WO2020116600A1

WO2020116600A1 - Fiber treatment agent

Info

Publication number: WO2020116600A1
Application number: PCT/JP2019/047744
Authority: WO
Inventors: 繁宏松原; 祐樹阿部; 和啓杉山
Original assignee: 花王株式会社
Priority date: 2018-12-07
Filing date: 2019-12-06
Publication date: 2020-06-11

Abstract

A fiber treatment agent according to the present invention is characterized by containing components A, B, and C, wherein the content of an antibacterial agent, which is the component B, is not less than 4 ppm. The component A is a silicone graft polymer that has a main chain having a siloxane bond and a side chain having a molecular weight of not less than 800, and that has an IOB value of not less than 0.7. The component B is an antibacterial agent, and the component C is an organic solvent. The antibacterial agent, which is the component B, is preferably piroctone olamine. The ratio of the IOB value of the silicone graft polymer, which is the component A, with respect to the IOB value of the antibacterial agent, which is the component B, is preferably 0.4-3.0 in terms of former/latter ratio.

Description

Textile treatment agent

The present invention relates to a fiber treatment agent capable of imparting water repellency to textile articles such as clothing and exhibiting an antibacterial effect.

Conventionally, silicone compounds have been used for the purpose of imparting water repellency, flexibility and smoothness to textile articles such as clothing. For example, Patent Document 1 discloses a fiber treatment agent containing a specific amino-modified silicone. Patent Document 2 discloses, as a water repellent treatment agent capable of imparting water repellency to fibers and removable by washing, those containing a specific silicone-containing polymer copolymer.

Further, a hair styling product that can fix and maintain the hair in a desired shape and keep the hair in a natural feel without making it stiff or sticky is desired. As such, a polymer containing a polymer segment derived from a specific unsaturated monomer in a side chain of an organopolysiloxane segment which is a main chain and containing an organopolysiloxane graft polymer having a specific ratio is proposed (Patent References 3 and 4).

JP-A-4-163374 JP-A-2003-34784 Japanese Patent Laid-Open No. 10-306163 JP, 2014-77112, A

The present invention is a fiber treatment agent containing the following components A, B and C, and the content of the antibacterial agent of component B being 4 ppm or more.
Component A: Silicone graft polymer having a main chain having a siloxane bond and a side chain having a molecular weight of 800 or more and having an IOB value of 0.7 or more Component B: Antibacterial agent Component C: Organic solvent

Further, the present invention is characterized in that the fiber treating agent of the present invention is a sheet-like solid material. That is, the present invention includes a sheet-type product obtained by molding the above-mentioned fiber treatment agent of the present invention into a sheet-like solid material.
Further, the present invention is characterized in that the above-mentioned fiber treatment agent of the present invention is a stick-like solid material. That is, the present invention includes a stick-type product obtained by molding the above-mentioned fiber treatment agent of the present invention into a stick-shaped solid material.
The present invention is also a spray product obtained by filling a spray container with the fiber treatment agent of the present invention.
The present invention is also a roll-on product obtained by filling the roll-on container with the fiber treatment agent of the present invention.

FIG. 1 is a diagram showing an example of use of the fiber treatment agent of the present invention, and is a diagram schematically showing a wearing state of pants to which the fiber treatment agent is applied. FIG. 2A is a schematic view showing an antibacterial mechanism by the antibacterial agent, and FIG. 2B is a view schematically showing an antibacterial mechanism by the fiber treatment agent of the present invention.

Detailed Description of the Invention

U Generally, the urine remaining in the urethra after urination may come out and wet the inner clothing such as underwear. This is a phenomenon called “Post Micturition Dribble: PMD”, which is also called “small leak” because the amount of urine output is as small as about 0.1 mL to 2 mL compared to urinary incontinence. In particular, men have a longer urethra than women, and the urethra of men has a structure in which the urethra is bent at two places, and urine is likely to remain in the urethra, so that a slight leak is likely to occur. A small leak not only causes discomfort due to the wetting of inner garments such as pants, but it may also cause urine to seep over the outer garments such as pants worn over the inner garments. There is a problem that the urine spots are noticeable depending on the type of color. Incontinence pads have been proposed to deal with problems caused by such a small leak, but many people feel reluctant to use the incontinence pad, and take measures against a small leak without using the incontinence pad. The reality is that there is a strong demand for it.

As a method to prevent stains (urine stains) on the outer clothing due to a slight leak, treat the inner clothing with a commercially available waterproof spray to impart water repellency to it so that the urine released by a short leak does not transfer to the outer clothing. There are possible ways to do it. However, many commercially available waterproof sprays are configured so that the active ingredient such as silicone that contributes to the development of the water-repellent effect firmly adheres to the object to be treated so that the water-repellent effect lasts as long as possible. When the inner garment treated with the waterproof spray is washed with a washing machine after wearing, the active ingredient may remain without being removed, which is a hygienic problem.

In addition, human skin and underwear that are worn usually have intestinal bacteria such as skin-resident bacteria and stool-derived Escherichia coli, and if a slight leak occurs under such circumstances, those Bacteria may multiply by leaking urine as a nutrient source and cause skin problems such as rash. A treatment agent capable of preventing stains on the outer garment due to slight leakage and preventing bacteria from growing due to urine to maintain good hygiene of the skin, and capable of being washed and removed has not yet been provided.

Therefore, the present invention relates to a fiber treatment agent that prevents the inconvenience of body fluid such as urine oozing into clothes and being visible from the outside, has an excellent antibacterial effect, and can be removed by washing.

The fiber treatment agent of the present invention can impart wash-removable water repellency (waterproofness) to a fiber article which originally has no water repellency (waterproofness). For example, in a part of cotton men's pants that gets wet when a small amount of leakage occurs, typically in a part corresponding to the external urethral meatus of the wearer's penis at the front of the pants and in the vicinity thereof, a book should be prepared before wearing. By applying the fiber treatment agent of the invention, a barrier film that prevents the permeation of body fluids such as urine is formed in the applied part, and this barrier film can solve the above-mentioned problem of urine spots due to slight leakage. .. In the fiber treatment agent of the present invention, the main component of such a barrier coating is the component A silicone graft polymer.

FIG. 1 is a schematic diagram of an example of use of the fiber treatment agent of the present invention, in which a male wearer 100 wears pants 1 (inner clothing) having a barrier coating 2 formed on an outer surface (non-skin-facing surface) 1b. In addition, a state in which the outer garment 3 such as trousers is worn from above is shown. The barrier coating 2 is formed by applying the fiber treatment agent of the present invention to the outer surface 1b of the pants 1 by spraying or the like. Although the barrier coating 2 is laminated on the outer surface 1b of the pants 1 in FIG. 1, the barrier coating 2 is not necessarily formed as shown in FIG. Further, the fiber treatment agent of the present invention may be applied to the inner surface (skin-facing surface) 1a of the pants 1, or may be applied to both the inner surface 1a and the outer surface 1b.

When the pants 1 shown in FIG. 1 is worn, a so-called “small leak” occurs in which a small amount of urine of about 0.1 mL to 2 mL is unintentionally excreted from the external urethral opening of the penis of the wearer 100, and the excreted urine is generated. Even if is transferred from the inner surface 1a side of the pants 1 to the outer surface 1b side, transfer of excreted urine to the outer clothing 3 side is prevented by the water-repellent barrier coating 2 formed on the outer surface 1b side, and The inconvenience of urinary stains visible from the outside is prevented. If the barrier coating 2 cannot be removed by ordinary washing, the stain may not be sufficiently removed even when the pants 1 having the barrier coating 2 formed thereon is washed, and not only the appearance but also the hygiene. There is also a problem. For example, when the pants with the barrier coating are washed after use and still have the barrier coating remaining on the pants, when the pants are worn again, the components contained in the remaining barrier coating are Since components in urine which may cause hydrophobic interaction easily adhere to the remaining barrier coating, there is a possibility that disadvantages such as yellowing of pants and easy propagation of bacteria may occur. On the other hand, the barrier coating 2 according to the present invention can be removed by washing, and by washing the pants 1 on which the barrier coating 2 is formed according to a conventional method, the pants 1 do not have the barrier coating 2 in a normal state. Since it is reset to, the pants 1 are not yellowed and are hygienic. When it is desired to take measures against the small leak again on the pants 1 thus reset, the fiber treatment agent of the present invention may be applied to a desired portion of the pants 1.

Further, the fiber treatment agent of the present invention is excellent not only in the effect of preventing urinary spots but also in the antibacterial effect, and prevents the inconvenience of bacterial growth using excrement including urine as a nutritional source, and thus bacterial growth. It can prevent skin troubles caused by. In the fiber treatment agent of the present invention, the antibacterial effect of the component B is directly related to the expression of the antibacterial effect, but the silicone graft polymer of the component A also indirectly contributes to the expression of the antibacterial effect. That is, for example, as shown in FIG. 2(a), by spraying an antibacterial agent on the underwear for the purpose of preventing the growth of bacteria caused by urine that has leaked out a little, bacteria such as skin-resident bacteria When the antibacterial agent 51 is applied to the environment where 50 exist, the number of the antibacterial agent 51 to the number of bacteria 50 per unit volume tends to be insufficient because the antibacterial agent 51 thus applied is spread over a wide range. , There is a possibility that sufficient antibacterial effect may not be obtained. On the other hand, when the fiber treatment agent of the present invention is applied to underwear, as described above, as shown in FIG. 1, the undergarment is mainly composed of the silicone graft polymer of the component A and physically inhibits migration of urine. When the barrier coating 2 is formed, in this barrier coating 2, as shown in FIG. 2( b ), the antibacterial agent 51 (the antibacterial agent-derived component of the component B) is distributed at a relatively high density, The antibacterial agent 51 can act directly on the bacteria 50 on the barrier coating 2. Therefore, as shown in FIG. 2A, a sufficient antibacterial effect can be exhibited even with a small amount of the antibacterial agent 51 as compared with the case where the antibacterial agent 51 is used alone against the bacteria 50. That is, the antibacterial effect exhibited by the fiber treatment agent of the present invention is exhibited by the cooperation of the component A silicone graft polymer and the component B antibacterial agent, and when the antibacterial agent is used alone, This is a particularly advantageous effect that is not achieved. This is also clear from the comparison between the example and the comparative example described later.

Also, according to the fiber treatment agent of the present invention, a deodorizing effect can be expected as a secondary effect. In other words, the initial urinary odor itself, which is shortly after excretion, does not normally give off an unpleasant odor though there are physical conditions and individual differences. It is believed that the fiber treatment agent of the present invention suppresses urinary spoilage due to its excellent antibacterial effect, and naturally suppresses the spoiled odor of urine. As described above, the fiber treatment agent of the present invention is particularly effective in suppressing the putrid odor of urine that may occur after a certain period of time has passed after urination.

The fiber treatment agent of the present invention can be applied to various fiber articles, and as described above, even if the "fiber article originally has no water repellency (waterproofness)", It is possible to impart water repellency (waterproofness) that can be removed by washing. As a specific example of the “fiber article that originally has no water repellency (waterproofness)”, a “fiber article capable of retaining body fluid” can be exemplified.

[Component A: Silicone graft polymer]
The silicone graft polymer of component A has a main chain having a siloxane bond and a side chain. The chemical structure of the silicone graft polymer of component A is not particularly limited, but preferred specific examples include those having a modified organopolysiloxane segment represented by the following general formula (1) or (2).

In the general formulas (1) and (2), R ^1's each independently represent an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ² contains a hetero atom. Represents an alkylene group which may be present. p represents a number of 2 or more and 4000 or less, and q represents a number of 2 or more and 250 or less. In the formula, the bonding mode of the p repeating units and the q repeating units may be such that the repeating units may be connected in a block form or may be connected in a random form.

In the general formula (1) or (2), the siloxane bond (—Si—O—Si—) is the main chain, and R ¹ and R ² are side chains, respectively. (For example below, polymer segment derived from an unsaturated monomer) other atoms (e.g., hydrogen atom) or other functional groups in R ² if are attached, R ² and those other atoms or functional groups The entire conjugate of is a side chain.

In the above general formulas (1) and (2), two or more functional groups (for example, a polymer segment derived from an unsaturated monomer, which will be described later) have a “hetero” structure at any silicon atom constituting the main chain. It is preferably bound through R ² which is an “alkylene group which may include an atom”, more preferably bound to one or more silicon atoms excluding both ends via R ^2. It is more preferable that the two or more silicon atoms excluding the ends are bound via R ² .

In the general formulas (1) and (2), examples of the alkyl group represented by R ¹ include a linear, branched, or cyclic alkyl group, and the number of carbon atoms of the alkyl group represented by R ¹ is From the viewpoint of water dispersibility of the silicone graft polymer of component A, it is preferably 1 or more and 10 or less, more preferably 6 or less. Specific examples of the alkyl group represented by R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group, nonadecyl group, eicosyl group, docosyl group and the like. The above "water dispersibility of the silicone graft polymer" refers to the property that the silicone graft polymer can be stably dispersed in a composition containing water as a main component, and if this property is good, It is preferable because it enhances the washing removability required in the invention.

The carbon number of the aryl group represented by R ¹ is preferably 6 or more and 12 or less, and more preferably 9 or less from the viewpoint of water dispersibility of the silicone graft polymer of the component A. Specific examples of the aryl group represented by R ¹ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthryl group and a phenanthryl group.

Among these, R ¹ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear chain having 1 to 3 carbon atoms, from the viewpoint of water dispersibility of the silicone graft polymer of component A. Alternatively, a branched chain alkyl group is more preferable, and a methyl group is still more preferable.

In the general formulas (1) and (2), p represents a number of 2 or more and 4000 or less, and q represents a number of 2 or more and 250 or less.
From the viewpoint of enhancing the water repellency (waterproofness) required in the present invention, p is preferably a number of 50 or more, more preferably 80 or more, still more preferably 100 or more, and water dispersion of the silicone graft polymer of component A. From the viewpoint of sex, the number is preferably 2000 or less, more preferably 1300 or less, and further preferably 700 or less.
q is preferably a number of 3 or more, more preferably 5 or more, from the viewpoint of water dispersibility of the silicone graft polymer of the component A, and preferably 50 or less, from the viewpoint of enhancing the washing removability required in the present invention. The number is preferably 30 or less.

In the general formulas (1) and (2), a part or all of R ² , which is an “alkylene group which may contain a hetero atom”, is derived from another functional group (for example, an unsaturated monomer derived from the after-mentioned). Polymer segment) and functions as a linking group with other functional groups. When there is R ² that is not bonded to another functional group (polymer segment derived from an unsaturated monomer), the R ² is bonded to a hydrogen atom.

In the present invention, the carbon number of R ² is preferably 2 or more, more preferably 3 or more from the viewpoint of availability of raw materials at the time of producing the component A silicone graft polymer, and the number of carbon atoms of the component A silicone graft polymer is From the viewpoint of water dispersibility, it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less.

In the present invention, R ² may be separated by one or more atoms or functional groups selected from an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and —NR ³ CO—. .. That is, R ^{2 which} is an “alkylene group which may contain a hetero atom” has a structure of “—(alkylene group moiety 1)—(the above-mentioned atom or functional group)—(alkylene group moiety 2)—”. In this case, the carbon number of the alkylene group means the sum of the carbon number of the alkylene group portion 1 and the carbon number of the alkylene group portion 2. Here, R ³ is an alkyl group having 1 to 3 carbon atoms. When the alkylene group, which may contain a hetero atom, is cleaved by the atom or functional group, it may be cleaved by —NHCO— from the viewpoint of easy production of the silicone graft polymer of the component A. preferable.

In the present invention, R ² is a hydroxyl group, an amino group, an alkyl (having 1 to 3 carbon atoms) amino group, a dialkyl (having 1 to 3 carbon atoms) amino group, an amino group and a fatty acid having 2 to 4 carbon atoms are dehydrated. One or more monovalent groups selected from an amide group obtained by condensation, a carboxy group, and an alkyl (having 1 to 3 carbon atoms) ester group may be substituted. In this case, the carbon number of R ² does not include the carbon number of the substituent. From the viewpoint of easy availability of raw materials during production of the component A silicone graft polymer, R ² is at least one selected from an acetamide group, an alkyl (having 1 to 3 carbon atoms) amino group, and an amino group. It is preferred that the valent group be substituted.

In the present invention, R ² , which is an “alkylene group which may contain a hetero atom”, is a divalent divalent selected from —O—, —S—, —NH—, —NR ³⁰ — and —COO—. A hetero atom or a divalent group containing a hetero atom may be substituted. Here, R ³⁰ is an alkyl group which may be substituted with a dimethylamino group (having 1 to 3 carbon atoms). This hetero atom, or a divalent group containing a hetero atom, has a structure in which R ² acts as a linking group with another functional group (for example, a polymer segment derived from an unsaturated monomer described later). It is bonded to another functional group. In other cases, it is bonded to a hydrogen atom.

From the viewpoint of ease of production of the silicone graft polymer of the component A, R ² is preferably substituted with —S—.
R ² is a hetero atom contained in R ² , preferably a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a sulfur atom, through another functional group (for example, a polymer derived from an unsaturated monomer described later). Segment).
Therefore, R ² (the alkylene group which may contain a hetero atom) is (i) an unsubstituted alkylene group, (ii) an oxygen atom, a sulfur atom, —NH—, —COO—, —NHCO—, and — Alkylene group separated by one or more atoms or functional groups selected from NR ³ CO—, (iii) hydroxyl group, amino group, alkyl (having 1 to 3 carbon atoms) amino group, dialkyl (having 1 to 3 carbon atoms) ) Amino group, one or more monovalent group selected from an amide group obtained by dehydration condensation of an amino group and a fatty acid having 2 to 4 carbon atoms, a carboxy group, and an alkyl (1 to 3 carbon atom) ester group An alkylene group substituted by a group, (iv) a divalent hetero atom selected from —O—, —S—, —NH—, —NR ³⁰ — and —COO—, or a divalent group containing a hetero atom. In addition to the alkylene group substituted by, the alkylene group formed by the combination of the above (ii), (iii), and (iv) is applicable.

Specific examples of R ² which is the “alkylene group which may contain a hetero atom” in the present invention include the following formulas (i) to (xii). Above all, R ² is preferably the following formulas (xi) and (xii) from the viewpoint of ease of production of the component A silicone graft polymer.

In the formulas (i) to (xii), * represents a site bonded to a silicon atom constituting the main chain in the general formula (1) or (2), and ** represents another atom (hydrogen atom). Alternatively, it represents a site that binds to another functional group (for example, a polymer segment derived from an unsaturated monomer described later).
In the above formula (xii), X ¹ is at least one selected from —O—, —OCO—, —COO—, —CONH—, and —NHCO—, and is easy to prepare for the component A silicone graft polymer. From the viewpoint, —CONH— or —NHCO— is preferable, and —NHCO— is more preferable.

In the formula (xii), R ⁴ is a hydroxyl group, an amino group, an alkyl (having 1 to 3 carbon atoms) amino group, a dialkyl (having 1 to 3 carbon atoms) amino group, an amino group and 2 to 4 carbon atoms. It is an alkylene group which may be substituted with one or more monovalent groups selected from an amide group, a carboxy group and an alkyl (having 1 to 3 carbon atoms) ester group obtained by dehydration condensation of the following fatty acids. The substituent is preferably an acetamide group, an alkyl (having 1 to 3 carbon atoms) amino group, and an amino group from the viewpoint of availability of raw materials during production. The number of carbon atoms of the alkylene group represented by R ⁴ is preferably 2 or more, more preferably 3 or more, from the viewpoint of ease of production of the component A silicone graft polymer, and the component A silicone graft polymer. From the viewpoint of water dispersibility, it is preferably 10 or less, more preferably 6 or less.
Specific examples of R ⁴ include the following formulas (xiii) to (xv).

In the formula (xiv), X ⁻ represents an anion such as a chloride ion, a halide ion such as a bromide ion, an acetate ion, and an alkyl (having 1 to 3 carbon atoms) sulfate ion.

In the present invention, other specific examples of R ² (an alkylene group which may contain a hetero atom) include a C 2-20 alkylene group containing a nitrogen atom, an oxygen atom and/or a sulfur atom, preferably these. An alkylene group having 2 to 20 carbon atoms and containing 1 to 3 hetero atoms can be exemplified. Specifically, it is obtained by adding (B) secondary amine, tertiary amine, (B) secondary amine, and H ⁺ to a tertiary amine at the carbon-carbon and/or terminal of the alkylene chain. Examples thereof include an ammonium salt, (iii) a quaternary ammonium salt, and (iv) an alkylene group having 2 to 20 carbon atoms and containing an oxygen atom and/or (v) a sulfur atom. Among these, specific examples of preferable ones include the following formulas (xvi) to (xx).

The silicone graft polymer of component A is characterized by having side chains with a molecular weight of 800 and above. For example, when the silicone graft polymer of the component A has a modified organopolysiloxane segment represented by the general formula (1) or (2), one of the side chains bonded to the siloxane bond which is the main chain of the segment is used. A certain R ² (alkylene group which may contain a hetero atom) and another functional group (for example, a polymer segment derived from an unsaturated monomer described later) has a molecular weight of 800 or more.

The fiber treatment agent of the present invention is characterized in that it imparts “washable and removable water repellency” to the fiber article which originally has no water repellency, rather than simply imparting water repellency. One of the factors closely related to providing washable water repellency is the molecular weight of the side chain of the silicone graft polymer of component A. As described above, the silicone graft polymer of the component A is the main component of the barrier coating formed on the object to be treated (fiber article) when the fiber treating agent of the present invention is applied to the object. When the molecular weight of the side chain is 800 or more, the barrier coating is easily removed by usual washing of clothes. If the silicone graft polymer of the component A does not have a side chain having a molecular weight of 800 or more, it becomes difficult to impart "wash-removable water repellency" to the object to be treated.

The molecular weight of the “side chain having a molecular weight of 800 or more” contained in the component A silicone graft polymer is preferably 900 or more, and more preferably 1000 or more. The upper limit of the molecular weight of the side chain is not particularly limited, but if the molecular weight of the side chain is too large, the water repellency of the barrier coating may be decreased, and the urine stain prevention effect may be decreased. Considering the above, the molecular weight of such a side chain is preferably 50,000 or less, more preferably 35,000 or less, and further preferably 25,000 or less.

When the silicone graft polymer of the component A has a modified organopolysiloxane segment represented by the above general formula (1) or (2), R ² (even if it contains a hetero atom, with respect to the siloxane bond of the main chain) It is preferable that the “polymer segment derived from an unsaturated monomer” is bonded via a good alkylene group). In that case, the molecular weight of the side chain as the “combination of R ² and a polymer segment derived from an unsaturated monomer” is preferably in the above range, and the polymer segment derived from an unsaturated monomer, that is, It is more preferable that the molecular weight of the portion excluding R ² from the conjugate is within the above range.

The silicone graft polymer as the component A may have at least one side chain having a molecular weight of 800 or more, but from the viewpoint of more reliably exhibiting the above-described action and effect, the side chain having a molecular weight of 800 or more is 5 The above is preferable.

On the other hand, the molecular weight of the main chain of the silicone graft polymer of the component A, more specifically, the siloxane bond is not particularly limited, but from the viewpoint of exhibiting water repellency (waterproofness), preferably 10,000 or more, more preferably 30,000 or more. , And preferably 200,000 or less, more preferably 100,000 or less. The molecular weight of the main chain or side chain of the silicone graft polymer of component A can be controlled by appropriately selecting the polymerization conditions.

The molecular weight of the main chain or side chain of the silicone graft polymer of the component A can be determined, for example, as a polystyrene-reduced number average molecular weight or weight average molecular weight in gel permeation chromatography (GPC) analysis. The specific measurement conditions are as follows. When a commercially available product is used as the silicone graft polymer of the component A, the molecular weight of its main chain or side chain may be the value described in catalogs or the like.
・Column: K-804L+K-804L (Shodex (registered trademark), Showa Denko KK)
Eluent: 1 mmol Pharmin DM2098 (manufactured by Kao Corporation)/CHCl ₃
・Eluent flow rate: 1.0 mL/min
・Column temperature: 40℃
・Detector: RI
・Sample concentration: 5 mg/mL
・Sample injection volume: 100 μL

In order to impart the above “washable and removable water repellency” to the object to be treated (fiber article), it is not sufficient that the silicone graft polymer of component A has a side chain with a molecular weight of 800 or more. It is necessary that the IOB value of the graft polymer is 0.7 or more. The IOB (Inorganic Organic Balance) value is a measure of the “inorganic value/organic value”, which is the ratio of the inorganic value and the organic value of a substance.

In general, the properties of a substance are largely controlled by various intermolecular forces between molecules, and this intermolecular force is mainly composed of Van Der Waals force due to molecular mass and electrical affinity due to the polarity of molecules. If each of the Van Der Waals force, which has a great influence on the change in the property of a substance, and the electrical affinity can be individually grasped, the properties of an unknown substance or a mixture thereof can be predicted from the combination. be able to. This idea is a theory well known as "organic conceptual diagram theory". The organic conceptual diagram theory includes, for example, "Organic Analysis" written by Minoru Fujita (Kaniya Shoten, Showa 5), "Systematic Organic Qualitative Analysis (Pure Product Edition)" by Minoru Fujita (Kyoritsu Publishing, 1953), Minoru Fujita The book "Reorganized Chemistry and Experiments-Organic Chemistry" (Kawade Shobo, 1971), "Systematic Organic Qualitative Analysis (Mixture)" by Minoru Fujita and Masami Akatsuka (Kazama Shobo, 1974), and Yoshio Koda It is described in detail in Shiro Sato and Yoshio Honma's "New edition: Organic Conceptual Diagram: Basics and Applications" (Sankyo Publishing, 2008). In the organic conceptual diagram theory, regarding the physicochemical properties of substances, the degree of physical properties mainly due to VanDer Waals force is called “organic”, and the degree of physical properties mainly due to electrical affinity is called “inorganic”, The physical properties of a substance are considered as a combination of "organic" and "inorganic". Then, one carbon (C) is defined as organic 20, and the inorganic and organic values of various polar groups are defined as shown in Table 1 below, and the sum of the inorganic values and the organic The sum of the values is calculated and the ratio of the two is defined as the IOB value.

The silicone graft polymer of the component A is a copolymer, and the IOB value is calculated according to the following procedure according to the molar ratio of the monomers used for the copolymerization. That is, the copolymer is obtained from the monomer A and the monomer B, the organic value of the monomer A is OR _A , the inorganic value is IN _A , the organic value of the monomer B is OR _B , and the inorganic value is Is IN _B and the molar ratio of monomer A/monomer B is M _A /M _B , the IOB value of the copolymer is calculated from the following formula.

The IOB value of the silicone graft polymer as the component A is 0.7 or more as described above, preferably 0.9 or more, more preferably 1.1 or more, and further preferably 1.2 or more. The upper limit of the IOB value is not particularly limited, but if the IOB value is too large, the water repellency of the barrier coating may be reduced, and the urine stain prevention effect may be reduced. Considering the above, the IOB value is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.0 or less.

The IOB value of the component A silicone graft polymer is as described above, and the organic value itself is preferably 20,000 or more, more preferably 30,000 or more, further preferably 40,000 or more, and preferably 700,000 or less, more preferably It is 600,000 or less, more preferably 500000 or less. The inorganic value itself of the component A silicone graft polymer is preferably 30,000 or more, more preferably 40,000 or more, further preferably 50,000 or more, and preferably 900,000 or less, more preferably 800,000 or less, further preferably 700,000 or less. Is.

The "polymer segment derived from an unsaturated monomer" constituting the side chain of the silicone graft polymer of the component A will be further described. The polymer segment derived from the unsaturated monomer is an aqueous dispersion of the silicone graft polymer of the component A. From the viewpoint of property, the repeating unit derived from N,N-dimethylacrylamide (hereinafter also referred to as “DMAAm”) in the polymer segment derived from unsaturated monomer is preferably 50% by mass or more, more preferably 70% by mass. Or more, and more preferably 75 mass% or more. Further, from the viewpoint of reducing stickiness of the fiber article after applying the fiber treatment agent of the present invention to the fiber article, the content of the repeating unit derived from DMAAm in the polymer segment derived from the unsaturated monomer is: It is preferably 100% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.
In the present invention, the repeating unit derived from an unsaturated monomer refers to a repeating unit formed during polymerization of the unsaturated monomer.
In the silicone graft polymer of component A, the content of the repeating unit derived from DMAAm in the polymer segment derived from an unsaturated monomer can be measured by the NMR method.

In the polymer segment derived from an unsaturated monomer, the portion other than the repeating unit derived from DMAAm is composed of a 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. In the polymer segment derived from unsaturated monomer, the portion other than the repeating unit derived from DMAAm may be composed of a repeating unit derived from a single type of unsaturated monomer copolymerizable with DMAAm, or two types. It may be composed of repeating units derived from the above unsaturated monomers.

Regarding the above-mentioned “repeating unit derived from an unsaturated monomer copolymerizable with DMAAm”, specific examples of the olefin 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.

Regarding the above-mentioned “repeating unit derived from an unsaturated monomer copolymerizable with DMAAm”, specific examples of the (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, (meth ) Propyl acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid 2 -(Meth)acrylic acid ester having an alkyl group having 1 to 16 carbon atoms such as ethylhexyl, decyl (meth)acrylate, dodecyl (meth)acrylate, and cyclohexyl (meth)acrylate; (meth)acrylic acid 2- Examples thereof include (meth)acrylic acid ester having an alkyl group having 1 to 16 carbon atoms in which a hydroxyl group such as hydroxyethyl is substituted; and polyethylene glycol (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, and the like.

Regarding the above-mentioned “repeating unit derived from an unsaturated monomer copolymerizable with DMAAm”, specific examples of (meth)acrylamides excluding DMAAm include (meth)acrylamides such as acrylamide and methacrylamide; N,N- N,N-dialkyl(meth)acrylamides such as diethyl(meth)acrylamide (excluding DMAAm); N-isopropyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-alkyl(meth)acrylamides such as N-tert-octyl(meth)acrylamide; N-monosubstituted (meth)acrylamides having a carbonyl group on the substituent on the nitrogen atom such as diacetone(meth)acrylamide; N, N-monosubstituted (meth)acrylamides having an amino group as a substituent on the nitrogen atom such as N-dimethylaminopropyl (meth)acrylamide; N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, etc. Examples thereof include N-monosubstituted (meth)acrylamides having a hydroxyl group as a substituent on the nitrogen atom.

Among these, as the above-mentioned “repeating unit derived from an unsaturated monomer copolymerizable with DMAAm”, from the viewpoint of maintaining the water repellency (waterproofness) of the fiber article to which the fiber treatment agent of the present invention is applied, , (Meth)acrylamides and/or (meth)acrylates excluding DMAAm are preferable, and acrylamide, methacrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-tert-butyl(meth) ) Acrylamide, diacetone (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-methylol (meth)acrylamide, methyl (meth)acrylate, (meth)acrylic acid More preferred are ethyl, propyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate, and N-tert. -Butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, diacetone (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate, N,N-dimethyl Aminopropyl(meth)acrylamide is more preferable, N-tert-butyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, diacetone(meth)acrylamide, methyl(meth)acrylate, ethyl(meth)acrylate, ( Even more preferred is tert-butyl (meth)acrylate, even more preferred is N-tert-butyl (meth)acrylamide.

A preferred specific example of the polymer segment derived from an unsaturated monomer is a poly(N-acylalkyleneimine) segment represented by the following general formula (3).

In the general formula (3), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents 2 or 3. Examples of the alkyl group having 1 to 3 carbon atoms represented by R ²⁰ include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. The degree of polymerization of the repeating unit represented by the general formula (3) is not particularly limited, but is 1 to 500, for example.

Preferred specific examples of the component A silicone graft polymer include compounds (polyoxazoline-modified silicone) represented by the following formulas (A1) and (A2).

In the formula (A1), r represents a number of 5 or more and 100 or less.
In the formula (A2), Ac represents an acetyl group “CH ₃ C(═O)—”, s represents a number of 100 or more and 300 or less, and t represents a number of 0 or more and 50 or less.
In the formulas (A1) and (A2), p and q have the same meanings as p and q in the formulas (1) and (2), respectively.

The overall constitution of the silicone graft polymer of the component A will be further described. The silicone graft polymer of the component A has an organopolysiloxane segment such as the modified organopolysiloxane segment represented by the general formula (1) or (2). In this case, the content of the organopolysiloxane segment in the silicone graft polymer is preferably 20% by mass or more, more preferably from the viewpoint of maintaining the water repellency (waterproofness) of the fiber article to which the fiber treatment agent of the present invention is applied. Is 30% by mass or more, more preferably 40% by mass or more, and from the viewpoint of water dispersibility of the silicone graft polymer of the component A, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass. % Or less. The content of the organopolysiloxane segment in the silicone graft polymer of the component A can be measured by NMR.

Further, from the viewpoint of water dispersibility of the silicone graft polymer of the component A, and the water repellency (waterproofness) of the fiber article to which the fiber treatment agent of the present invention is added, the organopolysiloxane segment (a), The mass ratio (a/b) with the polymer segment (b) derived from an unsaturated monomer is preferably 20/80 or more, more preferably 30/70 or more, further preferably 40/60 or more, and , Preferably 99/1 or less, more preferably 95/5 or less, still more preferably 90/10 or less.

In the present specification, the above-mentioned mass ratio (a/b) refers to "the radical-reactive organopolyamine charged during production" when the silicone graft polymer of the component A is produced from a known radical-reactive organopolysiloxane. From "total mass (c) of polysiloxane" and "total mass (d) of unsaturated monomer charged at the time of production", "derived from unsaturated monomer not bonded to organopolysiloxane produced at the time of manufacturing" The value (c/(d−e))”, which is the value obtained by subtracting “the total mass (e) of the polymer” from the formula (I) below.
a/b=c/(de) (I)

Further, the number average molecular weight (MNg) of the organopolysiloxane segment between polymer segments derived from adjacent unsaturated monomers (hereinafter, sometimes referred to as “molecular weight between grafting points”) is water-repellent (waterproof). From the viewpoint of, preferably 500 or more, more preferably 700 or more, further preferably 1000 or more, still more preferably 1500 or more, from the viewpoint of water dispersibility of the silicone graft polymer of the component A, preferably 10,000 or less, It is more preferably 5000 or less, still more preferably 3000 or less, still more preferably 2500 or less.
Here, the "organopolysiloxane segment between polymer segments derived from adjacent unsaturated monomers" means, as shown in the following general formula (4), an organopolysiloxane segment of a polymer segment derived from an unsaturated monomer. A portion surrounded by a broken line between two points from the bonding point (bonding point A) to the siloxane segment to the bonding point (bonding point B) of the polymer segment derived from the unsaturated monomer adjacent thereto, It refers to a segment composed of one R ¹ SiO unit, one R ² , and y+1 R ¹ ₂ SiO units.

In the general formula (4), each R ¹ independently represents an alkyl group having 1 to 22 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ² is an alkylene group which may contain a hetero atom. , -W-R ⁵ represents a polymer segment derived from an unsaturated monomer, R ⁵ represents a residue or hydrogen atom of a polymerization initiator, and y represents a positive number.

The molecular weight between grafting points is the average value of the molecular weight of the part surrounded by the broken line in the general formula (4), and is the mass of the organopolysiloxane segment per mol of the polymer segment derived from the unsaturated monomer (g. /Mol). The molecular weight between grafting points is the case where the silicone graft polymer of the component A is produced from a known radical-reactive organopolysiloxane, and all radical-reactive functional groups and polymers derived from unsaturated monomers are When bonded, it is considered to be the same as the reciprocal value of the number of moles (mol/g) of the radical-reactive functional group present per unit mass of the radical-reactive organopolysiloxane.

When the silicone graft polymer of the component A has an organopolysiloxane segment such as the modified organopolysiloxane segment represented by the general formula (1) or (2), the weight average molecular weight of the organopolysiloxane segment ( MWsi) is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 15,000 or more, from the viewpoint of maintaining water repellency (waterproofness). MWsi is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 60,000 or less, still more preferably 50,000 or less, from the viewpoint of the water dispersibility of the component A silicone graft polymer. In the present specification, MWsi is measured by gel permeation chromatography (GPC) and converted into polystyrene, and the measurement conditions of GPC at that time are as described above.

When the silicone graft polymer of the component A is produced from a known radical-reactive organopolysiloxane, the MWsi is a radical-reactive organopolysiloxane because the organopolysiloxane segment has a common skeleton with the radical-reactive organopolysiloxane. It is almost the same as the weight average molecular weight (MWra) of siloxane and is regarded as the same in the present invention. In the present specification, MWra is measured by gel permeation chromatography (GPC) and converted into polystyrene, and the measurement conditions of GPC at that time are as described above.

The weight average molecular weight (MWt) of the silicone graft polymer of component A is preferably 10,000 or more, more preferably 14,000 or more, still more preferably 17,000 or more, still more preferably 30,000 or more, from the viewpoint of maintaining water repellency (waterproofness). From the viewpoint of water dispersibility of the silicone graft polymer of the component A, it is preferably 200,000 or less, more preferably 160,000 or less, further preferably 130000 or less, still more preferably 95,000 or less. Within this range, the fiber article can be imparted with sufficient water repellency (waterproofness) and, in addition, the water dispersibility of the silicone graft polymer of the component A will be excellent. The agent can be excellent in washability. In the present specification, MWt is measured by gel permeation chromatography (GPC) and converted into polystyrene, and the measurement conditions of GPC at that time are as described above.

Further, when the silicone graft polymer of the component A is produced from the radical-reactive organopolysiloxane, the component A of the component A obtained by using the following formula (II) from MWra and the reciprocal of the above mass ratio (a/b). The calculated weight average molecular weight (MWtcalc) of the silicone graft polymer imparts sufficient water repellency (waterproofness) to the fiber article and enhances the water dispersibility of the component A silicone graft polymer to improve the fiber treatment agent. Is preferably 10,000 or more, more preferably 14,000 or more, still more preferably 17,000 or more, still more preferably 30,000 or more, from the viewpoint of water dispersibility of the component A silicone graft polymer. It is preferably 200,000 or less, more preferably 160000 or less, still more preferably 130000 or less, still more preferably 95,000 or less.
MWtcalc = MWra x {1 + mass ratio (b/a)} (II)

The silicone graft polymer of the component A is, for example, (i) an organopolysiloxane having a reactive functional group, and a polymer segment derived from an unsaturated monomer having a functional group capable of reacting with the reactive functional group at the terminal. Can be produced by a graft-onto method (polymer reaction method) of reacting with a. or (ii) a graft-from method of radically polymerizing an unsaturated monomer in the presence of a radical-reactive organopolysiloxane. Among these, the manufacturing method (ii) is preferable from the viewpoint of reducing the load during manufacturing. The silicone graft polymer as the component A is, for example, the production method described in Patent Document 3 (for example, the production method described in [0016] to [0023] of the same document) or the production method described in Patent Document 4 (for example, the same document). [0036] to [0067]).

In the fiber treatment agent of the present invention, the content of the silicone graft polymer of the component A is the effect obtained by this, in particular, the effect of imparting water repellency to the object to be treated and the effect of increasing the antibacterial effect by the antibacterial agent of the component B. From the viewpoint of more reliably producing the above-mentioned, the total amount of the fiber treating agent is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and preferably Is 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. Regarding the "total mass of the fiber treatment agent", when the fiber treatment agent is a so-called spray type (in the case of the fiber treatment agent in a spray product obtained by filling a spray container with the fiber treatment agent), the fiber When the treating agent contains a propellant, the "total mass of the fiber treating agent" does not include the mass of the propellant. The same applies to the "total mass of the fiber treatment agent" unless otherwise specified.

[Component B: antibacterial agent]
As the antibacterial agent of component B, those capable of suppressing the growth of bacteria can be used without particular limitation, and those that act to cut off the source of odor, that is, indigenous bacteria or enterobacteria causing odor, Those having an action of suppressing the growth of these bacteria-derived enzymes are preferable. Examples thereof include inorganic antibacterial agents and organic antibacterial agents that suppress or kill the growth and growth of bacteria involved in the generation of urine odor, and one of these may be used alone or two or more thereof may be used in combination.

Specific examples of the inorganic antibacterial agent include, for example, silver, zinc, copper, magnesium, calcium, aluminum, antimony, bismuth antibacterial metal ions or salts as a carrier, zeolite, silica gel, low molecular weight glass, calcium phosphate, Examples thereof include zirconium phosphate, silicate, and fine particle powder or acicular crystals supported on titanium oxide.

Specific examples of the organic antibacterial agent include piroctone olamine [1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone monoethanolamine salt], oleic acid K, anionic surfactants such as Na linoleate, Na 1-pentasulfonate, Na 1-decanesulfonate, Na butylnaphthalene sulfonate, Na dodecyl sulfate, Na dodecylbenzene sulfonate, and Na hexadecyl sulfate, cetyl phosphate Cationic surfactants such as benzalkonium, benzethonium chloride, benzalkonium chloride, cetylpyridinium chloride, oolong tea extract, ages extract, sardine extract, saccharum extract, sardine extract, olive extract, chamomile extract, chamomile extract, karin extract, Licorice extract, yellowfin extract, kumazasa extract, clara extract, black tea extract, hawthorn extract, hawthorn extract, shikon extract, perilla extract, peony extract, gall extract, honeysuckle extract, golden locust extract, peppermint extract, sage extract, thyme extract, pearl millet extract. Extract, Cha extract, Clove extract, Camellia extract, Tonin extract, Dokudami extract, Nagikada extract, Garlic extract, Neubara extract, Hikikoshi extract, Bisabolol extract, Butcher bloom extract, Benihana extract, Button extract, Hop extract, Mukuroji extract, Murasaki extract. , Peach extract, eucalyptus extract, yukinoshita extract, mugwort extract, lavender extract, rosemary extract, wild thyme extract, cabbage extract, etc., phenoxyethanol, sodium tocopheryl phosphate, o-cymene-5-ol, oyster tannin, caprylyl-. Examples thereof include 2-glyceryl ascorbic acid, isopropylmethylphenol, xylit, xylitol, chlorhexidine hydrochloride, chlorhexidine gluconate, triclocarban, triclosan, halocarban, and paraoxybenzoic acid ester.

The IOB value of the component B antibacterial agent is preferably similar to the IOB value of the component A silicone graft polymer used in combination. By making the IOB values of both components A and B close to each other, the compatibility of both components is enhanced, and as a result, under the action mechanism involving formation of the barrier coating as shown in FIG. An excellent antibacterial effect can be exhibited by the cooperation of the components A and B. If the IOB values of the component A and the component B are close to each other, the distribution density of the antibacterial agent-derived component of the component B in the barrier coating is higher than that in the case where they are not close to each other. A sufficient antibacterial effect can be exhibited even when the amount is relatively small. From this point of view, the ratio of the IOB value of the silicone graft polymer of the component A and the IOB value of the antibacterial agent of the component B is preferably 0.4 or more, more preferably 0.5 or more, further preferably as the former/latter. Is 0.6 or more, and preferably 3.0 or less, more preferably 2.5 or less, and further preferably 2.0 or less.

The IOB value of the antibacterial agent of the component B is preferably 0.7 or more, more preferably 0.9 or more, further preferably 1.1 or more, and preferably 5.0 or less, more preferably 4.0 or less, More preferably, it is 3.0 or less.
The organic value itself for determining the IOB value of the antibacterial agent of the component B is preferably 100 or more, more preferably 200 or more, further preferably 300 or more, and preferably 2000 or less, more preferably 1500 or less, further preferably It is 1000 or less.
The inorganic value itself for determining the IOB value of the antibacterial agent of the component B is preferably 300 or more, more preferably 400 or more, further preferably 500 or more, and preferably 3000 or less, more preferably 2000 or less, further preferably It is 1000 or less.

As a preferred specific example of the component B antibacterial agent, a compound represented by the following formula (B1), that is, 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)- Pyridone monoethanolamine salt (1-Hydroxy-4-methyl-6-(2,4,4-trimethyl-pentyl)-2(1H)-pyridone; combinationwith 2-aminoethanol(1:1)] (CAS registration number 68890-66-4), also known as piroctone olamine (or piroctone ethanolamine). The IOB value of piroctone olamine is 1.40. As piroctone olamine, an antibacterial agent sold by Clariant under the trade name "Octopirox" can be used.

Phenoxyethanol is another preferred specific example of the component B antibacterial agent. The IOB value of phenoxyethanol is 0.84. As the phenoxyethanol, an antibacterial agent sold under the trade name "Neoron PH100" by Dow Chemical Company can be used.

In the fiber treatment agent of the present invention, the content of the antibacterial agent as the component B is 4 ppm or more with respect to the total mass of the fiber treatment agent from the viewpoint of more reliably exhibiting the antibacterial effect produced by the component B. , Preferably 10 ppm or more, more preferably 20 ppm or more, still more preferably 50 ppm or more. If the content of the antibacterial agent as the component B is less than 4 ppm with respect to the total mass of the fiber treatment agent, the antibacterial effect may be insufficient. On the other hand, the upper limit of the content of the antibacterial agent of the component B is not particularly limited, but if the content is too large, the antibacterial agent causes too strong irritation to the skin, and the cost of the fiber-treated product becomes high. There is a risk of becoming too much. In consideration of the above, the content of the antibacterial agent as the component B is preferably 5% by mass or less, more preferably 1% by mass or less, and further preferably 5000 ppm or less.

[Component C: Organic solvent]
The organic solvent of the component C may be any solvent as long as it can dissolve the components contained in the fiber treating agent including the components A and B. For example, ethanol, isopropanol, hexane, butanol, isobutanol and the like having 4 or more carbon atoms. 6 or less straight or branched chain aliphatic alcohol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl Alcohol, 2-benzyloxyethanol, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, etc. may be mentioned, and one of these may be used alone or 2 A combination of two or more species can be used.

In the fiber treatment agent of the present invention, the content of the organic solvent of the component C (when a plurality of kinds of organic solvents are contained, the total content thereof) is the total amount of the fiber treatment agent from the viewpoint of the cost of the fiber treatment product. With respect to the mass, preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, and preferably 99 mass% or less, more preferably 97 mass% or less, further preferably 95 mass%. % Or less.

In addition to the components A to C described above, the fiber treatment agent of the present invention may further contain components used in this type of fiber treatment agent (water repellency imparting agent), depending on the purpose, application, dosage form, etc. can do. Examples of such optional components include solvents other than the component C (water, etc.); coloring agents such as dyes and pigments; viscosity modifiers such as hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, clay minerals; organic acids. , Sodium hydroxide, potassium hydroxide and the like, and the like, and one of these may be used alone or in combination of two or more.

The fiber-treating agent of the present invention can be prepared into various dosage forms according to a conventional method. For example, liquid substances; gel-like, paste-like, cream-like, wax-like semi-solid substances; sheet-like, stick-like etc. It can be a solid.

The fiber treating agent of the present invention can be applied to various fiber articles. Examples of fiber articles to which the fiber treatment agent of the present invention can be applied include inner garments represented by underwear such as pants, armpits, shirts, bras, girdles, socks; soccer shirts, golf shirts, tennis shirts, basket shirts. , Table tennis shirts, badminton shirts, running shirts, soccer pants, tennis pants, basketball pants, table tennis pants, badminton pants, running pants, golf pants, various sports undershirts, various sports innerwear, sweaters, T-shirts, jerseys , Sportswear such as trainers, windbreakers, shorts and leggings; light incontinence products such as urine leakage treatment pads, sanitary napkins, vampire sheets such as panty liners, breast milk pads, etc. The fiber treatment agent of the present invention is particularly useful as a measure against small leaks, and from this viewpoint, it is particularly effective when applied to men's pants.

The method for applying the fiber treatment agent of the present invention to a treatment target (fiber article) is not particularly limited, and can be appropriately selected according to the dosage form of the fiber treatment agent and the like. For example, when the fiber treatment agent of the present invention is a liquid material or a semi-solid material, dipping in the fiber treatment agent, spray coating, dipping method, roll-on method, transfer method, die coating, gravure coating Coating using a known liquid coating device such as coating according to printing, such as ink jet method and screen printing, and the like, and these can be used freely.

When the fiber-treating agent of the present invention is a sheet-like solid, the sheet-like solid is optionally bonded to a desired part of a fiber article (for example, the predecessor of men's pants by a joining means such as an adhesive). It can be used by pasting it on the outer surface). The thickness of the sheet-like solid fiber treatment agent is not particularly limited and may be appropriately adjusted according to the application etc., for example, when it is attached to the outer or inner surface of the front body of men's pants as a measure against slight leakage. , Preferably 50 μm or more, more preferably 100 μm or more, and preferably 2 mm or less, more preferably 1 mm or less.

Further, when the fiber treatment agent of the present invention is a stick-shaped solid material, a method of directly applying the stick-shaped solid material to the fiber-made article or applying it indirectly to the fiber-made article using a sponge or the like. Can be adopted. The stick-shaped solid fiber treating agent is configured similarly to, for example, lipstick or stick paste, and includes a stick-shaped solid substance of the fiber treating agent and a support portion that supports the solid substance.

The present invention includes a spray product obtained by filling a spray container with the fiber treatment agent of the present invention described above. The spray container typically has a spray main body having a storage portion for the fiber treatment agent therein, and a spray mechanism attached to the spray main body. The spray mechanism is not particularly limited, and may be, for example, a push spray type configured to suck up and spray the contents (fiber treatment agent) in the spray main body when the user pushes with a finger, or a trigger. It may be a trigger spray type in which the liquid in the cylinder communicating with the spray main body is jetted from the nozzle by pushing down the piston by rotating.

The spray product of the present invention may be an aerosol spray product obtained by filling a pressure resistant container for aerosol spray with the fiber treatment agent and the propellant of the present invention. Examples of the propellant include those using compressed gas such as nitrogen gas and carbon dioxide gas, and those using liquefied gas such as liquefied petroleum gas (LPG) and dimethyl ether (DME). The content of the propellant in the fiber treatment agent of the present invention is preferably 5% by mass or more, more preferably 20% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less.

The spray product of the present invention may be a manual spray product obtained by filling a container equipped with a manual sprayer with the fiber treatment agent of the present invention. This manual spray product is a spray product that does not use a propellant such as gas, and specifically, for example, a manual trigger sprayer and an ultrasonic type can be exemplified. It is preferable because the fineness of the particle diameter of the mist and the uniformity of the mist diameter are good.

The present invention also includes a roll-on product obtained by filling a roll-on container with the above-described fiber treatment agent of the present invention. The roll-on container is a container in which an inner stopper for rotatably holding a ball is arranged at the container mouth, and the content (fiber treatment agent) is distributed on the surface of the ball and applied to a desired portion. When the roll-on container is used, the container body is lifted upward while bringing the ball into contact with the fiber article to which the content is applied, and the content is brought into contact with the ball, and the ball is placed on the fiber article. The contents are distributed on the ball surface by rolling with. As the roll-on container, a known one can be used without particular limitation.

According to the fiber treatment agent of the present invention, the silicone graft polymer of the component A is mainly contained in only one surface of the fiber article having two opposite surfaces (front surface and back surface) to prevent permeation of body fluid such as urine. It is possible to form a barrier coating that does not form the barrier coating on the other surface. One of the merits of the "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 by a conventional method using a conventionally known water-repellent treatment agent, the water-repellent property is unnecessarily advanced, and physical properties such as water absorption, flexibility, and air permeability which are not desired to be deteriorated. Although it may decrease significantly, the fiber treatment agent of the present invention can make one side of a fiber article water repellent depending on the usage.

Examples of the method of using the fiber treatment agent of the present invention capable of realizing water repellent on one side of a fiber article include, for example, 1) sticking the fiber treatment agent which is a sheet-like solid on one surface of the fiber article. Method, 2) a method of applying the fiber treatment agent which is a stick-like solid by directly contacting one surface of a fiber article, and 3) using a spray product obtained by filling the fiber treatment agent in a spray container. Method of spraying the fiber treatment agent on one surface of a fiber article, 4) Using a roll-on product obtained by filling the roll-on container with the fiber treatment agent, coating the fiber treatment agent on one surface of the fiber article There is a method of doing.

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, blood, solids, and breast milk as body fluids excreted from the body. The water absorbent fiber article is typically composed mainly of water absorbent fibers, and 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 0.01 to 5 mm, and more specifically, any one or more of woven fabric (woven fabric), knitted fabric, non-woven fabric, and paper. Can be included.

The fiber treatment agent of the present invention can be used for water-repellent one side of various fiber articles including water-absorbent fiber articles, and the aforementioned one-sided water-repellent inner clothing such as men's pants In addition to the prevention of stains on the outer garment due to leakage (dropping of urine after urination), it is suitable for the following uses (1) to (10). 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. The drip sheet is a sheet-like material that absorbs and holds drip such as blood that exudes from food materials such as meat and fish, and is used to maintain the freshness of food materials. By covering the food material with a drip sheet made of a non-woven fabric whose hiding property is improved by making it water repellent on one side, the water repellency on one side (the side opposite to the food side) of the non-woven fabric prevents the drip strike-through. At the same time, the drip of blood or the like that exudes from the food material becomes difficult to see 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). When the fiber treatment agent of the present invention is applied to the following uses (11) to (15), spraying of the fiber treatment agent with the spray product is particularly preferable. Note that 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 more specifically by way of examples, but the present invention is not limited to such examples.

(Synthesis of Silicone No. 1)
In the formula (A1), a compound (polyoxazoline-modified silicone) in which p is 1346 and q is 5 is synthesized, and silicone No. It was set to 1. Specifically, 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline was mixed with 27.7 g of ethyl acetate, and the mixture was mixed with molecular sieves (trade name: Zeorum A-4, Tosoh Corporation). It was dehydrated at 2.0 g for 15 hours. Further, 100 g of a side chain primary aminopropyl-modified polydimethylsiloxane (KF-8015, weight average molecular weight 100,000, amine equivalent 20,000, manufactured by Shin-Etsu Chemical Co., Ltd.) and 203 g of ethyl acetate were mixed, and the mixture was mixed with molecular sieve 15. Dehydration was performed at 2 g for 15 hours. 0.77 g (0.005 mol) of diethyl sulfate was added to the above ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80° C. for 8 hours in a nitrogen atmosphere to obtain a poly(N-propionyl) having terminal reactivity. Ethyleneimine) was synthesized. This end-reactive poly(N-propionylethyleneimine) solution was added all at once to the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution described above, and the mixture was heated under reflux at 80° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubber-like solid (108 g, yield 95%). The mass ratio (a/b) of the organopolysiloxane segment (a) to the polymer segment (b) derived from the unsaturated monomer in the final product was 6.7, and the weight average molecular weight of the final product was 115,000. It was

(Synthesis of Silicone No. 2)
In the above formula (A1), a compound (polyoxazoline-modified silicone) in which p is 656 and q is 20 is synthesized, and silicone No. It was set to 2. Specifically, 41.8 g (0.42 mol) of 2-ethyl-2-oxazoline was mixed with 104.05 g of ethyl acetate, and the mixture was dehydrated with 9.5 g of molecular sieves for 15 hours. In addition, 153.75 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8003, weight average molecular weight 50000, amine equivalent 2000, manufactured by Shin-Etsu Chemical Co., Ltd.) and ethyl acetate 312.6 g were mixed, and a mixed solution was prepared. Dehydration was performed for 15 hours with 22.7 g of molecular sieve. 9.48 g (0.062 mol) of diethyl sulfate was added to the above ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80° C. for 8 hours in a nitrogen atmosphere to give poly(N-propionyl) having a terminal reactivity. Ethyleneimine) was synthesized. This end-reactive poly(N-propionylethyleneimine) solution was added all at once to the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution described above, and the mixture was heated under reflux at 80° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (190 g, yield 94%). The mass ratio (a/b) between the organopolysiloxane segment (a) and the polymer segment (b) derived from an unsaturated monomer in the final product was 3.0, and the weight average molecular weight of the final product was 40,000 (charged). Calculated value).

(Synthesis of Silicone No. 3)
In the above formula (A1), a compound (polyoxazoline-modified silicone) in which p is 656 and q is 20 is synthesized, and silicone No. It was set to 3. Specifically, 53.2 g (0.53 mol) of 2-ethyl-2-oxazoline was mixed with 127.5 g of ethyl acetate, and the mixed solution was dehydrated with 9.0 g of molecular sieves for 15 hours. In addition, 153.75 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8003, weight average molecular weight 50000, amine equivalent 2000, manufactured by Shin-Etsu Chemical Co., Ltd.) and ethyl acetate 312.6 g were mixed, and a mixed solution was prepared. Dehydration was performed for 15 hours with 22.7 g of molecular sieve. To the above ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline was added 9.98 g (0.064 mol) of diethyl sulfate, and the mixture was heated under reflux at 80° C. for 8 hours in a nitrogen atmosphere to give poly(N-propionyl) having terminal reactivity. Ethyleneimine) was synthesized. This end-reactive poly(N-propionylethyleneimine) solution was added all at once to the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution described above, and the mixture was heated under reflux at 80° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (200 g, yield 92%). The mass ratio (a/b) of the organopolysiloxane segment (a) to the polymer segment (b) derived from the unsaturated monomer in the final product was 2.3, and the weight average molecular weight of the final product was 70400 (charged Calculated value).

(Synthesis of Silicone No. 4)
In the formula (A1), a compound (polyoxazoline-modified silicone) in which p is 393 and q is 12 is synthesized, and silicone No. It was set to 4. Specifically, 93.8 g (0.95 mol) of 2-ethyl-2-oxazoline was mixed with 203.3 g of ethyl acetate, and the mixed solution was dehydrated with 14.8 g of molecular sieves for 15 hours. In addition, 100 g of a side chain primary aminopropyl-modified polydimethylsiloxane (AP3651, weight average molecular weight 30,000, amine equivalent 2000, manufactured by Toray Dow Corning Co., Ltd.) and 203 g of ethyl acetate were mixed, and a mixed solution was prepared with a molecular sieve of 15.2 g. It was dehydrated for 15 hours. 6.17 g (0.04 mol) of diethyl sulfate was added to the above ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80° C. for 8 hours in a nitrogen atmosphere to obtain poly(N-propionyl) having terminal reactivity. Ethyleneimine) was synthesized. This end-reactive poly(N-propionylethyleneimine) solution was added all at once to the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution described above, and the mixture was heated under reflux at 80° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow solid (190 g, yield 95%). The mass ratio (a/b) of the organopolysiloxane segment (a) to the polymer segment (b) derived from the unsaturated monomer in the final product was 1.0, and the weight average molecular weight of the final product was 60,000. It was

(Synthesis of Silicone No. 5)
In the above formula (A2), a compound (dimethylacrylamide grafted organosiloxane) in which p is 656 and q is 20 is synthesized, and silicone No. It was set to 5. Specifically, first, radical-reactive organopolysiloxane was synthesized. As a 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 (KF-8003, weight average molecular weight 50,000, An amine equivalent of 2000, 100 g of Shin-Etsu Chemical Co., Ltd., and 8 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 A having a sulfanyl group.
76.7 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube, and a stirring device. The following solutions (a) and (b) were placed in separate dropping funnels while stirring ethanol under a nitrogen atmosphere under reflux at 80° C., and added dropwise simultaneously for 1 hour. Solution (a): A solution obtained by mixing 20.0 g of dimethylacrylamide and 20.0 g of ethanol. Solution (b): 80.0 g of the radical-reactive organopolysiloxane A, 0.02 g of 2,2′-azobis(2,4-dimethylvaleronitrile) (V-65B, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) , A solution obtained by mixing 53.3 g of ethanol.
After completion of dropping, the reaction mixture was stirred at 80° C. for 3 hours and then cooled. The reaction time is 4 hours in total. Ethanol was removed from the reaction mixture at room temperature (25° C.) under reduced pressure (20 kPa) for 4 hours to obtain a mixture containing dimethylacrylamide-grafted organosiloxane as a white solid.

(Synthesis of Silicone No. 6)
In the formula (A2), a compound (dimethylacrylamide/t-butylacrylamide grafted organosiloxane) in which p is 656 and q is 20 is synthesized, and silicone No. It was set to 6. Specifically, 75.0 g of ethanol was charged into a separable flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube, and a stirring device. The following solutions (a) and (b) were placed in separate dropping funnels while stirring ethanol under a nitrogen atmosphere under reflux at 80° C., and added dropwise simultaneously for 1 hour. Solution (a): A solution obtained by mixing 22.0 g of dimethylacrylamide, 3.0 g of t-butylacrylamide and 25.0 g of ethanol. Solution (b): A solution obtained by mixing 75.0 g of the radical-reactive organopolysiloxane A, 0.033 g of V-65B, and 50.0 g of ethanol.
After completion of dropping, the reaction mixture was stirred at 80° C. for 3 hours and then cooled. The reaction time is 4 hours in total. Ethanol was removed from the reaction mixture at room temperature (25° C.) under reduced pressure (20 kPa) for 4 hours to obtain a mixture containing dimethylacrylamide/t-butylacrylamide grafted organosiloxane as a white solid.

(Silicone No. 7)
In the following formula (A11), a compound in which m is 663 and n is 13 (amino-modified silicone, KF-864, weight average molecular weight 50000, amine equivalent 3800, manufactured by Shin-Etsu Chemical Co., Ltd.) is silicone No. It was set to 7.

(Silicone No. 8)
In the following formula (A11), a compound in which m is 1346 and n is 5 (amino-modified silicone, KF-8015, weight average molecular weight 100000, amine equivalent 20,000, manufactured by Shin-Etsu Chemical Co., Ltd.) is silicone No. It was set to 8.

(Silicone No. 9)
In formula (A12) below, a compound having a viscosity of 80 mm ² /s at 25° C. and an HLB of 10 (polyether-modified silicone, KF-6204, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 9.

(Silicone No. 10)
In formula (A12) below, a compound having a viscosity of 430 mm ² /s at 25° C. and an HLB of 10 (polyether-modified silicone, KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 10.

(Silicone No. 11)
In formula (A12) below, a compound having a viscosity of 920 mm ² /s at 25° C. and an HLB of 10 (polyether-modified silicone, KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 11.

(Silicone No. 12)
In formula (A12) below, a compound having a viscosity of 1600 mm ² /s at 25° C. and an HLB of 7 (polyether-modified silicone, KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 12.

(Silicone No. 13)
In the formula (A12) below, a compound having a viscosity of 130 mm ² /s at 25° C. and an HLB of 4 (polyether-modified silicone, KF-945, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 13.

(Silicone No. 14)
In formula (A12) below, a compound having a viscosity of 180 mm ² /s at 25° C. and an HLB of 4 (polyether-modified silicone, KF-6020, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 14.

(Silicone No. 15)
In formula (A12) below, a compound having a viscosity of 530 mm ² /s at 25° C. and an HLB of 5 (polyether-modified silicone, KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 15.

(Silicone No. 16)
In formula (A12) below, a compound having a viscosity of 4000 mm ² /s at 25° C. and an HLB of 5 (polyether-modified silicone, X-22-4515, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as Silicone No. It was set to 16.

(Silicone No. 17)
In the following formula (A13), a compound in which n is 11 (hydroxyl group at one terminal, silaplane FA-0411, weight average molecular weight 1000, manufactured by JNC Corporation) is used as silicone No. It was set to 17. In the formula (A13) below, Me represents a methyl group.

(Silicone No. 18)
In the following formula (A13), a compound in which n is 132 (hydroxyl group at one terminal, silaplane FA-0425, weight average molecular weight 10000, manufactured by JNC Corporation) was used as Silicone No. It was set to 18.

(Silicone No. 19)
In the following formula (A14), a compound in which n is 9 (one terminal hydroxyl group, silaplane FA-DA11, weight average molecular weight 1000, manufactured by JNC Corporation) was used as Silicone No. It was set to 19. In the formula (A14) below, Me represents a methyl group.

(Silicone No. 20)
In the following formula (A14), a compound in which n is 198 (one terminal hydroxyl group, silaplane FA-DA26, weight average molecular weight 15,000, manufactured by JNC Corporation) was used as Silicone No. It was set to 20.

(Silicone No. 21)
In the following formula (A15), a compound in which n is 10 (methacryloxy group at one end, silaplane FA-0711, weight average molecular weight 1000, manufactured by JNC Corporation) was used as Silicone No. It was set to 21. In the formula (A15) below, Me represents a methyl group.

(Silicone No. 22)
In the following formula (A15), a compound in which n is 131 (methacryloxy group at one end, silaplane FA-0725, weight average molecular weight 10000, manufactured by JNC Corporation) was used as Silicone No. It was set to 22.

(Synthesis of Silicone No. 23)
The silicone-containing polymer copolymer described in Patent Document 2 (Japanese Patent Laid-Open No. 2003-34784) was synthesized, and silicone No. 23. This silicone-containing polymer (Silicone No. 23) has a siloxane bond, but the main chain is a C—C bond, and the “main chain having a siloxane bond”. Does not have. Specifically, under a nitrogen atmosphere, a 500 mL separable flask containing 117.4 g of ethanol at 150 rpm was heated to 80°C. There, 21.0 g of silaplane FM-0711, 10.5 g of dimethylaminoethyl methacrylate, 42.0 g of methacrylic acid, 31.5 g of t-butyl methacrylate, 52.2 g of ethanol, 2,2-azobis(2-methylbutyro) Nitrile) (V-59, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After further heating at 80° C. for 3 hours, the solvent ethanol was dried to obtain a white polymer.

[Examples 1 to 11, Comparative Examples 1 to 24, Reference Example 1]
Any one of the above silicones is dissolved in an organic solvent to obtain a silicone solution having a silicone concentration of 5% by mass, and a predetermined amount of an antibacterial agent is dissolved in the silicone solution, and the fiber treatment of each Example and Comparative Example is performed. An agent (liquid substance) was prepared. In addition, as a comparative example, a fiber treatment agent (liquid material) not using silicone was prepared. As the organic solvent, ethanol, isopropanol or hexane was used. As the antibacterial agent, the above-mentioned piroctone olamine (the compound represented by the formula (B1), "Octopirox" manufactured by Clariant, antibacterial agent No. 1) or phenoxyethanol ("Neolone PH100" manufactured by Dow Chemical Co.). , Antibacterial agent No. 2) was used.

[Evaluation]
The fiber treatment agent to be evaluated was evaluated for water repellency-providing property, washability and antibacterial property by the following methods. The results are shown in Tables 2 and 3 below.

<Evaluation method for water repellency>
As a fiber article, 10 cm square Supima cotton in plan view (boxer pants made by Uniqlo Co., 93% by mass cotton, 7% by mass polyurethane) was prepared, and this Supima cotton was put into a commercially available washing machine (Hitachi Appliance Co., Ltd.). Co., Ltd., NW-500MX) and a commercially available powder detergent (Attack Bio EX, manufactured by Kao Co., Ltd.) were used for washing in a conventional manner. The washing conditions were 1.5 kg of laundry, 30 L of water, 20 g of detergent, 9 minutes of washing, 2 times of rinsing, 6 minutes of dehydration, and drying (leaving at room temperature of 27° C. and 45% RH for 8 hours). The fiber treatment agent to be evaluated was filled in a push-spray type spray container (PP spray vial No. 6 manufactured by Maru-M Co., Ltd.), and the entire area of one side of washed Supima cotton was washed under an environment of normal temperature and pressure. 0.72 g of the fiber treatment agent was applied to Supima cotton by spraying 6 pushes with a spray container (0.036 g in terms of solid content). After spraying, leave Supima cotton in the same environment for a while to completely remove the organic solvent that is the solvent for the fiber treatment agent, and then use a piece of Kimwipe (registered trademark) (Nippon Paper Crecia S-200) was laminated so as to cover the entire surface of the fiber treatment agent application surface to obtain a laminated body, and the laminated body was formed of Supima cotton without the fiber treatment agent application surface (Kimwipe (registered trademark)). Place it on a horizontal table so that the surface not coated with (trademark) is facing up, and from the upper surface of Supima cotton, that is, the surface on which the fiber treatment agent is not applied, 1 mL of physiological saline having a sodium chloride concentration of 0.9% by mass. Was injected. The injection of the physiological saline was performed by putting the physiological saline in a cup and tilting the cup. Immediately after injecting the physiological saline solution, the Kim towel is visually inspected, and when the physiological saline solution has not migrated to the Kim towel, it is evaluated as “having water repellency”, and when it has migrated, it is evaluated as “not having water repellency”. did. If the evaluation is “with water repellency,” the fiber treatment agent is judged to have excellent water repellency, and is highly evaluated.

<Evaluation method of washability>
As a fiber article, Supima cotton (made by Uniqlo Co., Ltd.) having a square shape of 10 cm in a plan view was prepared, and this Supima cotton was washed with a commercially available washing machine (NW-500MX manufactured by Hitachi Appliances Co., Ltd.) and a commercially available powder detergent ( It was washed in accordance with a conventional method using Attack Bio EX manufactured by Kao Corporation. The washing conditions were 1.5 kg of laundry, 30 L of water, 20 g of detergent, 9 minutes of washing, 2 times of rinsing, 6 minutes of dehydration, and drying (leaving at room temperature of 27° C. and 45% RH for 8 hours). After washing, the weight of Supima cotton was measured (the measured value is W0).
The fiber treatment agent to be evaluated was filled in a push-spray type spray container (PP spray vial No. 6 manufactured by Maru-M Co., Ltd.), and the entire area of one side of washed Supima cotton was washed under an environment of normal temperature and pressure. By applying 40 push sprays with a spray container, 5 g of the fiber treatment agent was applied to Supima cotton (0.25 g in terms of solid content). After spraying, the Supima cotton was left in the same environment for 12 hours to completely remove the organic solvent as the solvent of the fiber treatment agent, and the weight of the Supima cotton was measured (the measured value is W1).
Washing water is prepared by dissolving 0.33 g of a powder detergent (Attack, manufactured by Kao Corporation) in 500 mL of tap water, and 500 mL of the washing water having a water temperature of 20° C. and a cylindrical stirrer (diameter 8 mm) are prepared in a beaker having a capacity of 500 mL. , An axial length of 5 mm) and a magnetic stirrer (HANNA, HI304) are used to rotate the stirrer at a rotation speed of 200 rpm to stir the washing water, and the washing water under stirring is added to the support member. The entire Supima cotton with the fiber treatment agent supported in the hanging state was soaked so that the Supima cotton did not come in contact with the stirring bar, and allowed to stand for 5 minutes in that state, and then the Supima cotton was washed in a beaker. After taking it out of water, rinsing it under running water for 10 seconds, dehydrating it with a squeeze squeeze, and leaving it for 24 hours in an environment of normal temperature and normal pressure to dry it, and then measuring the weight of Supima cotton (measured value is W2 To).
The treatment agent removal rate was calculated by substituting the measured values W0, W1, and W2 of the weight of Supima cotton in the following formula. When the removal rate of the treatment agent was 15% or more, it was determined as "having washability", and when it was less than 15%, it was determined as "no washability". It is judged that the higher the treating agent removal rate, the more easily the textile treating agent can be removed by washing, and the more excellent the washing removability is, and it is highly evaluated.
Treatment agent removal rate (%)={(W1-W2)/(W1-W0)}×100

<Antibacterial evaluation method>
First, 64 g of SCD agar medium “Daigo” (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was dissolved in 1600 mL of distilled water at 70° C. with stirring, and autoclaved at 120° C. for 20 minutes (manufactured by Hirayama Seisakusho Co., Ltd., Hiclave HVA-110). ). Before the obtained solution was solidified, it was poured into a 90 mmφ polystyrene petri dish (manufactured by As One Co., Ltd.) to prepare an agar medium.
Next, by performing 6 push spraying of the fiber treatment agent to be evaluated, 0.72 g (0.036 g in terms of solid content) of the fiber treatment agent was put into a 50 mL screw tube (manufactured by Maru-M Co., Ltd.). The fiber treatment agent was dried and solidified in a vacuum dryer at 40°C.
As the bacterial solution, 40 mL of urine was collected from each of four healthy subjects, and the collected urine was mixed with indigenous bacteria of the skin collected from the male genital surface of the same subject. The skin indigenous bacteria were collected using 3 culture swabs (BD BBL Culture Swab EZII, manufactured by Nippon Becton Dickinson Co., Ltd.), and the tip (cotton ball) of the swab was moistened with sterile physiological saline. , The male genital surface of the test subject was rubbed with the tip of the swab 10 times.
After adding 1 mL of the prepared bacterial solution to a 50 mL screw tube in which the fiber treatment agent was dried and solidified, static culture was carried out at 37°C, and the number of viable cells in the stationary phase (stationary phase) after 24-hour culture was quantified. did.
As a quantitative method for the number of bacteria in accordance with the agar plate dilution method, 10 ^1-fold culture medium cultured for 24 hours in sterile saline, 10 ^twice, 10 ^three times, 10 ⁴ times, 10 ⁵ times, 10 ⁶ times, The culture solution diluted 10 ⁷ times, 10 ⁸ times, and 10 ⁹ times was spread on the agar medium described above by 100 μL and developed, and then statically cultured at 30° C. for 24 hours, and the colonies formed on the medium were counted. The smaller the number of bacteria after culturing for 24 hours (“the number of bacteria after 24 hours” in Tables 2 and 3 below), the higher the antibacterial property is judged and the higher the evaluation.

As shown in Table 2, since the fiber treatment agent of each Example contains the silicone graft polymer of the component A described above, the fiber treatment agent is made of a fiber as compared with the fiber treatment agents of Comparative Examples 1 to 7 containing no silicone. It was excellent in imparting water repellency to the article. Further, from the comparison between Examples 3 to 7 and Comparative Examples 2 to 6 and the comparison between Example 11 and Comparative Example 7, in addition to the antibacterial agent, silicone (a silicone graft polymer of component A) was used in combination, It can be seen that the antibacterial property is improved. That is, it is understood that the silicone graft polymer of the component A has an action of amplifying the antibacterial effect of the antibacterial agent.

As shown in Table 3, each of the fiber treatment agents of Comparative Examples and Reference Examples did not contain an antibacterial agent, and thus the result was inferior to the fiber treatment agents of the Examples shown in Table 2 in antibacterial properties. Became. Further, from the comparison between Reference Example 1 and Comparative Examples 8 to 23, a fiber treatment agent having excellent water repellency-providing property and wash-removing property and capable of imparting wash-removable water-repellent property (waterproof property) to a fiber article is obtained. In order to achieve this, it is necessary for the silicone (silicone graft polymer of component A) to have a side chain molecular weight of 800 or more, and an IOB value of about 0.6 is not sufficient. It turns out that the above is necessary. In addition, since Comparative Example 24 using a silicone having no siloxane bond in the main chain had a result that the treatment agent removal rate was 0% and did not have washability, the fiber treatment using silicone was performed. It can be seen that the silicone must have a "main chain having a siloxane bond" in order to impart washability to the agent.

ADVANTAGE OF THE INVENTION According to this invention, while preventing the inconvenience that body fluids, such as urine, seep out to clothes and become visible from the outside, the fiber treatment agent which is excellent in antibacterial effect and can be removed by washing is provided. The fiber treatment agent of the present invention is particularly useful for a person who suffers from a slight leak. For example, by a simple operation such as spraying the fiber treatment agent on underwear, the above-mentioned urine stains and bacterial growth The problem of deterioration of hygiene can be solved, and since the fiber treatment agent has washability, the underwear treated with the fiber treatment agent can be reset by washing, which is hygienic. is there.

Claims

A fiber treatment agent containing the following components A, B and C, and the content of the antibacterial agent of component B being 4 ppm or more.
Component A: Silicone graft polymer having a main chain having a siloxane bond and a side chain having a molecular weight of 800 or more and having an IOB value of 0.7 or more Component B: Antibacterial agent Component C: Organic solvent
The fiber treating agent according to claim 1, wherein the antibacterial agent of component B is piroctone olamine.
The fiber treating agent according to claim 1 or 2, wherein the ratio of the IOB value of the silicone graft polymer of component A to the IOB value of the antibacterial agent of component B is 0.4 or more and 3.0 or less as the former/latter.
The fiber treatment agent according to any one of claims 1 to 3, which is a solid sheet.
The fiber treatment agent according to any one of claims 1 to 3, which is a stick-shaped solid substance.
A spray product obtained by filling a spray container with the fiber treatment agent according to any one of claims 1 to 3.
A roll-on product obtained by filling the roll-on container with the fiber treatment agent according to any one of claims 1 to 3.