against artificial urine, and the fiber treatment agents of Comparative Examples 1, 2, and 4, which satisfy only condition (II). It can be seen that the floor on which the film of is formed is slippery. Further, it was found that the fiber product treated with the fiber treatment agent of Example 1 has high barrier properties against artificial urine and further has high barrier properties against physiological saline. From the above, according to the fiber treatment agent of each example, the body fluid excreted from the body can be effectively prevented from seeping out from the clothes while using the clothes such as underwear that is usually used as it is. It can be expected that the floor will be less slippery even if it unintentionally adheres to the floor.

Claims (8)

comprising a volatile solvent and a mixture of two or more polymers soluble in the volatile solvent;
two or more of said polymers have a water solubility of less than 50 mg/100 g at 25°C;
The content ratio of the mixture of two or more of the polymers is 3% by mass or more and 15% by mass or less,
A mixture of two or more of the above polymers has a yield stress at 25° C. of 0.6 MPa or more,
A mixture of two or more of the above polymers has a contact angle with water of 90 degrees or more,
A mixture of two or more of the above polymers is composed of (A1) a polymer having a yield stress at 25° C. of 0.6 MPa or more and a contact angle with water of less than 90 degrees, and (A2) a yield stress at 25° C. is less than 0.6 MPa and the contact angle with water is 90 degrees or more,
Both the polymer (A1) and the polymer (A2) have a polysiloxane skeleton as a main chain,
The proportion of the polysiloxane skeleton in the polymer (A1) is 40% by mass or more and less than 70% by mass,
A fiber treatment agent , wherein the proportion of the polysiloxane skeleton in the polymer (A2) is 70% by mass or more . 2. The fiber treatment agent of claim 1 , wherein each polymer in the mixture of two or more of said polymers is a silicone graft copolymer. The graft chain of the silicone graft copolymer has a weight average molecular weight of 800 or more, and the side chain is at least one of N-acylalkyleneimine, acrylic acid, acrylic acid ester, and acrylamide. 2. The fiber treatment agent according to 2 . The fiber treatment agent according to any one of claims 1 to 3 , wherein the proportion of the polymer (A1) in the polymer mixture is 20% by mass or more and 80% by mass or less. The fiber treatment agent according to any one of claims 1 to 4 , which has a viscosity of 20 mPa·s or less at 25°C. The fiber treatment agent according to any one of claims 1 to 5 , comprising (B) a polymer having a solubility in water of 50 mg/100 g or more at 25°C in addition to two or more of said polymers. A fiber surface treatment article comprising the fiber treatment agent according to any one of claims 1 to 6 and a manually operated mist spray container filled with the fiber treatment agent. A fiber surface treatment product, in which the fiber treatment agent according to any one of claims 1 to 6 is filled in a spray container or a coating container.