WO2020116598A1 - Fiber treating agent and fiber surface treatment article including same - Google Patents

Abstract

The fiber treating agent according to the present invention comprises: a volatile solvent; and one polymer or a mixture of two or more polymers, which is dissolvable in said volatile solvent. The one polymer or the two or more polymers have a solubility of less than 50 mg/100g in water at 25°C. The content proportion of the one polymer or the mixture of two or more polymers is 3-15 mass%. The one polymer or the mixture of two or more polymers have a yield stress of at least 0.6 MPa at 25°C. In addition, the one polymer or the mixture of two or more polymers exhibits a contact angle of at least 90 degrees with respect to water.

Description

Fiber treatment agent and fiber surface treatment article containing the same

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

A type of absorbent article that is attached to the inside of textiles such as undergarments and absorbs mainly urine is known. Patent Document 1 includes, as a kind of such absorbent article, a leak-proof cuff for blocking the lateral flow of excreted urine for the purpose of preventing a large amount of urine from leaking even if it is excreted at once. Men's incontinence pad is described. The male incontinence pad described in the document is sufficiently satisfactory for users who excrete a large amount.

Apart from this technique, the present applicant has previously proposed a silicone-based fiber surface-treating agent as a fiber surface-treating agent that improves the flexibility, smoothness, and water repellency of fibers and is excellent in darkening. Proposed (see Patent Document 2). In this document, a spraying method is described as a method for attaching the fiber surface treatment agent to the surface of the fiber.

JP, 2005-188714, A JP-A-4-163374

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

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

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

Detailed Description of the Invention

　Many elderly men have a problem that they cannot exhaust all of their urine when they urinate, and a small amount of urine leaks after urination ends, in other words, urine drip after urination occurs and urine seeps into their 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 pad with a high absorption capacity, but in that case, due to the high absorption capacity, the pad becomes bulky, and as a result, other people should be aware that they wear the pad. There are many people who have anxiety about whether to leave. In addition, some users feel resistance to the use of the pad itself. Therefore, there is a high demand for a technique capable of solving the above problems without using a large-scale article such as a male incontinence pad and using clothes such as underwear for everyday use, and the technique is not yet provided. Absent.

Regarding the coating method of the treatment agent described in Patent Document 2, since the spraying method is adopted, the user can easily apply the water repellent agent uniformly. However, the technique described in Patent Document 2 is not supposed to be used by the above-mentioned user having a small excretion amount.

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

In view of the above circumstances, the present invention effectively prevents the body fluid excreted from the body from seeping out of the clothing while using the clothing that is normally used such as undergarments as it is, and unintentionally flooring the clothing. The present invention relates to a fiber treatment agent which makes it difficult for the floor to slip even if it adheres to the surface.

The present invention will be described below based on its preferred embodiments. The fiber treatment agent of the present invention is generally a liquid in its use state. The fiber treatment agent of the present invention is contained in, for example, a manual mist spray container, and is sprayed onto the fiber 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 use temperature of the fiber treatment agent. Examples of the volatile solvent 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 the volatile solvent composed of an organic solvent include alcohol, ester, nitrile, ether, hydrocarbon, ketone, amine, acetic acid and the like. These volatile solvents may be used alone or in combination of two or more. When two or more volatile solvents are used in combination, the saturated vapor pressure means 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, and one or two kinds selected from the group consisting of water, ethanol and propanol, from the viewpoint of achieving both the solubility of the polymer described below and the drying time of the fiber treatment agent. It is more preferable to use the above combination.

When an 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, for example, More preferably, ethanol, propanol and butanol are 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 preferred, and an ester of a monohydric aliphatic alcohol having 1 to 2 carbon atoms and a monohydric fatty acid having 1 to 4 carbon atoms, for example, ethyl acetate, methyl propionate and butyl acetate. And the like are more preferably used. When nitrile is used as the volatile solvent, it is preferable to use an nitrile of an alkane having 2 to 3 carbon atoms, such as acetonitrile. Further, from the viewpoint of preventing ignition and ignition, it is preferable to use water in combination with another volatile solvent, and it is preferable to contain 5 parts by mass or more of water in a total of 100 parts by mass of the volatile solvent, preferably 10 parts by mass. It is more preferable to contain at least 1 part by mass, and preferably 50 parts by mass or less, 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 above-mentioned volatile solvent as long as the effect of the present invention is 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 that the effect of the present invention is reliably exhibited.

The fiber treatment agent of the present invention contains, in addition to a volatile solvent, a polymer soluble in the volatile solvent. The polymer soluble in a volatile solvent is a polymer compound having a solubility in 100 g of a volatile solvent used in the present fiber treating agent of 1 g or more at 25°C. The fiber treating agent of the present invention contains only one type of polymer soluble in the volatile solvent contained therein, or contains it in the form of a mixture of two or more types. As long as the effects of the present invention are not impaired, the fiber treatment agent of the present invention is allowed to contain a polymer that is insoluble in the volatile solvent contained therein. However, it is preferable that the fiber treatment agent of the present invention contains only a polymer that is soluble in the volatile solvent contained therein, from the viewpoint that the effect of the present invention is reliably exhibited. In the following description, a polymer that can be dissolved in a volatile solvent is also referred to as “soluble polymer”. Since the fiber treating agent of the present invention contains a soluble polymer, the fiber treated with the fiber treating agent of the present invention has 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 added in a closed container while stirring at 25° C., and a soluble polymer is added thereto and stirred for 24 hours to be dissolved. The amount of the soluble polymer added to the volatile solvent was increased, and it was visually confirmed that the soluble polymer could not be completely dissolved and remained in the liquid. ). When the soluble polymer is a solid, it is dissolved in the state of a powder of 16 mesh under.

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 fiber article with a polymer having a solubility in water at 25° C. of less than 50 mg/100 g can effectively prevent body fluid from seeping out from 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, and even more preferably from the viewpoint of easily imparting water repellency to the fiber surface. It is preferably less than 20 mg/100 g.

From the viewpoint of increasing the water repellency of the fiber or the fiber-made article that is the object of treatment, the fiber treatment agent of the present invention has a soluble polymer content of preferably 3% by mass or more, more preferably 4% by mass or more, It is more preferably 4.5% by mass or more. Further, 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 treatment efficiency of the fiber treatment agent and the ease of spraying. The following are more preferable. 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 preferable. The above-mentioned content is the content of the soluble polymer when the fiber treatment agent of the present invention contains only one type of the soluble polymer, and when the fiber treatment agent contains two or more types of the soluble polymer, It means the total content of the soluble polymer.

The soluble polymer contained in the fiber treatment agent of the present invention has a yield stress at 25° C. of preferably 0.6 MPa or more, more preferably 1 MPa or more, and 1.5 MPa, from the viewpoint that the effect of the present invention is reliably exhibited. The above is more preferable. The upper limit of the yield stress of the soluble polymer is not particularly limited, but from the viewpoint of good spraying, the yield stress at 25° C. is preferably 20 MPa or less, more preferably 10 MPa or less, and 5 MPa or less. More preferably, When the yield stress of the soluble polymer is not less than the above value, when the fiber treatment agent of the present invention is unintentionally attached to an article other than the object to be treated, for example, when attached to the floor, the floor is slippery. Is effectively prevented. 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 coating formed from the fiber treatment agent becomes hard. The reason why the yield stress is measured at 25° C. is that the fiber treating agent of the present invention is usually used at room temperature.

The yield stress of a 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 soluble polymer in the form of a mixture of two or more kinds, it means the yield stress of the mixture of the soluble polymers. When the fiber-treating agent of the present invention contains the soluble polymer in the state of a mixture of two or more kinds, each of the components constituting the mixture as long as the yield stress of the mixture of the soluble polymer is the above value or more. The yield stress of the soluble polymer need not be above the above value. Specifically, as long as the yield stress of the mixture of the soluble polymers is the above value or more, (i) the yield stress of a part of the soluble polymer constituting the mixture of the soluble polymers is the above value or more, and The yield stress of the rest of the soluble polymer may be less than the above value, and (ii) the yield stress of all the soluble polymers that make up the mixture of soluble polymers may be greater than or equal to the above value, or (Iii) The yield stress of all soluble polymers that make up the soluble polymer mixture may be less than the above values.

The yield stress of the soluble polymer is measured by the method described below. That is, the fiber treatment agent of the present invention was allowed to stand for 5 hours, and after sufficiently removing air bubbles, cast on a vat, dried at 25° C. and 50% RH for 48 hours, and further heated in a vacuum dryer at 80° C. And dried for 48 hours to form a 1 mm thick film. A rectangular test piece having a width of 2 mm and a length of more than 10 mm is cut out from this film. Each end of the test piece in the longitudinal direction is set on each chuck of the tensile tester. As the tensile tester, for example, Tensilon "RTC series" manufactured by A&D Co., Ltd. is used. The distance between chucks is 10 mm. It is pulled at a pulling speed of 1000 mm/min, and the stress at which plastic deformation starts 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° or more, more preferably 100° 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 effect of the present invention is sufficiently exhibited.

The above contact angle is the contact angle between the soluble polymer and water 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 soluble polymer in the form of a mixture of two or more kinds, the above-mentioned contact angle means the contact angle between the mixture of the soluble polymer and water. When the fiber-treating agent of the present invention contains the soluble polymer in the form of a mixture of two or more kinds, as long as the contact angle of the mixture of the soluble polymers is 90 degrees or more, each of the melts constituting the mixture is dissolved. The contact angle of the polymer is not required to be 90 degrees or more. In detail, as long as the contact angle of the mixture of soluble polymers is 90 degrees or more, (i) the contact angle of a part of the soluble polymers constituting the mixture of soluble polymers is 90 degrees or more, and the balance of The contact angle of the soluble polymer may be less than 90 degrees, (ii) the contact angle of all soluble polymers that make up the mixture of soluble polymers may be 90 degrees or more, or (iii) dissolution The contact angle of all soluble polymers that make up the mixture of soluble polymers may be less than 90 degrees.

Contact angle is measured by the following method. The film of the measurement sample is formed in the same manner as the yield stress described above. That is, the fiber treatment agent of the present invention was allowed to stand for 5 hours, and after sufficiently removing air bubbles, cast on a vat, dried at 25° C. and 50% RH for 48 hours, and further heated in a vacuum dryer at 80° C. Dry for 48 hours to form a film. This film is used as a measurement sample. The measurement environment is 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 to be measured for the contact angle in the measurement sample, and the state from the side where the contact surface between the droplet and the membrane is visible is recorded. The contact angle is measured based on a plurality of images obtained by recording. For example, a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd. is used as a measuring device. From among the plurality of images, 10 images with clear droplet contours are selected, and the contact angle of the droplet with respect to the reference plane is measured for each of the 10 images. The average value of those contact angles is taken as the contact angle between the soluble polymer and water.

The advantages of imparting water repellency to fibers by the fiber treatment agent of the present invention are as follows. On the outer surface of the undergarment which is a fiber article such as briefs and trunks, if water repellency is imparted by the fiber treatment agent of the present invention, the fibers present on the inner surface of the undergarment absorb a small amount of urine instead of the pad, Since the exudation of absorbed urine to the outer surface is suppressed, it is extremely effective as a measure against a small amount of urine leakage, in other words, as a measure against urine drip after urination, without wearing an article such as an incontinence pad.

When the fiber treatment agent of the present invention contains the soluble polymer in the form of a mixture of two or more kinds, at least one kind of the soluble polymer constituting the mixture of the soluble polymers is (A1) yielded 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, and at least one of the other soluble polymers has a (A2) yield stress at 25° C. of 0. A soluble polymer having a contact angle with water of less than 6 MPa and 90° or more is preferable from the viewpoint of preventing slippage. From the viewpoint of making this effect more remarkable, the yield stress of the soluble polymer (A1) is more preferably 0.6 MPa or more, further preferably 1.5 MPa or more. The contact angle of the soluble polymer (A1) is more preferably 70 degrees or less, further preferably 50 degrees or less. On the other hand, the yield stress of the soluble polymer (A2) is more preferably 0.4 MPa or less. Further, the soluble polymer (A2) has a contact angle of preferably 90° or more, more preferably 100° or more. The soluble polymer (A1) may be used alone or in combination of two or more. Similarly, as the soluble polymer (A2), one type may be used alone, or two or more types may be used in combination.

When the fiber treatment agent of the present invention contains the soluble polymer in the form of a mixture of two or more kinds, the soluble polymer constituting the mixture of the soluble polymers has the solubility of the above (A1) and (A2). It may be only the polymer, or the soluble polymers of (A1) and (A2), and the other soluble polymers. From the viewpoint of making the effect of preventing slippage more remarkable, it is preferable that the soluble polymers constituting the mixture of the soluble polymers are only the soluble polymers of the above (A1) and (A2).

The yield stress of the soluble polymer (A1) and the contact angle with water are measured by the methods described above. In this case, a solution in which the soluble polymer of (A1) is dissolved in a volatile solvent is prepared, a film for measurement is formed according to the method described above using the solution, and the yield stress and the 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 above-mentioned 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 preventing slippage. Mass% or more is preferable, 30 mass% or more is more preferable, and 40 mass% or more is further preferable. 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 preferably 50% by mass or less. preferable. The proportion of the soluble polymer (A1) with respect 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 preferably 50% by mass or more. preferable. From the viewpoint of preventing slippage, the proportion of the soluble polymer (A2) with respect to the total amount of the soluble polymer is preferably 80% by mass or less, more preferably 70% by mass or less, and further 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 The mass of the soluble polymer in (4)/the mass of the soluble polymer in (A2)] is preferably 0.25 or more, more preferably 0.43 or more, and 0.7 or more from the viewpoint of preventing slippage. More preferable. The value of [mass of soluble polymer of (A1)/mass of soluble polymer of (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 of (A1)/mass of soluble polymer of (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. It is more preferably 1 or less.

The soluble polymer contained in the fiber treatment agent of the present invention is preferably a silicone polymer from the viewpoint of preventing slippage and imparting water repellency to the fiber surface. Examples of the silicone-based polymer include silicone resins, (acrylic acid/dimethicone) copolymers, and silicone graft copolymers, and of these, the silicone graft copolymers are more preferable. From the viewpoint of making these advantages more remarkable, 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. More preferably. When the fiber treatment agent of the present invention contains only one soluble polymer, the weight average molecular weight of the graft chain of the soluble polymer is preferably the above value or more. When the fiber treatment agent of the present invention contains the soluble polymer in the form of a mixture of two or more kinds, (i) the weight of the graft chain of at least one soluble polymer constituting the mixture of the soluble polymer. The average molecular weight is preferably the above value or more, and more preferably the weight average molecular weight of the graft chains of all the soluble polymers constituting the mixture of the (ii) soluble polymer is the above value or more. The weight average molecular weight can be determined as a standard polystyrene conversion value by, for example, gel permeation chromatography (GPC) (DP-8020) manufactured by Tosoh Corporation.

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-mentioned solubility and the above-mentioned 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, and silicone graft copolymers. As a result of various studies by the present inventor, the polysiloxane skeleton has a main chain as a soluble polymer. It has been found that the use of the silicone graft copolymer described below gives very satisfactory results. The polysiloxane skeleton is a structure composed of —O—Si—O—Si— bonds, and typically includes silicone. It is preferable to use various modified silicones as the silicone from the viewpoint of further preventing slippage. Modified silicones include, but are not limited to, fatty acid modified silicones and acrylic silicones. Among the modified silicones, the use of a silicone graft copolymer is preferable because the effect of the present invention becomes more remarkable. When the fiber treatment agent of the present invention contains only one soluble polymer, the soluble polymer is preferably a silicone graft copolymer. When the fiber treatment agent of the present invention contains the soluble polymer in the form of a mixture of two or more kinds, (i) at least one kind of the soluble polymer constituting the mixture of the soluble polymers is a silicone graft copolymer. It is preferable that all of the soluble polymers constituting the mixture of (ii) the soluble polymers are silicone graft copolymers.

As the silicone graft copolymer, one having a polysiloxane skeleton as a main chain and having a group derived from N-acylalkyleneimine, acrylic acid, acrylic acid salt, acrylic acid ester or acrylamide in the side chain is used. It is preferable from the viewpoint of anti-slip property and the viewpoint of imparting water repellency to the fiber. The silicone graft copolymer is roughly classified into two types, that is, a physical cross-linked product in which cross-linking points are generated by a physical interaction, and a chemical cross-linked product in which a cross-linking point is formed by a covalent bond. From the viewpoint of being easily dissolved in a volatile solvent, it is preferable to use a physical crosslinked product in the present invention.

Physically crosslinkable 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 (JP 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 Examples thereof include PEG block polymers (Japanese Patent Laid-Open No. 4-234307). Of these, poly(N-acylalkyleneimine)-modified silicone and poly(N,N-dimethylacrylamide)-modified silicone are preferably used because of their high solubility in volatile solvents.

The above-mentioned poly(N-acylalkyleneimine)-modified silicone has, for example, a poly(N-acylalkyleneimine) segment and an organopolysiloxane segment in the molecule, and the end of the organopolysiloxane segment or It is preferable that the above-mentioned segment of poly(N-acylalkyleneimine) is bonded to at least one of the silicon atoms 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 hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom may be used between adjacent methylene groups in the alkylene group or at the terminal of the alkylene group. The number of heteroatoms is preferably 1 to 3.

Specific examples of preferable poly(N-acylalkyleneimine)-modified silicone include poly(N-formylethyleneimine)-modified silicone, poly(N-acetylethyleneimine)-modified silicone, poly(N-propionylethyleneimine)-modified silicone. Silicone etc. are mentioned. Above all, a poly(N-propionylethyleneimine)-modified silicone having a weight average molecular weight of about 20,000 to 200,000 and a proportion of poly(N-propionylethyleneimine) segment in the polymer of about 3 to 50% by mass ( INCI name: Polysilicone-9) is preferred.

Examples of the above-mentioned poly(N,N-dimethylacrylamide)-modified silicone include, for example, an organopolysiloxane segment and a polymer segment derived from an unsaturated monomer in the molecule, and the organopolysiloxane segment has a terminal end. Alternatively, it is preferable that the polymer segment derived from the unsaturated monomer is bonded to at least one of the side chain silicon atoms via an alkylene group. Specific examples thereof include an organopolysiloxane graft polymer containing a repeating unit derived from N,N-dimethylacrylamide (DMAAm) in a polymer segment derived from an unsaturated monomer. The alkylene group preferably has 2 to 20 carbon atoms. Instead of this alkylene group, a group containing a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom may be used between adjacent methylene groups in the alkylene group or at the terminal of the alkylene group. The number of heteroatoms is preferably 1 to 3. In the polymer segment derived from the unsaturated monomer, the portion other than the repeating unit derived from DMAAm is composed of the repeating unit derived from an unsaturated monomer (excluding DMAAm) copolymerizable with DMAAm. Examples of the repeating unit derived from an unsaturated monomer copolymerizable with DMAAm include olefins, halogenated olefins, vinyl esters, (meth)acrylic acid esters, and (meth)acrylamides (excluding DMAAm). The repeating unit derived from an unsaturated monomer is mentioned.

Specific examples of olefins 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, vinyl versatate and the like. 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; having an alkyl group having 1 to 16 carbon atoms substituted with a hydroxyl group such as 2-hydroxyethyl (meth)acrylate (meta) ) Acrylic acid ester; and (meth)acrylic acid polyethylene glycol, (meth)acrylic acid polyethylene glycol monomethyl ether and the like. Specific examples of (meth)acrylamides excluding DMAAm include (meth)acrylamides such as acrylamide and methacrylamide; N,N-dialkyl(meth)acrylamides such as N,N-diethyl(meth)acrylamide (where DMAAm is 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 a nitrogen atom such as (meth)acrylamide; an amino group as a substituent on a nitrogen atom such as N,N-dimethylaminopropyl (meth)acrylamide N-monosubstituted (meth)acrylamides having; N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide and the like having N-monosubstituted (meth)acrylamides having a hydroxyl group as a substituent on the nitrogen atom. Be done.

Specific examples of preferable poly(N,N-dimethylacrylamide)-modified silicone include N,N-dimethyl in which the proportion of the poly(N,N-dimethylacrylamide) segment in the polymer is about 50% by mass to 90% by mass. An acrylamide modified silicone is mentioned.

When the above-mentioned silicone graft copolymer is used as the soluble polymer contained in the fiber treating agent of the present invention, the reason why the anti-slip property is further improved is not completely clear, but the present inventors have the following. thinking. When the volatile solvent volatilizes from the fiber treatment agent and the soluble polymer coagulates to form a film, the main chain polysiloxane skeleton, which is the water-repellent site, gathers on the surface of the film and the side that is the hydrophilic site. The chains will collect inside the membrane. As a result, a hard film is likely to be formed, which is considered to improve the anti-slip property of the film. However, the scope of the 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 of (A1) and the soluble polymer of (A2), these (A1) and The soluble polymer (A2) is preferably 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, and more preferably 50% by mass or more and less than 70% by mass. When the proportion of the polysiloxane skeleton in the soluble polymer (A1) is within this range, the physical properties of the graft chain, not the silicone main chain, become dominant, and the advantageous effect of increasing the yield stress is achieved. It

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, and 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, and more preferably 70% by mass or more and 90% by mass or less. When the proportion of the polysiloxane skeleton in the soluble polymer (A2) is within this range, the advantageous effect that the hydrophobic property of silicone is exhibited is exhibited.

The proportion of the polysiloxane skeleton in the soluble polymer of (A1) and (A2) is, for example, by dissolving the soluble polymer in deuterated chloroform and using a nuclear magnetic resonance ( ¹ H-NMR) device “Mercury 400” (manufactured by Varian). ) Can be used for measurement.

As the acrylic resin, for example, one obtained by homopolymerizing or copolymerizing an acrylic acid derivative such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid ester, or methacrylic acid ester as a main component is used. be able to. Specifically, (acrylic acid/acrylamide/ethyl acrylate) copolymers such as (acrylic acid/t-butyl acrylamide) copolymers and (acrylic acid/acrylamide/acrylic acid/acrylamide/ethyl acrylate) copolymers Acrylic acid alkyl ester) copolymer, (alkyl acrylamide/acrylic acid/alkyl aminoalkyl acrylamide/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 (Acrylic acid alkyl ester/acrylamide) copolymers such as (alkyl ester/t-butyl acrylamide) copolymers, (acrylic acid alkyl ester/octyl acrylamide) copolymers, (acrylic acid/acrylic acid alkyl ester/t-butyl) (Acrylamido) copolymer (acrylic acid/acrylic acid alkyl ester/alkyl acrylamide) copolymer, (methacrylic acid/acrylic acid alkyl ester/alkyl acrylamide) copolymer, (methacryloyloxyethyl carboxybetaine/methacrylic acid alkyl ester) ) Copolymer, (alkyl acrylamide/alkyl aminoalkyl acrylamide/polyethylene glycol methacrylate) copolymer, (octyl acrylamide/hydroxypropyl acrylate/butyl aminoethyl methacrylate) copolymer, (alkyl acrylamide/alkyl acrylate/ Alkylaminoalkyl acrylamide/polyethylene glycol methacrylate) copolymer, (acrylic acid alkyl ester/diacetone acrylamide) copolymer, (styrene/acrylic acid) copolymer, (styrene/acrylic acid alkyl ester) copolymer, ( (Styrene/acrylamide) copolymer, urethane-acrylic copolymer, (vinylpyrrolidone/acrylic acid/methacrylic acid) copolymer, (vinylpyrrolidone/alkyl acrylate/methacrylic acid) copolymer, (octyl acrylamide/ Hydroxypropyl acrylate/butylaminoethyl methacrylate) polymer, (methacryloyloxyethyl carboxybetaine/meth Acrylic acid alkyl ester) polymer, (acrylic acid/acrylic acid alkyl ester/methacrylic acid ethylamine oxide) copolymer, and the like.

Examples of the above-mentioned fluorine-based polymer include those obtained by polymerizing a fluorinated olefin such as polytetrafluoroethylene and polyvinylidene fluoride, and those partially modified.

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

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° 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 contained. 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. More preferably, it is 3.5 mass% or less.

Examples of the polymer (B) include a nonionic resin that does not ionize when dissolved in a volatile solvent, a water-soluble polymer having a high water-soluble monomer content in the acrylic resin or the like, and a water-soluble polymer that forms a salt. .. Examples of the nonionic resin include (vinylpyrrolidone/methacrylamide/vinylimidazole) copolymers and polyvinylcaprolactam.

The fiber treatment agent of the present invention may contain other components in addition to the above-mentioned volatile solvent and soluble polymer. Examples of such other components include deodorants/antibacterial agents/fragrances for the purpose of reducing urine odor, surfactants/plasticizers for the purpose of improving removability by washing, and speed of excreted urine. Examples thereof include a water absorbing agent for improving dryness, and dyes and pigments for improving visibility after treatment. These other components are contained in the fiber treating agent of the present invention in a total amount of preferably 5% by mass or less. From the viewpoint of making the effect of the invention more remarkable, the fiber treating agent of the present invention preferably contains only a volatile solvent and a soluble polymer. The volatile solvent serves as a medium in which the component contained in the fiber treatment agent can be dissolved, and the content of the volatile solvent in the fiber treatment agent can be the balance of the component.

The fiber treating 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, further preferably 10 mPa·, from the viewpoint of the uniformity of mist when sprayed. s or less. The lower limit of the viscosity is not particularly limited, and the lower the lower limit, the better. However, the lower the viscosity is about 5 mPa·s, the effect of the present invention is sufficiently exhibited. The viscosity of the fiber treatment agent is measured using a B-type 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 rotations 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, these are also collectively referred to as “fibers and the like”). When the fiber treatment agent of the present invention is applied to a fiber or the like by spraying, a fiber surface treatment article containing the fiber treatment agent in a manual mist spray container may be used. When using this fiber surface treatment article, the fiber treatment agent may be sprayed onto the fibers or the like from a mist spray container. A manual mist spray container comprises a manual sprayer. The fiber surface treatment article is, instead of the mist spray container, a spray container such as an aerosol spray container, or a coating container such as a stick container or a roll-on container, and the fiber treatment agent of the present invention in the spray container or the coating container. May be filled.

　The manual sprayer is a sprayer that does not use a propellant such as gas, and can specifically exemplify a spray trigger for fingers. The mist spray container may be a pressure-accumulation type container provided with a compression means from the viewpoint that the mist particle size is fine and the mist diameter is uniform.

The amount of applying the fiber treatment agent of the present invention to the fiber or the like, from the viewpoint of improving the water repellency of the fibers and the like, preferably at 2 g / m ² or more, more preferably 6 g / m ² or more, 20g /M ² or more is more preferable. Further, it is preferably 160 g/m ² or less, more preferably 100 g/m ² or less, and further preferably 60 g/m ² or less. The amount of applying the fiber treatment agent of the present invention to the fiber or the like, is preferably 2 g / ^{m 2} or more 160 g / ^{m 2} or less, more preferably 6 g / ^{m 2} or more 100 g / ^{m 2} or less, 20 g / More preferably, it is not less than m ^{2 and not} more than 60 g/m ² .

When the fiber treatment agent of the present invention is applied to, for example, underwear that directly contacts the user's skin, among the surfaces of the underwear, the surface far from the user's skin and the surface close to the user's skin Can be applied to at least one side of the. Since the fiber treatment agent of the present invention can impart water repellency to the underwear, it is preferable to apply the fiber treatment agent to the surface far from the user's skin, because the exudation of liquid can be effectively prevented. .. In particular, by imparting water repellency to the outer surface of the undergarment such as briefs and trunks by the fiber treatment agent of the present invention, the undergarment absorbs a small amount of urine instead of the pad and exudates the absorbed urine to the outer surface. Since it suppresses, it becomes extremely effective as a measure against a small amount of urine leakage, in other words, against urine drip after urination, without wearing an article such as an incontinence pad.

According to the fiber treatment agent of the present invention, a coating for preventing the permeation of body fluid such as urine is formed only on one surface of a fiber article having two surfaces (for example, the front surface and the back surface) facing each other, and the other surface. It is possible not to form the coating on the substrate. An advantage of such "one-sided water-repellent property of the fiber-made article" is that the water-repellent property of the fiber-made article is suppressed to a necessary minimum and various physical properties originally possessed by the fiber-made article are maintained. When a fiber article is made water-repellent according to a conventionally known water-repellent treatment method, the water-repellent property may be unnecessarily advanced, and physical properties such as water absorption, flexibility, and air permeability, which should not be deteriorated, may be largely reduced. However, according to the fiber treatment agent of the present invention, it is possible to easily make one side of a fiber article water repellent. Moreover, the fiber treatment agent of the present invention can effectively prevent the floor from becoming slippery even if it is unintentionally attached to, for example, the floor other than the object to be treated.

As an example of a fiber article to be 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 further preferably 1 second or less. Examples thereof include those having water absorbency (hereinafter, also referred to as “articles made of water absorbent fiber”). The water-absorbent fiber article can absorb water and various aqueous liquids, and can absorb, for example, sweat, urine, and blood, which are one type of body fluid. The water-absorbent fiber article is typically composed mainly of water-absorbent fibers. As the water-absorbent fibers, for example, natural fibers such as wood pulp, cotton and hemp are used. The content of the water absorbent fibers in the water absorbent fiber article is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total mass of the water absorbent fiber article. The water-absorbent fiber article is, for example, a sheet-like fiber article having a thickness of about 0.3 to 20 mm, and more specifically, any one or more of a woven fabric (woven fabric), a knitted fabric, a non-woven fabric, and paper. Can be included.

The fiber treatment agent of the present invention can be used for making one surface of a variety of fiber articles including water-absorbent fiber articles water-repellent, and is suitable for the following applications (1) to (10), for example. Generally, the following (1) to (6) are applications for absorbing a relatively small amount of liquid, specifically about 1 mL or less, more preferably about 0.5 mL or less of the liquid, and the following (7) ) To (10) are applications for absorbing a larger amount of liquid, specifically about 1 to 100 mL, more preferably about 1 to 10 mL.

(1) Prevention of migration of foot sweat to shoes and insoles (deodorization of shoes) by making the non-skin-facing surface of socks (water-absorbent fiber article) water-repellent. The "non-skin-facing surface" referred to here is a surface (side relatively far from the user's skin) facing the side opposite to the user's skin side when using the water absorbent fiber article, and particularly Unless otherwise noted, it is the same. The surface of the water absorbent fiber article opposite to the non-skin facing surface (the surface facing the user's skin side during use) is the “skin facing surface”.
(2) Prevention of migration of excrement (clothes, 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-absorbent fiber article) water-repellent.
(3) Preventing the transfer of breast milk to clothes by making the non-skin-facing surface of a female brassiere (water-absorbent fiber article) water-repellent.
(4) Prevention of offset of the water-based ink by making the back surface of the drawing paper (article made of water-absorbent fiber) water-repellent.
(5) Improving the hiding property by making one surface of the nonwoven fabric (water-absorbent fiber article) water-repellent. A nonwoven fabric having improved hiding properties is suitable as a drip sheet, for example. A drip sheet is a sheet-like material that absorbs and holds drips (blood, etc.) that ooze out from foodstuffs such as meat and fish, and is used to maintain the freshness of foodstuffs. By covering the food material with a drip sheet made of a non-woven fabric, the water-repellent one surface of the non-woven fabric (the surface opposite to the food material side) prevents the strike-through of the drip and the blood oozing out from the food material. It is difficult to see the drip from the outside.
(6) Preventing the transfer of dirt to the table by making the back surface of the table cloth water repellent.

(7) Prevents dirt from sticking to your hands by making one side of the cloth and wipe (water absorbent fiber article) water repellent. (8) The inside of the bib (the water absorbent fiber article) (the surface on the side of the user's body) is made water repellent to prevent the transfer of dirt to clothes and spilled food.
(9) Prevention of floor wetting, slippage, and propagation of mold and other bacteria by making one side of the foot-wiping mat (article made of water-absorbent fiber) water-repellent.
(10) Prevents migration of sweat to the duvet, quilt, and pillow by making the back surface of the sheets, the duvet cover, and the pillow cover (article made of water-absorbent fiber) (the surface opposite to the user's body side) water-repellent ( 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) do not need to be water repellent on one side as described above, and there may be a case where both opposing surfaces of the fiber article may be water repellent.

(11) Prevention of adhesion of urine stains by making the skin-facing surface of the pants (water absorbent fiber article) water-repellent.
(12) The stickiness of sweat is reduced by making the skin-facing surface of shoes, socks, and hats (water-absorbent fiber articles) water-repellent.
(13) The stickiness of sweat is reduced by making the surface (the surface of the user's body side) of the sheets (the water absorbent fiber article) water-repellent.
(14) The tackiness of sweat is reduced by making the skin-facing surface of the underwear (water-absorbent fiber article) water-repellent.
(15) Prevention of sweat stains by making the non-skin-facing surface of underwear (water-absorbent fiber article) water-repellent.

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

[Examples 1 to 6 and Comparative Examples 1 to 7]
The silicone graft copolymer shown in Table 1 below was used as the soluble polymer. 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.
The fiber treatment agent was filled in a manual mist spray container to manufacture a fiber surface treatment article. 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 amount of 0.15 mL per push. As the bottle, PH-100 No. 2 white manufactured by Takemoto Container Co., Ltd. was used.

[Examples 7 to 22]
The polymers and polymer mixtures shown in Table 3 below were used as soluble polymers. A volatile solvent and a polymer content were blended as shown in Table 3 to prepare a fiber treatment agent. The fiber treatment agent was filled in a manual mist spray container to manufacture a fiber surface treatment article. 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 amount of 0.15 mL per push. As a bottle, PH-100 No. 2 white manufactured by Takemoto Container Co., Ltd. was used.

Details of the polymers used in Examples and Comparative Examples are as shown in Table 2. The yield stress at 25° C. of each polymer and the contact angle with water are shown in Table 2.
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 of 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, proportion of polysiloxane skeleton: 75% by mass, to 100 g of ethanol at 25° C. Solubility 50g.
Polymer E: poly(acrylic acid)-modified silicone, weight average molecular weight: about 60,000, weight average molecular weight of graft chain: about 2000, proportion of polysiloxane skeleton: 80% by mass, solubility at 25° C. in 100 g of ethanol: 50 g. The polymer E was manufactured by the manufacturing method described below.
Polymer F: (Acrylates/lauryl acrylate/stearyl acrylate/ethylamine oxide methacrylate) copolymer (Diaformer Z-631, manufactured by Mitsubishi Chemical Co., active ingredient 30% by mass, ethanol 63% by mass, water 7% by mass) ).
Polymer G: (Acrylates/lauryl acrylate/stearyl acrylate/ethylamine oxide methacrylate) copolymer (Diaformer Z-632, manufactured by Mitsubishi Chemical Co., active ingredient 30% by mass, ethanol 54% by mass, water 16% by mass) ).
Polymer H: (Acrylates/lauryl acrylate/stearyl acrylate/ethylamine oxide methacrylate) copolymer (Diaformer Z-651, manufactured by Mitsubishi Chemical Corporation, 30% by mass of active ingredient, 60% by mass of ethanol, 10% by mass of water) ).
Polymer I: Silicone resin (KR-251, manufactured by Shin-Etsu Chemical Co., Ltd., 20 mass% active ingredient, 80 mass% toluene).
Polymer J: (Acrylates/Dimethicone) copolymer (KP-541, manufactured by Shin-Etsu Chemical Co., Ltd., 60 mass% active ingredient, 40 mass% isopropanol).
Polymer K: tri(trimethylsiloxy)silylpropylcarbamate pullulan (TSPL-30-ID, manufactured by Shin-Etsu Chemical Co., Ltd., 30 mass% active ingredient, 70 mass% isododecane).
-Polymer L: (vinyl methyl ether/isopropyl maleate) copolymer (Gantrez ES-335I, manufactured by ISPE Japan Co., Ltd., active ingredient 50% by mass, isopropanol 50% by mass).
Polymer M: (Vinyl methyl ether/butyl maleate) copolymer (Gantrez ES-435, manufactured by ISPE Japan Co., Ltd., active ingredient 50% by mass, isopropanol 50% by mass).
-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 Ltd.).
Polymer P: (methacryloyloxyethyl carboxybetaine/alkyl methacrylate) copolymer (Yukaformer 202, manufactured by Mitsubishi Chemical Corporation, active ingredient 30% by mass, ethanol 70% by mass).
Polymer Q: vinyl acetate/vinylpyrrolidone copolymer (Rubiscor VA37E, manufactured by BASF, active ingredient 50% by mass, ethanol 50% by mass).
-Polymer R: (vinylpyrrolidone/methacrylamide/vinylimidazole) copolymer (rubisette Clear AT2, manufactured by BASF, weight average molecular weight: 270,000, active ingredient 25% by mass, water 75% by mass).
-Polymer S: Polyvinylcaprolactam (Rubiscol 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 to 30% by mass of active ingredient, 70 to 80% by mass of water, less than 5% by mass 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>
As a polyfunctional organopolysiloxane having a reactive functional group in a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer, a side chain primary aminopropyl-modified organopolysiloxane (weight average molecular weight of 50,000, per unit mass) Amino group mol number: 1/1970 mol/g, 200 g of Shin-Etsu Chemical Co., Ltd., and 16 g of N-acetyl-DL-homocysteine thiolactone were charged. In 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 a sulfanyl group.
<Synthesis of Polymer E>
17 g of ethanol was placed in a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer. The following solutions (a) and (b) were placed in separate dropping funnels while stirring under a nitrogen atmosphere under reflux at 80° C., and simultaneously 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 Fuji Film Wako Pure Chemical Industries, Ltd.) and 110 g of ethanol.
Solution (b): Radical-reactive organopolysiloxane synthesized in the above Synthesis Example 30 g, 2,2'-azobis(2,4-dimethylvaleronitrile) "V-65B" (Fuji Film Wako Pure Chemical Industries, Ltd.) Manufactured by Azo Polymerization Initiator) 0.4 g and ethanol 30 g.
Solution (c): 0.4 g of 2,2′-azobis(2,4-dimethylvaleronitrile) “V-65B” (azo polymerization initiator manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 20 g of ethanol Mixed solution.
After the 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 of measuring solubility in water>
Water (500 g) was added to a 1 L glass beaker, and a rotor (made of fluororesin (PTFE), φ8 mm×50 mm) was used and the temperature was kept in a thermostat at 25° C. while stirring at a rotation speed of 100 rpm. 0.1 g of each polymer is added, and after 10 minutes, it is visually confirmed whether or not it is in a uniformly transparent state. Add 0.1 g of each polymer in addition until it is not uniformly transparent, and measure the solubility in water. When each polymer was obtained as a solution dissolved in a solvent, the solvent was removed before the measurement.
When 50 g of the polymer is added and the mixture is uniformly transparent, the measurement is stopped at that point, and the solubility in 100 g of water at 25° C. is judged to be 10 g or more. If 0.1 g of the polymer is not uniformly transparent when added, it is determined that the solubility in 100 g of water at 25° C. is less than 20 mg.
Water: Pure water having an electric conductivity of 1 μS/cm or less at 25° C., which is manufactured by a pure water device G-10DSTSET manufactured by Organo Corporation.

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

[Evaluation]
Fiber articles were treated using the fiber surface-treated articles obtained in Examples and Comparative Examples, and the anti-slip property of the fiber treatment agent and the liquid barrier property of the fiber treatment agent 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 rectangular in shape with a length of 909 mm and a width of 151.5 mm. The floor surface of the flooring finishing material was treated with a floor wax (Rinlay all manufactured by Rinrei Co., Ltd.) three times under standard use conditions to obtain a floor surface for evaluation. Standard as use conditions, were treated floor wax in a ratio of floor ^{5 mL} / m 2 per unit area of ~ 15mL / ^{m 2.} The floor surface is divided at a position where the floor surface for evaluation is divided into two parts in the vertical direction, and the entire area of the floor surface from the position 20 cm above the floor surface with respect to one half of the floor surface area. On the other hand, the mist spray container was pushed a plurality of times to uniformly spray the fiber treatment agent so that 150 mg/m ^{2 of the} fiber treatment agent adhered thereto, and then the mixture was allowed to stand for 5 minutes to dry. The other half of the floor area was not sprayed with the fiber treatment agent. In this way, a floor surface for slip resistance evaluation was prepared in which one bisected area was the treated surface on which the treatment agent film was formed and the other bisected area was the untreated surface. Five panelists wearing socks of 85% by mass of polyester, 10% by mass of cotton and 5% by mass of polyurethane were made to walk from the untreated surface to the treated surface in the longitudinal direction of the floor surface for slip resistance evaluation. .. Then, the degree of slippage when making a U-turn on the treated surface was evaluated. The average of the panelists' evaluation was used as the evaluation result of the anti-slip property. The larger the evaluation point, the higher the evaluation.
(Evaluation criteria for risk of slippage)
1 point: extremely slippery as compared with the untreated surface.
2 points: It slides much more than the untreated surface.
3 points: slippery compared to the untreated surface.
4 points: Slightly slippery compared to the untreated surface.
5 points: Does not slip to the same extent as the untreated surface.

[Artificial urine barrier properties with fiber treatment agents]
A first fiber article (Kanakin No. 3 manufactured by the Japanese Standards Association) made of a cloth of 10 cm×10 cm was placed on a vertical table, and the upper surface of the fiber article was placed 10 cm above the fiber article. The mist spray container was pushed six times over the entire area to spray the fiber treatment agent, and then left still for 10 minutes to dry. Thus, a treatment agent-provided fiber article in which the fiber treatment agent was applied to the entire one surface of the fiber article was obtained. Then, another second textile article (Kanakin No. 3 manufactured by Japanese Standards Association) consisting of 10 cm×10 cm cloth was placed on a horizontal table, and treated on the second textile article. The agent-provided fiber article was overlaid with the treatment agent-applied side facing the second fiber article. The first fiber product is intended for underwear, and the second fiber product is intended for outer clothing pants. Under this condition, 0.5 mL of artificial urine was dropped toward the surface of the treated article to which the treatment agent was not applied. Immediately after the dropping, an acrylic plate having a bottom area larger than the areas of the first and second fibrous articles was placed thereon, and a pressure of 1 g/cm ² was applied for 60 seconds. This pressure is assumed to be the mounting pressure applied to the undergarment. Then, the acrylic plate was removed, and the mass of the first fibrous article before and after the dropping of the artificial urine was measured to determine the change in mass. This value is defined as the mass change amount (W1) of the first fiber product. Similarly, the mass of the second fibrous article before and after the dropping of the artificial urine was measured to determine the change in mass. This value is defined as the exudation amount (W2) of artificial urine. The ratio of the mass change amount (W1) of the first fiber article to the total value of the mass change amount (W1) and the exudation amount (W2) of the first fiber article was calculated as the barrier property (%). .. As for the barrier property, the closer the value is to 100%, the smaller the amount of exudation and the higher the barrier property. In this evaluation, the case where the barrier property is 90% or more is “A”, and the case where it is less than 90% is “B”.

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

Regarding Example 1, physiological saline (Otsuka raw food injection, manufactured by Otsuka Pharmaceutical Factory Co., Ltd.) was used instead of artificial urine, and the barrier property of physiological saline by the fiber treatment agent was 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 is satisfied, and the condition (II) that the contact angle with water is larger than 90 degrees. It can be seen that the fiber articles treated with the fiber treatment agent of each example satisfying the above conditions have a high barrier property against artificial urine and the floor on which the film of the fiber treatment agent of each example is formed is not slippery. On the other hand, the fiber articles of Comparative Examples 3 and 5 to 7 satisfying only the condition (I) have low barrier properties against artificial urine, and the fiber treating agents of Comparative Examples 1, 2 and 4 satisfying only the condition (II). It can be seen that the floor on which the film is formed is slippery. It was also found that the fiber article treated with the fiber treatment agent of Example 1 has a high barrier property against artificial urine and a high barrier property against physiological saline. From the above, according to the fiber treatment agent of each example, it is possible to effectively prevent the body fluid excreted from the body from seeping out of the clothing while using the clothing such as the undergarment that is usually used as it is. It is possible to expect that the floor will not be slippery even if it is unintentionally attached to the floor.

ADVANTAGE OF THE INVENTION According to this invention, while using the clothes, such as undergarments, which are usually used, as they are, while effectively preventing the body fluid excreted from the body from seeping out from the clothes, they unintentionally adhered to the floor. Even if the floor is slippery.

Claims (11)

A volatile solvent and one polymer or a mixture of two or more polymers soluble in the volatile solvent,
One of the polymers or two or more of the polymers have a solubility in water at 25° C. of less than 50 mg/100 g,
The content ratio of one kind of the polymer or a mixture of two or more kinds of the 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,
The fiber treating agent wherein the one kind of the polymer or the mixture of two or more kinds of the polymers has a contact angle with water of 90 degrees or more. Comprising a mixture of two or more of the above polymers,
The polymer mixture (A1) has a yield stress of 0.6 MPa or more at 25° C. and a contact angle with water of less than 90°, and (A2) a yield stress of 0.6 MPa at 25° C. The fiber treating agent according to claim 1, further comprising a polymer having a smaller contact angle with water of 90 degrees or more. The fiber treatment agent according to claim 1 or 2, wherein each polymer in the one kind of polymer or a mixture of two or more kinds of polymers has a polysiloxane skeleton as a main chain. The fiber treating agent according to any one of claims 1 to 3, wherein one polymer or each polymer in the mixture of two or more 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 a side chain thereof is at least one of N-acylalkyleneimine, acrylic acid, acrylic acid ester, and acrylamide. The fiber treatment agent according to item 4. The polymer of (A1) and the polymer of (A2) each have a polysiloxane skeleton as a main chain,
The ratio of the polysiloxane skeleton in the polymer (A1) is 40% by mass or more and less than 70% by mass,
The fiber treating agent according to claim 2, wherein the proportion of the polysiloxane skeleton in the polymer (A2) is 70% by mass or more. The fiber treatment agent according to claim 6, wherein the proportion of the polymer (A1) in the mixture of polymers is 20% by mass or more and 80% by mass or less. The fiber treatment agent according to any one of claims 1 to 7, which has a viscosity at 25°C of 20 mPa·s or less. The fiber according to any one of claims 1 to 8, which comprises, in addition to one polymer or two or more polymers, (B) a polymer having a solubility in water at 25°C of 50 mg/100 g or more. Processing agent. A fiber surface treatment article comprising the fiber treatment agent according to any one of claims 1 to 9 and a manual mist spray container filled with the fiber treatment agent. A fiber surface treatment article in which the fiber treatment agent according to any one of claims 1 to 9 is filled in a spray container or a coating container.