TW202031965A - Fiber treatment agent - Google Patents

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

Fiber treatment agent

The present invention relates to a fiber treatment agent that imparts water repellency to fiber articles such as clothes and can exhibit antibacterial effects.

In the past, silicone compounds have been used for the purpose of imparting water repellency, softness, smoothness, and the like to fibrous articles such as clothes. For example, Patent Document 1 discloses a fiber treatment agent containing a specific amino-modified silicone. In Patent Document 2, as a water-repellent treatment agent that can impart water repellency to fibers and can be removed by washing, a polymer copolymer containing a specific silicone is disclosed.

In addition, for hair dressing agents, it is required to fix and maintain the hair in the desired shape, not to make the hair stiff or sticky, and to maintain a natural touch. At this time, as a hair dressing agent that can meet this requirement, it is proposed to contain organopolysilicon In the case of an oxane graft polymer, the organopolysiloxane graft polymer is based on the side chain of the organopolysiloxane segment as the main chain with a specific ratio of polymer chains derived from unsaturated monomers Paragraphs (Patent Documents 3 and 4). Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 4-163374 Patent Document 2: Japanese Patent Laid-Open No. 2003-34784 Patent Document 3: Japanese Patent Laid-Open No. 10-306163 Patent Document 4: Japanese Patent Laid-Open No. 2014-77112

The present invention is a fiber treatment agent which contains the following components A, B and C, and the content of the antibacterial agent of component B is 4 ppm or more. Component A: silicone grafted polymer, which has a main chain containing siloxane bonds and side chains with a molecular weight of 800 or more, and an IOB (Inorganic Organic Balance) value of 0.7 or more Ingredient B: Antibacterial agent Component C: organic solvent

In addition, the present invention is characterized in that the fiber treatment agent of the present invention is a sheet-like solid material. That is, the present invention includes a sheet-shaped product obtained by molding the fiber treatment agent of the present invention into a sheet-like solid material. Furthermore, the present invention is characterized in that the fiber treatment agent of the present invention is a rod-shaped solid substance. That is, the present invention includes a rod-shaped product in which the fiber treatment agent of the present invention is molded into a rod-shaped solid material. In addition, the present invention is a spray product obtained by filling the above-mentioned fiber treatment agent of the present invention in a spray container. In addition, the present invention is a roll-coated product obtained by filling the fiber treatment agent of the present invention in a roll-coating container.

Generally speaking, the urine remaining in the urethra after urination may slightly come out to wet underwear and other underwear. It is a phenomenon called "Post Micturition Dribble" (PMD). Compared with urinary incontinence, the urine output is less, about 0.1 mL to 2 mL, so it is also called "mild urine leakage." Especially male urethra is longer than female urethra, and male urethra has a curved structure in two places, urine is easy to remain in the urethra, so it is easy to cause slight urine leakage. Minor leakage of urine not only causes the discomfort caused by the wetting of underwear such as shorts, but also the case that urine even oozes into the underwear while wearing outer clothing such as pants. Depending on the color of the outer clothing, there is a The problem of conspicuous urine stains. Although incontinence pads have been proposed to deal with the problem caused by such slight urine leakage, the actual situation is that many people feel resistance to using incontinence pads, and there is a strong demand for mild urine leakage instead of using incontinence pads.

As a method to prevent dirt (urine stains) on outer clothing caused by slight urine leakage, consider the following method: Use a commercially available waterproof spray to treat the underwear to give it water repellency, and let the urine come out due to slight urine leakage. Will not transfer to outer clothing. However, most of the water-repellent sprays on the market are composed of effective ingredients such as silicone, which help to show the water-repellent effect, firmly adhere to the object to be treated by maintaining the water-repellent effect for as long as possible. When the spray-treated underwear is washed in a washing machine after being worn, the active ingredients may not be removed but remain, which may cause hygiene problems.

In addition, human skin and underwear usually have intestinal bacteria such as skin resident bacteria and stool-derived Escherichia coli. If slight urine leakage occurs under this condition, these bacteria may be caused by slight urine leakage. The urine that comes out is a source of nutrients to multiply, causing skin troubles such as macula. There is no treatment agent that can prevent the dirt on the outer clothes caused by slight urine leakage, and prevent the bacteria from the urine from proliferating and maintain the skin's hygienic state, and can be washed and removed.

Therefore, the present invention relates to a fiber treatment agent, which prevents defects such as urine and other body fluids from oozing into clothes and visible from the outside, has excellent antibacterial effect, and can be removed by washing.

The fiber treatment agent of the present invention can impart water repellency (water repellency) that can be washed and removed to fiber articles that do not originally have water repellency (water repellency). For example, by treating the wetted part of cotton men’s shorts when slight urine leakage occurs, typically the part of the front part of the shorts that corresponds to the outer urethral opening of the wearer’s penis and its vicinity. The fiber treatment agent of the present invention is preliminarily provided, and a barrier coating film that prevents body fluids such as urine from penetrating is formed on the imparted portion. The barrier coating film can solve the problem of urine stains caused by slight urine leakage. In the fiber treatment agent of the present invention, the main body of the barrier film is the silicone graft polymer of component A.

Fig. 1 is a schematic diagram of a usage example of the fiber treatment agent of the present invention, and shows the following state: a male wearer 100 wears shorts 1 (underwear) with a barrier film 2 formed on the outer surface (non-skin facing surface) 1b ), and outer clothes 3 such as outer pants are worn thereon. The barrier film 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. In addition, in FIG. 1, the barrier film 2 is laminated on the outer surface 1b of the shorts 1, but in fact, the barrier film 2 is not limited to being formed as shown in FIG. 1. In addition, the fiber treatment agent of the present invention may be applied to the inner surface (skin facing surface) 1a of the shorts 1, or may be applied to both the inner surface 1a and the outer surface 1b.

In the wearing state of shorts 1 shown in Figure 1, "slight leakage of urine" occurred from the urethral orifice outside the penis of the wearer 100 unintentionally excreting a small amount of urine of about 0.1 mL to 2 mL, even if the urine was excreted from the shorts The inner surface 1a side of 1 transfers to the outer surface 1b side, and the water-repellent barrier film 2 formed on the outer surface 1b side prevents the transfer of excreted urine to the outer clothing 3 side, and prevents the outer clothing 3 from generating from Bad condition of urine stains visible on the outside. In addition, if the barrier film 2 is something that cannot be removed by normal washing, even if the shorts 1 on which the barrier film 2 is formed is washed, dirt may not be sufficiently removed, which may cause problems not only in appearance but also in hygiene. For example, even if the shorts formed with the barrier film are washed after use, the barrier film still remains on the shorts. When the shorts are worn again, it will cause hydrophobic interaction with the remaining barrier film. The components in the urine are easy to adhere to the remaining barrier film, so there is a risk of yellowing of shorts and easy propagation of bacteria. In contrast, the barrier film 2 of the present invention can be removed by washing. By washing the shorts 1 formed with the barrier film 2 according to a conventional method, the shorts 1 are restored to their normal state without the barrier film 2, so the shorts 1 Does not yellow and is hygienic. When it is desired to apply a slight urine leakage countermeasure to the shorts 1 restored in this way, it is only necessary to apply the fiber treatment agent of the present invention to the required parts of the shorts 1.

In addition, the fiber treatment agent of the present invention is not only excellent in preventing urine stains, but also excellent in antibacterial effect. It can prevent bacteria from proliferating using excrement represented by urine as a nutrient source, thereby preventing skin troubles caused by bacterial proliferation. The fiber treatment agent of the present invention is directly related to the antibacterial effect of the component B, but the silicone graft polymer of component A also indirectly contributes to the antibacterial effect. That is, for example, for the purpose of preventing the proliferation of bacteria caused by the slight leakage of urine, spray an antibacterial agent on underwear, etc., as shown in Figure 2(a), impart antibacterial to the environment where bacteria 50 such as resident bacteria on the skin exist. In the case of the agent 51, the antibacterial agent 51 imparted in this way spreads to a wide range, so the number of antibacterial agents 51 per unit volume is likely to be insufficient relative to the number of bacteria 50, and there is a possibility that sufficient antibacterial effects cannot be obtained. In contrast, when the fiber treatment agent of the present invention is applied to underwear, as described above, as shown in FIG. 1, the underwear is formed with a silicone graft polymer of component A as the main body and physically prevents urine. The transferred barrier film 2 is now in the barrier film 2, as shown in FIG. 2(b), the antibacterial agent 51 (component of the antibacterial agent derived from component B) is distributed at a relatively high density in the barrier film The antibacterial agent 51 on the film 2 can directly act on the bacteria 50. Therefore, compared with the case where the antibacterial agent 51 is used as a single component for the bacteria 50 as shown in FIG. 2(a), even a small amount of the antibacterial agent 51 can exhibit a sufficient antibacterial effect. That is, the antibacterial effect exerted by the fiber treatment agent of the present invention is exerted by the synergistic effect of the silicone graft polymer of component A and the antibacterial agent of component B, and cannot be exerted when the antibacterial agent is used as a single component. Its particularly advantageous effect. This can also be known from the comparison between Examples and Comparative Examples described later.

Furthermore, according to the fiber treatment agent of the present invention, an antibacterial effect can be expected as a secondary effect. That is, it is believed that although the urine smell itself at the early stage just after urination differs depending on the health status or individual differences, it usually does not emit an unpleasant smell, but after a certain period of time after urination, it emits an unpleasant smell due to bacteria. In this case, the fiber treatment agent of the present invention uses its excellent antibacterial effect to inhibit urine corruption and naturally inhibit urine corruption. In this way, the fiber treatment agent of the present invention is particularly effective in suppressing the putrefaction of urine that occurs after a certain period of time after urination.

The fiber treatment agent of the present invention can be applied to various fiber products. As described above, even if it is a "fiber product that does not originally have water repellency (water repellency)", the fiber product can be given water repellency that can be washed and removed. (Waterproof). As a specific example of the so-called "fibrous article that does not originally have water repellency (water repellency)", "fibrous article capable of retaining body fluids" can be exemplified.

[Component A: Silicone graft polymer] The silicone graft polymer of component A has a main chain and side chains containing siloxane bonds. The chemical structure of the silicone graft polymer of component A is not particularly limited. As a preferred specific example, one having a modified organopolysiloxane segment represented by the following general formula (1) or (2) can be cited .

[化1]

In the above general formulas (1) and (2), 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 represents an alkylene group that may also contain heteroatoms. . p represents a number from 2 to 4000 and q represents a number from 2 to 250. In the formula, the bonding mode of p repeating units and q repeating units can be that each repeating unit is connected in a block shape or in a random manner.

In the above general formula (1) or (2), the siloxane bond (-Si-O-Si-) is the main chain, and R ¹ and R ² are respectively side chains. When R ^{2 is} bonded with other atoms (such as hydrogen atoms) or other functional groups (such as polymer segments derived from unsaturated monomers described later), the bonding between R ² and these other atoms or functional groups The whole body is a side chain.

In the above general formulas (1) and (2), it is preferable that two or more functional groups (for example, the polymer segment derived from an unsaturated monomer described later) pass through as the "alkylene group that may also contain heteroatoms" R ² is bonded to any silicon atom constituting the main chain, more preferably bonded to one or more silicon atoms other than the two ends via R ² , and more preferably bonded to any silicon atom other than two via R ² More than 2 silicon atoms beyond the end.

In the above general formulas (1) and (2), the alkyl group represented by R ¹ includes linear, branched or cyclic alkyl groups. The water dispersibility of the silicone graft polymer of component A viewpoint, the carbon number of alkyl group shown in the ¹ R is preferably 1 or more 10 or less, more preferably 6 or less. Specific examples of the alkyl group represented by R ¹ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, and octyl. Base, nonyl, decyl, undecyl, dodecyl, octadecyl, nonadecyl, eicosyl, behenyl, etc. Furthermore, the so-called "water dispersibility of silicone graft polymer" refers to the property that the silicone graft polymer can be stably dispersed in a composition mainly composed of water. If this property is good, it will improve the present invention. It is better for washing and removing properties.

From the viewpoint of the water dispersibility of the silicone graft polymer of component A, 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. Specific examples of the aryl group represented by R ¹ include phenyl, tolyl, xylyl, naphthyl, biphenyl, anthryl, and phenanthryl.

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

In the above 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. Regarding p, from the viewpoint of improving the water repellency (water repellency) required in the present invention, it is preferably 50 or more, more preferably 80 or more, and still more preferably a number of 100 or more. In addition, for the silicon of component A From the viewpoint of the water dispersibility of the ketone graft polymer, it is preferably 2000 or less, more preferably 1300 or less, and still more preferably 700 or less. Regarding q, from the viewpoint of the water dispersibility of the silicone graft polymer of Component A, it is preferably 3 or more, more preferably a number of 5 or more, and from the viewpoint of improving the washing removal property required in the present invention In other words, it is preferably 50 or less, more preferably 30 or less.

In the above general formulas (1) and (2), part or all of R ² as "alkylene which may also contain heteroatoms" is combined with other functional groups (for example, polymer segments derived from unsaturated monomers described later) ) Bonding and functioning as a linking group with other functional groups. When there is R ^{2 that} is not bonded to other functional groups (polymer segments derived from unsaturated monomers), 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 the availability of raw materials for the production of the silicone graft polymer of component A. In addition, for component A From the viewpoint of the water dispersibility of the silicone graft polymer, it is preferably 20 or less, more preferably 10 or less, and still more preferably 8 or less.

In the present invention, R ² may be divided by one or more atoms or functional groups selected from oxygen atoms, sulfur atoms, -NH-, -COO-, -NHCO-, and -NR ³ CO-. That is, R ² as the "alkylene group which may also contain a hetero atom" may have a structure of "-(alkylene moiety 1)-(the above-mentioned atom or functional group)-(alkylene moiety 2)-", In this case, the carbon number of the alkylene group refers to the sum of the carbon number of the alkylene part 1 and the carbon number of the alkylene part 2. Here, R ³ is an alkyl group having 1 to ³ carbon atoms. In the case where the alkylene group that may also contain heteroatoms is broken by the above-mentioned atoms or functional groups, from the viewpoint of the ease of production of the silicone graft polymer of component A, it is preferably divided by -NHCO- Off.

In the present invention, R ² can also be selected from hydroxyl, amino, alkyl (carbon number 1 to 3), amino group, dialkyl (carbon number 1 to 3), amino group, and carbon number 2 or more. One or more monovalent groups among the amino group, carboxyl group, and alkyl (carbon number 1 to 3) ester group obtained by dehydration condensation of fatty acid of 4 or less are substituted. In this case, the so-called carbon number of R ² does not include the carbon number of the aforementioned substituents. From the viewpoint of the ease of raw material availability during the production of the silicone graft polymer of Component A, R ^{2 is} preferably selected from the group consisting of acetamido and alkyl (carbon number 1 to 3) amino group , And one or more monovalent groups in the amino group.

In the present invention, R ² as the "alkylene group that may also contain heteroatoms" can also be selected from the divalent heterocyclic group in -O-, -S-, -NH-, -NR ³⁰ -, and -COO- Atom or heteroatom-containing divalent group substitution. Here, R ³⁰ is an alkyl group which may be substituted with a dimethylamino group (a carbon number of 1 to 3). When R ² functions as a linking group with other functional groups (for example, polymer segments derived from unsaturated monomers described later), the heteroatom or heteroatom-containing divalent group and the other functional group Bond. In other cases, it is bonded to a hydrogen atom.

From the viewpoint of ease of manufacture of the silicone graft polymer of component A, R ^{2 is} preferably substituted with -S-. R ^{2 is} preferably via a hetero atom contained in R ² , preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a sulfur atom, and interacts with other functional groups (such as the polymer derived from unsaturated monomers described later) Chain segment) bonding. Therefore, R ² (alkylene which may also contain heteroatoms) is equivalent to (i) unsubstituted alkylene, (ii) selected from oxygen atom, sulfur atom, -NH-, -COO-, -NHCO -, and -NR ³ CO- in which one or more atoms or functional groups are broken by alkylene groups, (iii) selected from hydroxyl, amino, alkyl (carbon number 1 to 3), amino, two One of the amino group, carboxyl group and alkyl (carbon number 1 to 3) ester group obtained by dehydration condensation of alkyl (carbon number 1 to 3), amino group and fatty acid with carbon number 2 to 4 Alkylene substituted by the above monovalent group, (iv) divalent heteroatom or divalent heteroatom-containing divalent heteroatom selected from -O-, -S-, -NH-, -NR ³⁰ -and -COO- The alkylene substituted by a group is also equivalent to the alkylene containing the combination of (ii), (iii), and (iv) above.

As specific examples of R ² as the "alkylene group which may also contain a hetero atom" in the present invention, the following formulae (i) to (xii) can be exemplified. Among them, from the viewpoint of the ease of production of the silicone graft polymer of component A, R ^{2 is} preferably the following formulas (xi) and (xii).

[化2]

In the above formulas (i) to (xii), * represents the position bonded to the silicon atom constituting the main chain in the above general formula (1) or (2), and ** represents bonding to other atoms (hydrogen atoms) or Other functional groups (for example, polymer segments derived from unsaturated monomers described later). In the above formula (xii), X ¹ is one or more selected from the group consisting of -O-, -OCO-, -COO-, -CONH-, -NHCO-, which is important for the production of the silicone graft polymer of component A From the viewpoint of ease, -CONH- or -NHCO- is preferable, and -NHCO- is more preferable.

In addition, in the above formula (xii), R ⁴ is optionally selected from the group consisting of hydroxyl, amino, alkyl (carbon number 1 to 3), amino group, dialkyl (carbon number 1 to 3) amino group, amine An alkylene group substituted with one or more monovalent groups among the amino group, carboxyl group and alkyl (carbon number 1 to 3) ester group obtained by dehydration condensation of fatty acid with carbon number 2 or more and 4 or less. As the substituent, from the viewpoint of availability of raw materials at the time of production, an acetamido group, an alkyl group (a carbon number of 1 to 3), an amino group, and an amino group are preferred. Regarding the carbon number of the alkylene group represented by R ⁴ , from the viewpoint of the ease of production of the silicone graft polymer of component A, it is preferably 2 or more, more preferably 3 or more. From the viewpoint of water dispersibility of the silicone graft polymer of A, it is preferably 10 or less, and more preferably 6 or less. As specific examples of R ⁴ , the following formulae (xiii) to (xv) can be cited.

[化3]

In the above formula (xiv), X ^- represents a halide ion such as a chloride ion and a bromide ion, and an anion such as an acetate ion and an alkyl (carbon number 1 to 3) sulfate ion.

As other specific examples of R ² (the alkylene group that may also contain a hetero atom) in the present invention, a C 2-20 alkylene group containing a nitrogen atom, an oxygen atom and/or a sulfur atom can be exemplified, and it is preferably A C 2-20 alkylene group containing 1 to 3 of these heteroatoms. Specifically, it can include (a) secondary amines, tertiary amines, and (b) ammonium obtained by adding H ⁺ to secondary amines and tertiary amines in the carbon-carbon and/or terminal of the alkylene chain Salt, (c) quaternary ammonium salt, (d) oxygen atom and/or (e) sulfur atom having a carbon number of 2-20 alkylene. Among these, as specific examples of preferable ones, the following formulas (xvi) to (xx) can be cited.

[化4]

The silicone graft polymer of Component A is characterized by having side chains with a molecular weight of 800 or more. For example, when the silicone graft polymer of component A has a modified organopolysiloxane segment represented by the general formula (1) or (2), the bond in the segment is used as the main chain One of the side chains of the siloxane bond, that is, the bond between R ² (alkylene which may also contain heteroatoms) and other functional groups (for example, polymer segments derived from unsaturated monomers described later) The molecular weight is above 800.

The fiber treatment agent of the present invention is characterized by imparting "washable and removable water repellency" to fibrous articles that do not originally have water repellency, instead of only imparting water repellency. One of the closely related factors is the molecular weight of the side chain of the silicone graft polymer of component A. As described above, when the fiber treatment agent of the present invention is applied to the treatment object (fiber-made article), the silicone graft polymer of component A becomes the main body of the barrier film formed on the treatment object, but by using The molecular weight of the side chain is above 800, which makes it easy to remove the barrier film by washing ordinary clothes. If the silicone graft polymer of component A does not have a side chain with a molecular weight of 800 or more, it is difficult to impart "washable and removable water repellency" to the processed object.

The molecular weight of the "side chain with a molecular weight of 800 or more" possessed by the silicone graft polymer of component A is preferably 900 or more, more preferably 1,000 or more. The upper limit of the molecular weight of the side chain is not particularly limited. If the molecular weight of the side chain is too large, the water repellency of the barrier coating film may decrease, and the effect of preventing urine stains may decrease. Considering the above, the molecular weight of the side chain is preferably 50,000 or less, more preferably 35,000 or less, and still more preferably 25,000 or less.

When the silicone graft polymer of component A has the modified organopolysiloxane segment represented by the above general formula (1) or (2), it is preferably "polymer derived from unsaturated monomer The "segment" is bonded to the siloxane bond as the main chain via R ² (an alkylene group that may also contain a heteroatom). In this case, it is preferable that the molecular weight of the side chain as "the bond between R ² and the polymer segment derived from unsaturated monomer" is in the above range, and it is more preferably the polymer segment derived from unsaturated monomer That is, the molecular weight of the part obtained by removing R ² from the bond is in the above range.

The silicone graft polymer of Component A only needs to have at least one side chain with a molecular weight of 800 or more. From the viewpoint of more surely exerting the above-mentioned effects, the number of side chains with a molecular weight of 800 or more is preferably 5 or more.

On the other hand, the main chain of the silicone graft polymer of component A, more specifically the molecular weight of the silicone bond, is not particularly limited, but from the viewpoint of developing water repellency (water repellency), it is preferably 10,000 Above, more preferably 30,000 or more, more preferably 200,000 or less, and 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 its polymerization conditions.

The molecular weight of the main chain or side chain of the silicone graft polymer of component A can be obtained as the number average molecular weight or weight average molecular weight of polystyrene conversion in gel permeation chromatography (GPC) analysis, for example. The specific measurement conditions are as follows. Furthermore, when a commercially available product is used as the silicone graft polymer of component A, the molecular weight of the main chain or side chain can also use the values described in the catalog or the like.・Column: K-804L＋K-804L (Shodex (registered trademark), manufactured by Showa Denko Co., Ltd.) ・Lluent: 1 mmol Farmin DM2098 (manufactured by Kao Co., Ltd.)/CHCl ₃・Lluent 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-mentioned "washable and removable water repellency" to the processing object (fiber products), it is not enough that the silicone graft polymer of component A has a side chain with a molecular weight of 800 or more, and a silicone graft of component A is required The IOB value of the polymer is 0.7 or more. The IOB (Inorganic Organic Balance) value becomes the standard of "inorganic value/organic value" which is the ratio of the inorganic value to the organic value of a substance.

Generally speaking, the properties of a substance are largely influenced by various intermolecular forces between molecules, and the intermolecular forces mainly include the Van der Waals force based on molecular mass and the electrical affinity based on molecular polarity. If each of the Van der Waals force and the electrical affinity that have a greater impact on the change of the properties of the substance can be grasped individually, the properties of unknown substances can be predicted based on their combination or the properties of these mixtures can also be predicted. This view is a widely known theory as "organic conceptual graph theory". Organic Concept Graph Theory, such as in "Organic Analysis" by Mu Fujita (Kaniya Bookstore, 1930), "Systematic Organic Qualitative Analysis (Pure Matter)" by Mu Fujita (Kyoritsu Publishing, 1953), and by Mu Fujita "Adapted Chemical Experiments-Organic Chemistry" (Kawaide Shobo, 1971), "Systematic Organic Qualitative Analysis (Mixture Edition)" by Fujita Mu and Masami Akazuka (Kazama Shobo, 1974), and Koda Yoshio and Sato Shiro・Detailed in "The Basics and Application of the New Version of Organic Concept Map" (Sankyo Publishing, 2008) by Yoshio Honma. In organic conceptual graph theory, regarding the physical and chemical properties of matter, the degree of physical properties based mainly on Van der Waals force is called "organicity", and the degree of physical properties based mainly on electrical affinity is called "inorganic". The combination of "organic" and "inorganic" controls the physical properties of substances. Furthermore, one carbon (C) is defined as organic 20. In contrast, the inorganic and organic values of various polar groups are defined as described in Table 1 below, and the sum of the inorganic and organic values is calculated The ratio of the two values is defined as the IOB value.

N+-OH、-SO₃ H、-NHSO₂ -NH 250 -O-SO₃ H 20 220 -CO-NHCO-NHCO- 250 ＞SO₂ 40 170 ＞S-OH、-CONH-CONH-CONH-、-SO₂ NH- 240 ＞SO 40 140 CS-NH-、-CONH-CO- 230 -CSSH 100 80 =N-OH-、-NHCONH- 220 -SCN 90 80 =N-NH-、-CONH-NH₂ 210 -CSOH、-COSH 80 80 -CONH- 200 -NCS 90 75 -＞N-＞O 170 -Bi＜ 80 70 -COOH 150 -NO₂ 70 70 內酯環 120 -Sb＜ 60 70 -CO-O-CO- 110 -As＜、-CN 40 70 蒽環、菲環 105 -P＜ 20 70 -OH 100 -CSS

130 50 ＞Hg(有機性鍵) 95 -CSO

、-COS

80 50 -NH-NH、-O-CO-O- 80 -NO 50 50 -N＜(-NH₂ 、-NH

、-N

₂ )胺 70 -O-NO₂ 60 40 ＞CO 65 -NC 40 40 -COO

、萘環、喹啉環 60 -Sb=Sb- 90 30 ＞C=NH 50 -As=As- 60 30 -O-O- 40 -P=P-、-NCO 30 30 -N=N- 30 -O-NO、-SH、-S- 40 20 -O- 20 -I 80 10 苯環(芳香單環)、吡啶環 15 -Br 60 10 環(非芳香單環) 10 -S 50 10 三鍵 3 -Cl 40 10 雙鍵 2 -F 5 5 -(OCH₂ CH₂ )-、糖環-O- 75 異支鏈＞- -10 0 (20) 第三支鏈-＞- -20 0 [Table 1] Inorganic base value Organic and inorganic base value Inorganic Organicity Inorganic Light metal 500＜ R ₄ Bi-OH 80 250 Heavy metals, ammonium and ammonium salts 400＜ R ₄ Sb-OH 60 250 -AsO ₃ H ₂ 、＞AsSO ₂ H 300 R ₄ As-CH 40 250 -SO ₂ -NH-CO-, -N=N-NH ₂ 260 R ₄ P-OH 20 250

N+-OH, -SO ₃ H, -NHSO ₂ -NH 250 -O-SO ₃ H 20 220 -CO-NHCO-NHCO- 250 ＞SO ₂ 40 170 ＞S-OH, -CONH-CONH-CONH-, -SO ₂ NH- 240 ＞SO 40 140 CS-NH-, -CONH-CO- 230 -CSSH 100 80 =N-OH-, -NHCONH- 220 -SCN 90 80 =N-NH-, -CONH-NH ₂ 210 -CSOH, -COSH 80 80 -CONH- 200 -NCS 90 75 -＞N-＞O 170 -Bi＜ 80 70 -COOH 150 -NO ₂ 70 70 Lactone ring 120 -Sb＜ 60 70 -CO-O-CO- 110 -As＜、-CN 40 70 Anthracycline, phenanthrene ring 105 -P＜ 20 70 -OH 100 -CSS

130 50 ＞Hg (organic bond) 95 -CSO

, -COS

80 50 -NH-NH, -O-CO-O- 80 -NO 50 50 -N＜(-NH ₂ 、-NH

, -N

₂ ) Amine 70 -O-NO ₂ 60 40 ＞CO 65 -NC 40 40 -COO

, Naphthalene ring, quinoline ring 60 -Sb=Sb- 90 30 ＞C=NH 50 -As=As- 60 30 -OO- 40 -P=P-, -NCO 30 30 -N=N- 30 -O-NO, -SH, -S- 40 20 -O- 20 -I 80 10 Benzene ring (aromatic single ring), pyridine ring 15 -Br 60 10 Ring (non-aromatic monocyclic) 10 -S 50 10 Three keys 3 -Cl 40 10 Double bond 2 -F 5 5 -(OCH ₂ CH ₂ )-, sugar ring-O- 75 Different branch chain＞- -10 0 (20) The third branch ->- -20 0

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

[Number 1]

The IOB value of the silicone graft polymer of component A is 0.7 or more as described above, preferably 0.9 or more, more preferably 1.1 or more, and still more preferably 1.2 or more. There is no particular limitation on the upper limit of the IOB value, but if the IOB value is too large, the water repellency of the barrier film may decrease, and the urine stain prevention effect may decrease. Considering the above, the IOB value is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less.

When the IOB value of the silicone graft polymer of component A is as described above, 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 500,000 or less. In addition, the inorganic value itself of the silicone graft polymer of component A is preferably 30,000 or more, more preferably 40,000 or more, still more preferably 50,000 or more, and preferably 900,000 or less, more preferably 800,000 or less, and more It is preferably 700,000 or less.

The "polymer segment derived from unsaturated monomer" of the side chain of the silicone graft polymer of component A will be further explained, from the viewpoint of the water dispersibility of the silicone graft polymer of component A , The polymer segment derived from the unsaturated monomer is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 75% by mass in the polymer segment derived from the unsaturated monomer The above-mentioned repeating unit is derived from N,N-dimethylacrylamide (hereinafter also referred to as "DMAAm"). In addition, from the viewpoint of reducing the stickiness of the fiber product after the fiber treatment agent of the present invention is applied to the fiber product, the content of the repeating unit derived from DMAAm in the polymer segment derived from the unsaturated monomer It is preferably 100% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less. In the present invention, the repeating unit derived from an unsaturated monomer refers to the repeating unit formed during the 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 the unsaturated monomer can be measured by the NMR (Nuclear Magnetic Resonance) method.

The part of the polymer segment derived from unsaturated monomers except for the repeating unit derived from DMAAm contains the repeating unit derived from the unsaturated monomer copolymerizable with DMAAm (except for DMAAm). As repeating units derived from unsaturated monomers copolymerizable with DMAAm, examples include olefins, halogenated olefins, vinyl esters, (meth)acrylates or (meth)acrylamides (excluding DMAAm). ) Repeating units of unsaturated monomers. The part of the polymer segment derived from unsaturated monomers other than the repeating unit derived from DMAAm may include repeating units derived from a single unsaturated monomer copolymerizable with DMAAm, or may include repeating units derived from two or more kinds of unsaturated monomers. Repeating units of saturated monomers.

Regarding the aforementioned "repeating unit derived from an unsaturated monomer copolymerizable with DMAAm", specific examples of olefins include ethylene, propylene, and isobutylene. Specific examples of halogenated olefins include vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride. Specific examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl decanoate and the like.

Regarding the above-mentioned "repeating unit derived from an unsaturated monomer copolymerizable with DMAAm", specific examples of (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, Propyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate Ester, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. with carbon number 1 to 16 (Meth)acrylates of alkyl groups; (meth)acrylates having alkyl groups with 1 to 16 carbon atoms substituted by hydroxyl groups such as 2-hydroxyethyl (meth)acrylate; and (meth)acrylic acid polyacrylates Ethylene glycol, (meth)acrylic acid polyethylene glycol monomethyl ether, etc.

Regarding the aforementioned "repeating unit derived from an unsaturated monomer copolymerizable with DMAAm", specific examples of (meth)acrylamides other than DMAAm include: acrylamide, methacrylamide, etc. ( Meth)acrylamide; N,N-dialkyl(meth)acrylamide such as N,N-diethyl(meth)acrylamide (except DMAAm); N-isopropyl( (Meth)acrylamide, N-tert-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-octyl(meth)acrylamide and other N-alkanes (Meth)acrylamides; diacetone (meth)acrylamides equal to N-monosubstituted (meth)acrylamides with carbonyl substituents on the nitrogen atom; N,N-dimethylamino Propyl (meth)acrylamide is equivalent to N-monosubstituted (meth)acrylamides with an amino group as the substituent on the nitrogen atom; N-methylol (meth)acrylamide, N-hydroxyethyl The group (meth)acrylamide is equivalent to the N-monosubstituted (meth)acrylamides in which the substituent on the nitrogen atom has a hydroxyl group.

Among them, in terms of the sustainability of the water repellency (waterproofness) of the fiber article provided with the fiber treatment agent of the present invention, as the above-mentioned "repeating unit derived from an unsaturated monomer copolymerizable with DMAAm" is more Preferred are (meth)acrylamides and/or (meth)acrylates other than DMAAm, more preferred are acrylamide, methacrylamide, N,N-diethyl(meth)propylene Amide, N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, diacetone (meth)acrylamide, N,N-dimethylaminopropyl (Meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, Propyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, more preferably It is N-tertiary butyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, diacetone (meth) acrylamide, methyl (meth)acrylate, (meth) Ethyl acrylate, t-butyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, more preferably N-tert-butyl(meth)acrylamide, N-Hydroxyethyl (meth)acrylamide, diacetone (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate, further More preferred is N-tert-butyl(meth)acrylamide.

As a preferable specific example of the polymer segment derived from an unsaturated monomer, a poly(N-alkylideneimine) segment represented by the following general formula (3) can be cited.

[化5]

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

As a preferable specific example of the silicone graft polymer of Component A, the compounds represented by the following formulas (A1) and (A2) (polyoxazoline-modified silicone) can be cited.

[化6]

In the above formula (A1), r represents a number of 5 or more and 100 or less. In the above formula (A2), Ac represents the acetyl group "CH ₃ C(=O)-", s represents the number of 100 or more and 300 or less, and t represents the number of 0 or more and 50 or less. The p and q of the above formulas (A1) and (A2) are synonymous with the p and q of the above general formulas (1) and (2), respectively.

The overall structure of the silicone graft polymer of component A is further explained. The silicone graft polymer of component A has a modified organopolysiloxane chain as shown in the above general formula (1) or (2) In the case of a segmental organopolysiloxane segment, the content of the organopolysiloxane segment in the silicone graft polymer gives the fiber product with the fiber treatment agent of the present invention water repellency (Water resistance) From the viewpoint of sustainability, it is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. In terms of the water dispersibility of the silicone graft polymer of component A, From a viewpoint, it is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less. The content of the organopolysiloxane segment in the silicone graft polymer of component A can be determined by NMR.

In addition, from the viewpoint of the water dispersibility of the silicone graft polymer of Component A, and the viewpoint that the water repellency (water resistance) of the fiber article to which the fiber treatment agent of the present invention is imparted continues, organopolysiloxane The mass ratio (a/b) of the segment (a) to the polymer segment (b) derived from the unsaturated monomer is preferably 20/80 or more, more preferably 30/70 or more, and still more preferably 40/ 60 or more, more preferably 99/1 or less, more preferably 95/5 or less, and still more preferably 90/10 or less.

Furthermore, in this specification, when the silicone graft polymer of component A is manufactured from a known radical reactive organopolysiloxane, the above mass ratio (a/b) is regarded as equivalent to The total mass of free radical reactive organopolysiloxane (c)" and "the total mass of unsaturated monomers (d) put in during manufacturing" minus "the unbonded organopolysilicon produced during manufacturing" The ratio (c/(d-e)) (c/(d-e)) of the total mass of the polymer derived from the unsaturated monomer (e) "value" of the oxane (the following formula (I)). a/b=c/(d－e) (I)

In addition, regarding the number average molecular weight (MNg) of the organopolysiloxane segments between adjacent polymer segments derived from unsaturated monomers (hereinafter referred to as "molecular weight between graft points"), From the viewpoint of sustainability of water repellency (water resistance), it is preferably 500 or more, more preferably 700 or more, still more preferably 1000 or more, and even more preferably 1500 or more. For the water of the silicone graft polymer of component A From the viewpoint of dispersibility, it is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less, and still more preferably 2,500 or less. Here, the "organopolysiloxane segment between adjacent polymer segments derived from unsaturated monomers" means a polymer derived from unsaturated monomers as shown in the following general formula (4) The segment is the part surrounded by a dotted line between the bonding point of the organopolysiloxane segment (bonding point A) to the bonding point (bonding point B) of the adjacent polymer segment derived from the unsaturated monomer , And it is a segment containing 1 R ¹ SiO unit, 1 R ² and y+1 R ¹ ₂ SiO unit.

[化7]

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

The molecular weight between grafting points is the average of the molecular weight of the part surrounded by the dotted line in the general formula (4), which can be understood as the polymer segment derived from unsaturated monomer per 1 mole of organopolysiloxane segment The mass (g/mol). When the silicone graft polymer of component A is made of a known free radical reactive organopolysiloxane, and when all free radical reactive functional groups are bonded to polymers derived from unsaturated monomers , The molecular weight between grafting points is regarded as the value equivalent to the reciprocal of the number of moles (mol/g) of free radical reactive functional groups per unit mass of free radical reactive organopolysiloxane.

In addition, when the silicone graft polymer of component A has an organopolysiloxane segment like the modified organopolysiloxane segment represented by the general formula (1) or (2), From the viewpoint of continuous water repellency (water resistance), the weight average molecular weight (MWsi) of the organopolysiloxane segment is preferably 3,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, and even more preferably For more than 15,000. From the viewpoint of the water dispersibility of the silicone graft polymer of component A, the MWsi is preferably 200,000 or less, more preferably 100,000 or less, further preferably 60,000 or less, and even more preferably 50,000 or less. In this specification, MWsi is measured by gel permeation chromatography (GPC) and converted into polystyrene. At this time, the GPC measurement conditions are as described above.

When the silicone graft polymer of component A is made of a known radical reactive organopolysiloxane, the organopolysiloxane segment has a common skeleton with the free radical reactive organopolysiloxane, so The weight average molecular weight (MWra) of the MWsi and the radical-reactive organopolysiloxane is approximately the same, and is regarded as the same in the present invention. In this specification, MWra is measured by gel permeation chromatography (GPC) and converted into polystyrene. At this time, the GPC measurement conditions are as described above.

Regarding the weight average molecular weight (MWt) of the silicone graft polymer of component A, from the viewpoint of water repellency (water resistance) sustainability, it is preferably 10,000 or more, more preferably 14,000 or more, and still more preferably 17,000 or more, More preferably, it is 30,000 or more. From the viewpoint of the water dispersibility of the silicone graft polymer of component A, it is preferably 200,000 or less, more preferably 160,000 or less, still more preferably 130,000 or less, and still more preferably 95,000. the following. If it is within this range, it is possible to impart sufficient water repellency (water repellency) to the fiber article, and the silicone graft polymer of component A has excellent water dispersibility, so the fiber treatment agent can be washed and removed. Outstanding ones. In this specification, MWt is measured by gel permeation chromatography (GPC) and converted into polystyrene. The measurement conditions of GPC at this time are as described above.

In addition, when the silicone graft polymer of component A is produced from a radical-reactive organopolysiloxane, the following formula (II) is used for the reciprocal of MWra and the above-mentioned mass ratio (a/b) The calculated weight-average molecular weight (MWtcalc) of the silicone graft polymer of component A imparts sufficient water repellency (water resistance) to fiber articles and improves the performance of the silicone graft polymer of component A From the viewpoint of water dispersibility to make the fiber treatment agent excellent in washing and removing properties, it is preferably 10,000 or more, more preferably 14,000 or more, still more preferably 17,000 or more, and still more preferably 30,000 or more. For the silicon of component A From the viewpoint of the water dispersibility of the ketone graft polymer, it is preferably 200,000 or less, more preferably 160,000 or less, still more preferably 130,000 or less, and still more preferably 95,000 or less. MWtcalc=MWra×{1＋mass ratio(b/a)} (II)

The silicone graft polymer of component A can be produced, for example, by the following method: (i) The organopolysiloxane having a reactive functional group and the end having a functional group that can react with the reactive functional group The graft-onto method (polymer reaction method) in which the polymer segment of the saturated monomer reacts; or (ii) in the presence of free radical-reactive organopolysiloxane to make unsaturated Autonomous graft-from method in which monomers undergo free radical polymerization. Among these, the manufacturing method of (ii) above is preferable from the viewpoint of load reduction during manufacturing. The silicone graft polymer of component A can be manufactured in accordance with the manufacturing method described in Patent Document 3 (for example, the manufacturing method described in [0016] to [0023] of the document) or the manufacturing method described in Patent Document 4 (for example, the [0036] to [0067] of the literature).

In the fiber treatment agent of the present invention, regarding the content of the silicone graft polymer of component A, the effect exerted by it is more surely exerted, especially the effect of imparting water repellency to the treated object and the use of the antibacterial agent of component B From the viewpoint of the antibacterial effect enhancement effect, relative to the total mass of the fiber treatment agent, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and more preferably It is 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. In addition, regarding the above-mentioned "total mass of the fiber treatment agent", when the fiber treatment agent is a so-called spray type (when the fiber treatment agent is filled in a spray container with the fiber treatment agent in the spray product), When the fiber treatment agent contains a propellant, the "total mass of the fiber treatment agent" does not include the mass of the propellant. The "total mass of the fiber treatment agent" is the same as the following unless otherwise specified.

[Component B: Antibacterial agent] As the antibacterial agent of component B, those that can inhibit the proliferation of bacteria can be used without particular restrictions, and those that can cut off the source of odor, that is, inhibit the skin resident bacteria, the intestinal bacteria, and those that cause odor. The proliferation of the enzymes of these bacteria. For example, inorganic antibacterial agents, organic antibacterial agents, etc., which inhibit or exterminate the proliferation and growth of bacteria related to the production of urine odor, can be used alone or in combination of two or more.

As specific examples of inorganic antibacterial agents, for example, antibacterial metal ions or salts such as silver, zinc, copper, magnesium, calcium, aluminum, antimony, and bismuth are supported on zeolite, silica gel, low-molecular glass, Fine particles or needle crystals made of calcium phosphate, zirconium phosphate, silicate, and titanium oxide.

As a specific example of the organic antibacterial agent, piroctone ethanolamine [1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone Monoethanolamine salt], potassium oleate, sodium linoleate, sodium 1-pentyl sulfonate, sodium 1-decyl sulfonate, sodium butyl naphthalene sulfonate, sodium lauryl sulfate, dodecyl benzene sulfonate Anionic surfactants such as sodium and sodium cetyl sulfate; cationic surfactants such as cetyl benzalkonium phosphate, benzethonium chloride, benzalkonium chloride, cetylpyridinium chloride, etc.; oolong tea extraction Extracts, Scutellaria baicalensis Georgi extract, Cork extract, Coptis extract, Olive extract, Chamomile extract, Chamomile extract, Papaya extract, Licorice extract, Yellow barberry extract, Ursula vulgaris extract, Sophora flavescens extract, black tea extract, hawthorn extract, Chinese pepper extract, purple root extract, perilla extract, peony extract, calamus extract, honeysuckle extract, ivy extract, peppermint extract, sage Extract, thyme extract, thyme extract, tea extract, clove extract, camellia extract, peach kernel extract, houttuynia cordata extract, pseudoleaf tree extract, garlic extract, rose extract, coriander tea Extract, bisabolol extract, pseudoleaf extract, safflower extract, peony extract, hop extract, sapindus extract, comfrey extract, peach extract, eucalyptus extract, saxifrage extract Extracts, such as wormwood extract, lavender extract, rosemary extract, wild thyme extract, Sanguisorba vulgaris extract, etc.; phenoxyethanol, tocopherol sodium phosphate, o-cymene-5- Alcohol, persimmon tannin, octanoyl-2-glycerol ascorbate, isopropyl methylphenol, xylitol, xylitol, lohexidine hydrochloride, lohexidine gluconate, triclocarban, triclosan , Halocaban and parabens, etc.

The IOB value of the antibacterial agent of component B is preferably similar to the IOB value of the silicone graft polymer of component A used in combination. As the IOB values of the two components A and B are similar to each other, the compatibility of the two components with each other is improved. As a result, under the mechanism of the formation of the barrier film as shown in Figure 2(b) above, the two components can be displayed. Excellent antibacterial effect under the synergistic effect of ingredients A and B. If the IOB values of component A and component B are similar, the distribution density of the component B-derived antibacterial agent in the barrier film is increased compared with the case where the two are not similar, so even if the component B antibacterial agent is relatively small , Can also show sufficient antibacterial effect. From this point of view, 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 preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.6 Above, and preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.0 or less.

The IOB value of the antibacterial agent of 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, and still more preferably 3.0 or less. The inorganic value itself that determines the IOB value of the antibacterial agent of 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, and still more preferably Below 1000. The inorganic value itself which determines the IOB value of the antibacterial agent of 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, and still more preferably Below 1000.

As a preferred specific example of the antibacterial agent of component B, the compound represented by the following formula (B1), namely 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; combination with 2-aminoethanol(1:1 )] (CAS registration number 68890-66-4), alias piroctone olamine (or Piroctone ethanolamine). The IOB value of piroctone ethanolamine is 1.40. As piroctone ethanolamine, an antibacterial agent sold under the trade name "Octopirox" by Clariant can be used.

[化8]

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

In the fiber treatment agent of the present invention, the content of the antibacterial agent of component B is preferably 4 ppm or more relative to the total mass of the fiber treatment agent from the viewpoint of more reliably exerting the antibacterial effect exerted by it It is 10 ppm or more, more preferably 20 ppm or more, and still more preferably 50 ppm or more. If the content of the antibacterial agent of component B is less than 4 ppm relative to the total mass of the fiber treatment agent, the antibacterial effect may become insufficient. On the other hand, the upper limit of the content of the antibacterial agent of component B is not particularly limited, but if the content is too large, the antibacterial agent may cause excessive skin irritation, or the cost of the fiber treatment product may be too high. Considering the above, the content of the antibacterial agent of component B is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 5000 ppm or less.

[Component C: organic solvent] As the organic solvent of component C, it is only necessary to dissolve the components of the fiber treatment agent including components A and B. Examples include ethanol, isopropanol, hexane, butanol, isobutanol, and other carbon number 4 Straight or branched aliphatic alcohols below 6 above, 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., can be alone Use one of these or use two or more in combination.

In the fiber treatment agent of the present invention, the content of the organic solvent of Component C (in the case of containing multiple organic solvents, the total content), from the viewpoint of the cost of the fiber treatment product, it is relative to the fiber treatment agent The total mass is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, and still more preferably 95% by mass or less.

In the fiber treatment agent of the present invention, in addition to the above-mentioned components A to C, the components used in the fiber treatment agent (water repellency imparting agent) can be further appropriately formulated according to the purpose, use, dosage form, and the like. Examples of such arbitrarily blendable components include: solvents (water etc.) other than component C; colorants such as dyes and pigments; viscosity such as hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, and clay minerals Adjusting agents; pH adjusting agents such as organic acids, sodium hydroxide, potassium hydroxide, etc.; one of these can be used alone or in combination of two or more.

The fiber treatment agent of the present invention can be prepared into various dosage forms according to conventional methods, for example, it can be liquid; semi-solid such as gel, paste, cream, wax, etc.; solid such as sheet, stick, etc. .

The fiber treatment agent of the present invention can be applied to various fiber products. Examples of fiber articles to which the fiber treatment agent of the present invention can be applied include: shorts, loincloths, undershirts, bras, tights, socks and other underwear represented by underwear; football shirts, golf shirts, tennis shirts , Basketball shirts, table tennis shirts, badminton shirts, running shirts, football shorts, tennis shorts, basketball shorts, table tennis shorts, badminton shorts, running shorts, golf shorts, various sports underwear, various sports underwear, etc., sweaters , T-shirts, sweatshirts, training clothes, windproof jackets, shorts, tights and other sports clothing; pads for urine leakage treatment and other light incontinence supplies, menstrual sanitary napkins, sanitary pads and other vaginal secretion pads , Breast milk pad analogs, etc. The fiber treatment agent of the present invention is particularly useful for dealing with slight urine leakage. From this point of view, it is particularly effective when applied to shorts for men.

The method of applying the fiber treatment agent of the present invention to a treatment target (fiber-made 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 liquid or semi-solid, dipping into the fiber treatment agent, spray coating, dipping method, roll coating method, transfer method, die mouth coating Cloth, gravure coating, inkjet method, screen printing method, etc., coating by printing, etc., coating using a known liquid coating device, etc., can be used freely.

When the fiber treatment agent of the present invention is a sheet-like solid material, the sheet-like solid material can be attached to the desired part of the fiber article (for example, outside the front body of men’s shorts) through bonding methods such as adhesives as necessary. Surface) while using. The thickness of the fiber treatment agent as a sheet-like solid material is not particularly limited, as long as it is appropriately adjusted according to the application. For example, when it is attached to the outer surface or inner surface of the front body of men's shorts as a countermeasure for slight urine leakage At this time, it is preferably 50 μm or more, more preferably 100 μm or more, and preferably 2 mm or less, and more preferably 1 mm or less.

In addition, when the fiber treatment agent of the present invention is a rod-shaped solid material, a method of directly contacting the rod-shaped solid material with a fiber product for coating, or using a sponge or the like to indirectly coat the fiber product的方法。 The method. The fiber treatment agent of the rod-shaped solid substance has the same structure as lipstick, glue stick, etc., and includes the rod-shaped solid substance of the fiber treatment agent and a support portion that supports the solid substance.

The present invention includes a spray product obtained by filling the above-mentioned fiber treatment agent of the present invention in a spray container. The above-mentioned spray container typically has: a spray body with a fiber treatment agent containing portion inside; and a spray mechanism installed in the spray body. The spray mechanism is not particularly limited. For example, it may be a pressing spray type constructed by sucking up the contents (fiber treatment agent) in the spray body by the user pressing with a finger and spraying it, or may also be A trigger spray type in which the trigger is rotated and moved and the piston is depressed to cause the liquid in the barrel of the spray body to be sprayed from the nozzle.

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

The spray product of the present invention may be a manual spray product obtained by filling the fiber treatment agent of the present invention in a container equipped with a manual sprayer. The manual spray product is a spray product that does not use propellants such as gas. Specifically, for example, a manual trigger sprayer, an ultrasonic type, and especially a pressure accumulation type manual spray product can be exemplified due to the fineness of the droplet size. , The uniformity of the droplet diameter is good, so it is better.

In addition, the present invention includes a roll-coated product obtained by filling a roll-coating container with the fiber treatment agent of the present invention. The above-mentioned roller coating container is a container in which an inner stopper for rotatably holding the ball is arranged at the mouth of the container, and the content (fiber treatment agent) is distributed on the surface of the ball and applied to the desired part. When using the above-mentioned roll-coating container, the ball is brought into contact with the fibrous article to which the content is provided, and the container body is lifted upward so that the content is in contact with the ball, and the ball is rolled on the fibrous article. In this way, the content is distributed on the surface of the ball. As said roll coating container, a well-known thing can be used without a restriction|limiting in particular.

According to the fiber treatment agent of the present invention, it is possible to form a barrier coating with the silicone graft polymer of component A as the main body and prevent the penetration of body fluids such as urine on only one side of a fiber article having two opposite sides (front and back). The barrier film is not formed on the other side. The advantages of such "single-sided water repellency of fiber articles" include the following: the water repellency of fiber articles is suppressed to the minimum required, while maintaining the original physical properties of fiber articles . If a conventionally known water-repellent treatment agent is used to make the fiber-made article water-repellent, it will perform more than necessary water-repellency, resulting in a significant decrease in the properties of water absorption, flexibility, and air permeability that are not intended to be reduced. However, according to the fiber treatment agent of the present invention, the single-sided water repellency of fiber articles can be performed according to the method of use.

As a method of using the fiber treatment agent of the present invention that can realize water repellency on one side of a fiber article, for example, the following methods can be cited: 1) The fiber treatment agent is applied as a sheet-like solid to one side of the fiber article The method; 2) the method of directly contacting the fiber treatment agent as a rod-shaped solid substance on one side of the fiber article and coating; 3) using the spray product formed by filling the fiber treatment agent in the spray container, the A method of spraying a fiber treatment agent on one side of a fiber article; 4) A method of coating the fiber treatment agent on one side of a fiber article using a roll-coated product formed by filling the fiber treatment agent in a roll coating container.

As an example of fibrous articles that are subject to single-sided water repellency, the water absorption time obtained by the dripping method of JIS L-1907 is 30 seconds or less, preferably 20 seconds or less, more preferably 15 seconds or less, More preferably, it is water-absorbing for 1 second or less (hereinafter, also referred to as "water-absorbent fiber article"). Water-absorbent fiber products can absorb water and various aqueous liquids, for example, as body fluid excreted from the body, it can absorb sweat, urine, blood, vaginal secretions, and breast milk. The articles made of water-absorbent fibers typically mainly consist 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 fiber in the water-absorbent fiber article is preferably 50% by mass or more, and more preferably 70% by mass or more relative to the total mass of the water-absorbent fiber article. The absorbent fibrous article may be, for example, a sheet-like fibrous article with a thickness of about 0.01-5 mm, and more specifically, a form including any one or two or more of woven fabric (woven fabric), knitted fabric, non-woven fabric, and paper .

The fiber treatment agent of the present invention can be used for single-sided water repellency of various fiber products including water-absorbent fiber products, except for the aforementioned "single-sided water repellency of underwear such as men’s shorts to prevent slight urine leakage (urine) In addition to the dirt on outer clothing caused by post dripping, for example, it is suitable for the following purposes (1) to (10). In general, the following (1) to (6) are applications for absorbing a relatively small amount of liquid, specifically, preferably about 1 mL or less, and more preferably about 0.5 mL or less of liquid, the following (7) ~(10) is the use of a liquid with a larger amount of absorption, specifically, it is preferably about 1-100 mL, more preferably about 1-10 mL.

(1) Prevent the transfer of foot sweat to shoes and insoles by water repellency of the non-skin facing surface of the socks (water-absorbent fiber products) (shoe deodorization). The "non-skin facing surface" here refers to the surface facing the opposite side of the user's skin side (the side relatively far away from the user's skin) when the absorbent fiber product is used. The following is the same as long as there is no special explanation. In addition, the surface opposite to the non-skin facing surface of the absorbent fiber article (the surface facing the user's skin during use) is called the "skin facing surface". (2) Prevent excrement (vaginal secretions, menstrual blood, etc.) from transferring to the lower body (clothes worn on the lower body) by repelling the non-skin facing surface of women's underwear (absorbent fiber products). (3) Prevent the transfer of breast milk to clothing by repelling the non-skin facing surface of women's bra (absorbent fiber). (4) Prevent the water-based ink from penetrating through the water-repellent of the back of the drawing paper (absorbent fiber). (5) The concealment is improved by the water repellency of one side of the non-woven fabric (article made of absorbent fibers). The nonwoven fabric with improved concealment is suitable as a dripping pad, for example. The dripping pad is a sheet that absorbs and retains blood and other drips from foods such as meat or fish, and is used to maintain the freshness of the foods. The food material is covered with a drip pad including a non-woven fabric whose concealment is improved by water repellency on one side, so as to prevent dripping by using the water repellent one side of the non-woven fabric (the side opposite to the food material side) It is soaked, and it is difficult to see drops of blood and other liquid oozing from the food from the outside. (6) Prevent the transfer of dirt to the table by hydrating the back of the tablecloth.

(7) Prevent dirt from adhering to hands by repelling water on one side of wipes and wipes (articles made of absorbent fibers). (8) The inner surface (the side of the user's body) of the bib (absorbent fiber) is water-repellent to prevent the transfer of dirt from saliva or food to clothes. (9) Prevent the ground from wetting, non-slip, and prevent the reproduction of mold and other bacteria by the water repellency of the single side of the foot pad (absorbent fiber). (10) Prevent the transfer of sweat to mattresses, quilts and pillows by repelling the back of bed sheets, duvet covers and pillowcases (absorbent fiber articles) (the side opposite to the user's body). wet).

The fiber treatment agent of the present invention is also suitable for the following applications (11) to (15). When the fiber treatment agent of the present invention is applied to the following applications (11) to (15), it is particularly preferable to spray the fiber treatment agent with the above spray product. Furthermore, in the following (11) to (15), there may be cases where the above-mentioned one-side water repellency is not required, and the opposite sides of the fiber article may be water repellent.

(11) Prevent the adhesion of urine dirt by the water-repellent of the skin facing surface of the outer pants (article made of absorbent fibers). (12) Reduce sweat stickiness by hydrating the opposite side of the skin of shoes, socks, and caps (absorbent fiber products). (13) The surface of the bed sheet (absorbent fiber) (the surface of the user's body) is hydrated to reduce the stickiness of sweat. (14) Reduce the stickiness of sweat by repelling the opposite side of the skin of the underwear (absorbent fiber products). (15) Prevent perspiration by hydrating the non-skin facing surface of the underwear (absorbent fiber). Example

Hereinafter, the present invention will be described more specifically using examples, but the present invention is not limited to the examples.

(Synthesis of Silicone No.1) The compound (polyoxazoline-modified silicone) in which p is 1346 and q is 5 in the above formula (A1) was synthesized and set as silicone No. 1. Specifically, 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate were mixed, and 2.0 g of molecular sieve (trade name: Zeorum A-4, manufactured by Tosoh Co., Ltd.) was used. The mixed solution was dehydrated for 15 hours. In addition, 100 g of polydimethylsiloxane (KF-8015, weight average molecular weight of 100,000, amine equivalent of 20,000, manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd.) modified with a primary aminopropyl side chain and 100 g of Mix 203 g of ethyl ester, and use 15.2 g of molecular sieves to dehydrate the mixture for 15 hours. To the above dehydrated 2-ethyl-2-oxazoline ethyl acetate solution, 0.77 g (0.005 mol) of diethyl sulfate was added, and the mixture was heated and refluxed at 80°C for 8 hours under a nitrogen atmosphere to synthesize End-reactive poly(N-propyl ethyleneimine). Add the terminally reactive poly(N-propylene ethyleneimine) solution to the above-mentioned dehydrated side chain first-level aminopropyl modified polydimethylsiloxane solution at a time for 10 hours at 80°C Heat to reflux. The reaction mixture was concentrated under reduced pressure to obtain an N-propylene ethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (108 g, yield 95%). The mass ratio (a/b) of the organopolysiloxane segment (a) and 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.

(Synthesis of Silicone No.2) The compound (polyoxazoline-modified silicone) in which p is 656 and q is 20 in the above formula (A1) was synthesized, and set as silicone No.2. Specifically, 41.8 g (0.42 mol) of 2-ethyl-2-oxazoline was mixed with 104.05 g of ethyl acetate, and the mixed solution was dehydrated for 15 hours using 9.5 g of molecular sieves. In addition, 153.75 g of polydimethylsiloxane (KF-8003, weight average molecular weight of 50000, amine equivalent of 2000, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) modified with a primary aminopropyl side chain and 153.75 g and acetic acid 312.6 g of ethyl ester was mixed, and 22.7 g of molecular sieve was used to dehydrate the mixed solution for 15 hours. Add 9.48 g (0.062 mol) of diethyl sulfate to the above dehydrated 2-ethyl-2-oxazoline ethyl acetate solution, and heat and reflux at 80°C for 8 hours under a nitrogen atmosphere to synthesize End-reactive poly(N-propyl ethyleneimine). Add the terminally reactive poly(N-propylene ethyleneimine) solution to the dehydrated polydimethylsiloxane solution modified by the side chain with a primary aminopropyl group at one time, and take 10 hours Heat to reflux at 80°C. The reaction mixture was concentrated under reduced pressure to obtain an N-propylene ethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (190 g, yield 94%). The mass ratio (a/b) of the organopolysiloxane segment (a) and the polymer segment (b) derived from the unsaturated monomer in the final product is 3.0, and the weight average molecular weight of the final product is 40,000 (according to Added calculated value).

(Synthesis of Silicone No.3) The compound (polyoxazoline-modified silicone) in which p is 656 and q is 20 in the above formula (A1) was synthesized and set as silicone No. 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 for 15 hours using 9.0 g of molecular sieves. In addition, 153.75 g of polydimethylsiloxane (KF-8003, weight average molecular weight of 50000, amine equivalent of 2000, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) modified with a primary aminopropyl side chain and 153.75 g and acetic acid 312.6 g of ethyl ester was mixed, and 22.7 g of molecular sieve was used to dehydrate the mixed solution for 15 hours. Add 9.98 g (0.064 mol) of diethyl sulfate to the ethyl acetate solution of the dehydrated 2-ethyl-2-oxazoline, and heat to reflux at 80°C for 8 hours under a nitrogen atmosphere to synthesize End-reactive poly(N-propyl ethyleneimine). Add the terminally reactive poly(N-propylene ethyleneimine) solution to the dehydrated polydimethylsiloxane solution modified by the side chain with a primary aminopropyl group at one time, and take 10 hours Heat to reflux at 80°C. The reaction mixture was concentrated under reduced pressure to obtain an N-propylene ethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (200 g, yield 92%). The mass ratio (a/b) of the organopolysiloxane segment (a) and the polymer segment (b) derived from unsaturated monomers in the final product is 2.3, and the weight average molecular weight of the final product is 70400 (according to Added calculated value).

(Synthesis of Silicone No.4) The compound (polyoxazoline-modified silicone) in which p is 393 and q is 12 in the above formula (A1) was synthesized and set as silicone No. 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 for 15 hours using 14.8 g of molecular sieves. In addition, 100 g of polydimethylsiloxane (AP3651, weight average molecular weight of 30000, amine equivalent of 2000, manufactured by Toray Dow Corning Co., Ltd.) modified with a primary aminopropyl side chain and 100 g of ethyl acetate 203 g was mixed, and 15.2 g molecular sieve was used to dehydrate the mixed solution for 15 hours. 6.17 g (0.04 mol) of diethyl sulfate was added to the ethyl acetate solution of the dehydrated 2-ethyl-2-oxazoline, and the mixture was heated and refluxed at 80°C for 8 hours under a nitrogen atmosphere to synthesize End-reactive poly(N-propyl ethyleneimine). Add the terminally reactive poly(N-propylene ethyleneimine) solution to the dehydrated polydimethylsiloxane solution modified by the side chain with a primary aminopropyl group at one time, and take 10 hours Heat to reflux at 80°C. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow solid (190 g, yield 95%). The mass ratio (a/b) of the organopolysiloxane segment (a) and the polymer segment (b) derived from the unsaturated monomer in the final product is 1.0, and the weight average molecular weight of the final product is 60,000.

(Synthesis of Silicone No.5) The compound of the above formula (A2) with p being 656 and q being 20 (dimethylacrylamide grafted with organosiloxane) was synthesized and set as silicone No. 5. Specifically, first, a radical reactive organopolysiloxane is synthesized. To a separable flask equipped with a reflux cooling tube, a thermometer, a nitrogen introduction tube, and a stirring device, add organopolysiloxane (KF-8003 with a weight average molecular weight of 50,000, The amine equivalent is 2000, made by Shin-Etsu Chemical Industry Co., Ltd.) 100 g as an organopolysiloxane having a reactive functional group, and 8 g of N-acetyl-DL-homocysteine thiolactone is added. Under a nitrogen atmosphere, the temperature was raised to 100°C and stirred for 3 hours to synthesize a free radical reactive organopolysiloxane A with mercapto groups. Add 76.7 g of ethanol to a separable flask equipped with a reflux cooler, thermometer, nitrogen introduction tube, and stirring device. While stirring the ethanol under reflux at 80°C under a nitrogen atmosphere, the following solution (a) and solution (b) were put into different dropping funnels, and dropped simultaneously for 1 hour. Solution (a): A solution obtained by mixing 20.0 g of dimethyl acrylamide and 20.0 g of ethanol. Solution (b): 80.0 g of the above radical reactive organopolysiloxane A, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65B, Fujifilm Wako Pure Chemical Industries, Ltd.) Co., Ltd.) 0.035 g, 53.3 g ethanol mixed solution. After completion of the dropping, the reaction mixture was stirred at 80°C for 3 hours and then cooled. The total reaction time is 4 hours. The ethanol was removed from the reaction mixture at room temperature (25° C.) and reduced pressure (20 kPa) for 4 hours to obtain a mixture containing dimethyl acrylamide grafted organosiloxane as a white solid.

(Synthesis of Silicone No.6) The compound of the above formula (A2) where p is 656 and q is 20 (dimethyl acrylamide/tert-butyl acrylamide grafted with organosiloxane) was synthesized, and set as silicone No.6. Specifically, 75.0 g of ethanol was added to a separable flask equipped with a reflux cooler, a thermometer, a nitrogen introduction tube, and a stirring device. While stirring the ethanol under reflux at 80°C under a nitrogen atmosphere, the following solution (a) and solution (b) were put into different dropping funnels, and dropped simultaneously for 1 hour. Solution (a): a solution obtained by mixing 22.0 g of dimethyl acrylamide, 3.0 g of tertiary butyl acrylamide, and 25.0 g of ethanol. Solution (b): A solution of 75.0 g of the above radical reactive organopolysiloxane A, 0.033 g of V-65B, and 50.0 g of ethanol. After completion of the dropping, the reaction mixture was stirred at 80°C for 3 hours and then cooled. The total reaction time is 4 hours. The ethanol was removed from the reaction mixture at room temperature (25°C) and reduced pressure (20 kPa) for 4 hours to obtain a white solid containing dimethylacrylamide/tertiary butylacrylamide grafted organosiloxane A mixture of alkanes.

(Silicone No. 7) The compound in the following formula (A11) where m is 663 and n is 13 (amino-modified silicone, KF-864, weight average molecular weight is 50,000, amine equivalent is 3800, manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone No.7.

(Silicone No. 8) The following formula (A11) in which m is 1346 and n is 5 (amino-modified silicone, KF-8015, weight average molecular weight is 100,000, amine equivalent is 20,000, manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone No. 8.

(Silicone No. 9) The following formula (A12) has 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.) ) Is set to silicone No. 9.

(Silicone No. 10) The following formula (A12) has 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.) ) Is set to silicone No. 10.

(Silicone No.11) The compound (polyether modified silicone, KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) in the following formula (A12) with a viscosity of 920 mm ² /s at 25°C and an HLB of 10 ) Is set to silicone No. 11.

(Silicone No.12) The compound (polyether modified silicone, KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.) in the following formula (A12) with a viscosity of 1600 mm ² /s at 25°C and an HLB of 7 ) Is set to silicone No. 12.

(Silicone No.13) The following formula (A12) has 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. ) Is set to silicone No. 13.

(Silicone No.14) The following formula (A12) has 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. ) Is set to silicone No. 14.

(Silicone No.15) The compound (polyether modified silicone, KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd.) in the following formula (A12) with a viscosity of 530 mm ² /s at 25°C and an HLB of 5 ) Is set to silicone No. 15.

(Silicone No.16) The following formula (A12) has a viscosity of 4000 mm ² /s at 25°C and an HLB of 5 (polyether modified silicone, X-22-4515, Shin-Etsu Chemical Co., Ltd. Made by the company) set to silicone No. 16.

(Silicone No.17) The compound (single-terminal hydroxyl group, Silaplane FA-0411, weight average molecular weight 1000, manufactured by JNC Co., Ltd.) in which n is 11 in the following formula (A13) was set as silicone No.17. In addition, in the following formula (A13), Me represents a methyl group.

(Silicone No.18) The compound (single-terminal hydroxyl group, Silaplane FA-0425, weight average molecular weight of 10,000, manufactured by JNC Co., Ltd.) in which n is 132 in the following formula (A13) was set as silicone No. 18.

(Silicone No.19) The compound (single-terminal hydroxyl group, Silaplane FA-DA11, weight average molecular weight 1000, manufactured by JNC Co., Ltd.) in which n is 9 in the following formula (A14) was set as silicone No.19. In addition, in the following formula (A14), Me represents a methyl group.

(Silicone No. 20) The compound (single-terminal hydroxyl group, Silaplane FA-DA26, weight average molecular weight of 15000, manufactured by JNC Co., Ltd.) in which n is 198 in the following formula (A14) was set as silicone No. 20.

(Silicone No. 21) The compound in which n is 10 in the following formula (A15) (single-terminal methacryloxy group, Silaplane FA-0711, weight average molecular weight 1000, manufactured by JNC Co., Ltd.) is set as silicone No. 21. In addition, in the following formula (A15), Me represents a methyl group.

(Silicone No. 22) The compound (single-terminal methacryloyloxy group, Silaplane FA-0725, weight average molecular weight 10,000, manufactured by JNC Co., Ltd.) in which n is 131 in the following formula (A15) was set as silicone No. 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 set as silicone No. 23. Although the silicone-containing polymer copolymer (silicone No. 23) has siloxane bonds, the main chain is composed of C-C bonds and does not have a "main chain with siloxane bonds." Specifically, a 500 mL separable flask containing 117.4 g of ethanol was heated to 80°C under a nitrogen atmosphere at 150 rpm. Into it, 21.0 g of Silaplane FM-0711, 10.5 g of dimethylaminoethyl methacrylate, 42.0 g of methacrylic acid, 31.5 g of tert-butyl methacrylate, 52.2 g of ethanol, and 2,2- A mixture of azobis(2-methylbutyronitrile) (V-59, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). After further heating at 80°C for 3 hours, the solvent ethanol was dried to obtain a white polymer.

[化9]

[Examples 1 to 11, Comparative Examples 1 to 24, Reference Example 1] Dissolve any one of the aforementioned silicones in an organic solvent to obtain a silicone solution with a silicone concentration of 5% by mass, and dissolve a specific amount of antibacterial agent in the silicone solution to prepare the examples and comparative examples Fiber treatment agent (liquid). In addition, as a comparative example, a fiber treatment agent (liquid) without using silicone was also prepared. As the above-mentioned organic solvent, ethanol, isopropanol, or hexane is used. As the above-mentioned antibacterial agent, the above-mentioned piroctone ethanolamine (the compound represented by the above formula (B1), "Octopirox" manufactured by Clariant, antibacterial agent No. 1) or phenoxyethanol (manufactured by Dow Chemical, "Neolone PH100", antibacterial agent No. 2).

[Evaluation] For the fiber treatment agents to be evaluated, the water repellency imparting properties, washing removal properties, and antibacterial properties were evaluated by the following methods. The results are shown in Table 2 and Table 3 below.

＜Method of evaluating water repellency properties＞ Prepare super horse cotton (square shorts manufactured by UNIQLO Co., Ltd., with a square shape of 10 cm when viewed from above, 93% by mass cotton and 7% by mass polyurethane) as a fiber product. Use a commercially available washing machine (Hitachi Household NW-500MX) and commercially available powder lotion (manufactured by Kao Co., Ltd., Attack BioEX), and washing the super horse cotton according to conventional methods. The washing conditions are 1.5 kg of washing, 30 L of water, 20 g of lotion, washing for 9 minutes, rinsing twice, dehydrating for 6 minutes, and drying (at room temperature 27℃, 45%RH environment for 8 hours). Fill the fiber treatment agent of the evaluation object in a spray container (manufactured by Maruemu Co., Ltd., PP spray bottle No. 6), and use the spray container to wash the super horse cotton under normal temperature and pressure. The entire area of the single side is sprayed 6 times to apply 0.72 g of fiber treatment agent to Super Pima cotton (0.036 g in terms of solid content). After spraying, the Super Horse cotton is placed in the above environment for a period of time to completely remove the organic solvent as the solvent of the fiber treatment agent, and then a piece of Kimwipe (registered trademark) (manufactured by Nippon Paper Crecia, S-200) is placed on the Super The fiber treatment agent-imparted surface of horse cotton is overlapped so as to cover the entire area of the fiber treatment agent-imparted surface to obtain a laminate, and the laminate is superimposed on the fiber treatment agent non-imparted surface of super horse cotton (not Kimwipe (registered) Place it on a water platform with the trademark) covered surface facing upwards, and inject 1 mL of physiological saline with a sodium chloride concentration of 0.9% by mass from the upper surface of the super horse cotton, that is, the side where the fiber treatment agent is not provided. The injection of the physiological saline is performed by putting the physiological saline into the cup and pouring the cup. After the injection of the physiological saline, the Kim Towel was quickly observed visually, and the situation where the physiological saline was not transferred to the Kim Towel was evaluated as "water repellency imparting", and the situation where the physiological saline was transferred to Kim Towel was evaluated as "water repellency imparting property". If the evaluation is "there is water repellency", it is judged that the fiber treatment agent has excellent water repellency, which is a high evaluation.

＜Evaluation method of washing removal ability＞ Prepare a 10 cm square super horse cotton (manufactured by UNIQLO Co., Ltd.) as a fibrous product when viewed from above, using a commercially available washing machine (manufactured by Hitachi Home Appliances Co., Ltd., NW-500MX) and commercially available powder Lotion (manufactured by Kao Co., Ltd., Attack BioEX) to wash the super horse cotton according to a conventional method. The washing conditions are 1.5 kg of washing, 30 L of water, 20 g of lotion, washing for 9 minutes, rinsing twice, dehydrating for 6 minutes, and drying (at room temperature 27℃, 45%RH environment for 8 hours). After washing, the weight of Super Horse cotton is measured (the measured value is set to W0). Fill the fiber treatment agent of the evaluation object in a spray container (manufactured by Maruemu Co., Ltd., PP spray bottle No. 6), and use the spray container to wash the super horse cotton under normal temperature and pressure. The entire area of the single side is sprayed 40 times to apply 5 g of the fiber treatment agent to the super horse cotton (0.25 g in terms of solid content). After spraying, the Super Horse cotton is placed in the above environment for 12 hours to completely remove the organic solvent as the solvent of the fiber treatment agent, and the weight of the Super Horse cotton is measured (the measured value is set to W1). Dissolve 0.33 g of powder lotion (manufactured by Kao Co., Ltd., Attack) in 500 mL tap water to prepare washing water. Add 500 mL of the washing water with a water temperature of 20°C to a 500 mL beaker and a cylindrical stirrer ( The diameter is 8 mm, and the axial length is 5 mm). Use a magnetic stirrer (manufactured by HANNA, HI304) to rotate the stirrer at a speed of 200 rpm to stir the washing water. The washing water will be supported by a supporting member in a hanging state. The whole of the super horse cotton of the fiber treatment agent is immersed in the washing water during the stirring in such a way that the super horse cotton does not come into contact with the stirrer, and after standing in this state for 5 minutes, the super horse cotton is removed from the beaker Take out the washing water and rinse with running water for 10 seconds, and then spin the towel by twisting the towel, leave it to dry for 24 hours in an environment of normal temperature and pressure, and then measure the weight of super horse cotton (set the measured value as W2) . Substitute the measured values W0, W1, and W2 of the weight of the super horse cotton in the following formula to calculate the treatment agent removal rate. If the treatment agent removal rate is 15% or more, it is set as "with washing removability", and if it is less than 15%, it is set as "without washing removability". The higher the removal rate of the treatment agent, the more easily the fiber treatment agent can be removed by washing and the better the washing removal property, and the higher the evaluation. Treatment agent removal rate (%) = {(W1－W2)/(W1－W0)}×100

之聚苯乙烯製培養皿(AS ONE股份有限公司製造)，而製作瓊脂培養基。 其次，藉由將評價對象之纖維處理劑進行6次按壓噴霧，而將0.72 g(以固形物成分換算為0.036 g)之纖維處理劑加入至50 mL之螺旋管(Maruemu股份有限公司製造)。利用40℃之真空乾燥機使纖維處理劑乾燥固化。 作為菌液使用如下者：自4名健康之受驗者各採取40 mL尿，於該採取之各尿中混合自同一受驗者之男性生殖器表面採取之皮膚常駐菌而製作。皮膚常駐菌之採取藉由如下方式實施：使用3根CultureSwab (BD BBL CultureSwab EZII，日本Becton Dickinson股份有限公司製造)，將該拭子之前端部(棉球)以殺菌生理鹽水潤濕之後，利用該拭子之前端部對受驗者之男性生殖器表面擦拭10次。 於纖維處理劑已乾燥固化之50 mL螺旋管內添加所製備之菌液1 mL之後，於37℃之條件進行靜置培養，對24小時培養後之靜止期(stationary phase)之生菌數進行定量。 作為菌數之定量方法，依照瓊脂平板稀釋法，將經24小時培養之培養液利用殺菌生理鹽水稀釋至10¹ 倍、10² 倍、10³ 倍、10⁴ 倍、10⁵ 倍、10⁶ 倍、10⁷ 倍、10⁸ 倍、10⁹ 倍，將所得之培養液於上述瓊脂培養基中分散展開100 μL之後，於30℃靜置培養24小時，對形成於培養基上之菌落進行計數。24小時培養後之菌數(下述表2及表3之「24 h後菌數」)越少，判斷為抗菌性越優異，越為高評價。<Method for evaluating antibacterial properties> First, 64 g of SCD agar medium "Daigo" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 1600 mL of distilled water at 70°C and placed in an autoclave (Hirayama Manufacturing Co., Ltd.) at 120°C. Manufactured by Co., Ltd., HiClave HVA-110) 20 minutes. Before the resulting solution solidifies, flow into 90 mm

The polystyrene petri dishes (manufactured by AS ONE Co., Ltd.) were used to prepare agar medium. Next, 0.72 g (0.036 g in terms of solid content) of the fiber treatment agent was added to a 50 mL spiral tube (manufactured by Maruemu Co., Ltd.) by spraying the fiber treatment agent of the evaluation object 6 times. Use a vacuum dryer at 40°C to dry and solidify the fiber treatment agent. Use the following as a bacterial solution: 40 mL of urine is taken from each of 4 healthy subjects, and the urine is mixed with skin resident bacteria collected from the surface of the male genitals of the same subject. The collection of skin resident bacteria is carried out by using 3 CultureSwab (BD BBL CultureSwab EZII, manufactured by Becton Dickinson Co., Ltd., Japan), and moistening the tip of the swab (cotton ball) with sterile physiological saline, and then using The front end of the swab wiped the surface of the subject's male genitalia 10 times. After adding 1 mL of the prepared bacterial solution to a 50 mL spiral tube where the fiber treatment agent has been dried and solidified, perform static culture at 37°C, and measure the number of bacteria in the stationary phase after 24 hours of culture Quantitative. As a quantitative method for the number of bacteria in accordance with the agar plate dilution method, cultured for 24 hours after the culture using sterilized physiological saline solution was diluted to ¹⁰¹ times, ¹⁰² times, ¹⁰³ times, ¹⁰⁴ times, ¹⁰⁵ times, ¹⁰⁶ times , 10 ⁷ times, 10 ⁸ times, ¹⁰⁹ times, the obtained culture solution was spread in the above agar medium and spread 100 μL, then stand at 30 ℃ for 24 hours, and count the colonies formed on the medium. The smaller the number of bacteria after 24 hours of incubation (the "number of bacteria after 24 h" in Table 2 and Table 3 below), the more excellent the antibacterial properties are judged to be, and the higher the evaluation is.

[Table 2] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 Silicone Content (mass%) 5 5 5 5 5 5 5 5 5 5 5 - - - - - - - species No.1 No.2 No.3 No.3 No.3 No.3 No.3 No.4 No.5 No.6 No.3 - - - - - - - Existence of side chains with molecular weight above 800 Have Have Have Have Have Have Have Have Have Have Have - - - - - - - The molecular weight of the side chain with an amount of more than 800*1 2700 800 1000 1000 1000 1000 1000 2500 16249 22402 1000 - - - - - - - I0B value 0.71 1.12 1.21 1.21 1.21 1.21 1.21 1.62 1.55 1.58 1.21 - - - - - - - Antibacterial agents content 4 ppm 4 ppm 4 ppm 10 ppm 20 ppm 50 ppm 100 ppm 100 ppm 100 ppm 100 ppm 100 ppm - 4 ppm 10 ppm 20 ppm 50 ppm 100 ppm 100 ppm species No.1 No.1 No.1 No.1 No.1 No.1 No.1 No.1 No.1 No.1 No.2 - No.1 No.1 No.1 No.1 No.1 No.2 I0B value 1.40 1.40 1.40 1.40 1.40 1.40 1.40 1.40 1.40 1.40 0.84 - 1.40 1.40 1.40 1.40 1.40 0.84 Organic solvents Content (mass%) Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 species Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol I0B of silicone/IOB of antibacterial agent 0.51 0.80 0.86 0.86 0.86 0.86 0.86 1.16 1.11 1.13 1.44 - - - - - - - Evaluation Water repellency Have Have Have Have Have Have Have Have Have Have Have no no no no no no no Washing removal (treatment agent removal rate) Yes (17%) Yes (21%) Yes (21%) Yes (21%) Yes (21%) Yes (21%) Yes (21%) Yes (42%) Yes (29%) Yes (38%) Yes (21%) - - - - - - - Antibacterial Initial bacterial count (CFU/mL) 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ² 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ² Bacteria count after 24 h (CFU/mL) 8.0×10 ⁸ 1.1×10 ⁹ 1.8×10 ⁹ 8.6×10 ⁷ 3.3×10 ⁷ ＜1.0×10 ⁶ ＜1.0×10 ⁶ ＜1.0×10 ⁶ ＜1.0×l0 ⁶ ＜1.0×10 ⁶ ＜1.0×10 ⁵ 3.0×10 ¹² 5.2×10 ¹¹ 1.9×10 ¹¹ 2.3×10 ¹² 3.7×10 ¹⁰ 1.0×10 ⁸ 2.0×10 ⁷ *1: The molecular weight of the whole part of the silicon atom of the silicone bond bonded to the main chain *2: The total content of silicone, antibacterial agent and organic solvent is 100% by mass

As shown in Table 2, the fiber treatment agent of each example contains the silicone graft polymer of component A. Therefore, compared with the fiber treatment agent of Comparative Examples 1 to 7 that does not contain silicone, the fiber treatment agent has a better effect on fiber articles. Excellent water repellency. In addition, according to the comparison between Examples 3-7 and Comparative Examples 2-6 and the comparison between Example 11 and Comparative Example 7, it can be seen that the antibacterial agent is combined with silicone (the silicone graft polymer of component A). ), the antibacterial property will be improved. That is, it can be seen that the silicone graft polymer of component A has the effect of enhancing the antibacterial effect of the antibacterial agent.

[table 3] Reference example Comparative example 1 8 9 10 11 12 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four Silicone Content (mass%) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 species No.3 No.7 No. 8 No.9 No.10 No.11 No.12 No.13 No.14 No.15 No.16 No.17 No.18 No.19 No.20 No.21 No.22 No.23*3 Existence of side chains with molecular weight above 800 Have no no no no no no no no no no no no no no no no no Molecular weight of side chains with molecular weight above 800*1 1000 - - - - - - - - - - - - - - - - - IOB value 1.21 0.42 0.40 0.37～0.40 0.48 0.41 0.57 0.41 0.42 0.40 1.27 Antibacterial agents content - - - - - - - - - - - - - - - - - - IOB value - - - - - - - - - - - - - - - - - - Organic solvents Content (mass%) Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 Margin*2 species Ethanol Isopropanol Hexane Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Evaluation Water repellency Have Have Have no no no no no no no no no no no no no no Have Washing removal (treatment agent removal rate) Yes (21%) None (13%) None (8%) Yes (72%) Yes (75%) Yes (76%) Yes (80%) None (10%) None (13%) None (12%) Yes (78%) Yes (26%) Yes (28%) None (7%) Yes (20%) Yes (38%) Yes (25%) None (0%) Antibacterial Initial bacterial count (CFU/mL) 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ 1.0×10 ³ Bacteria count after 24 h (CFU/mL) 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² 3.0×10 ¹² *1: The molecular weight of the whole part of the silicon atom bonded to the silicone bond of the main chain *2: The total content of silicone, antibacterial agent and organic solvent is 100% by mass *3: The main chain does not have a silicone bond

As shown in Table 3, the fiber treatment agents of each comparative example and reference example did not contain an antibacterial agent, and as a result, the antibacterial properties were inferior to the fiber treatment agents of each example described in Table 2. In addition, according to the comparison between Reference Example 1 and Comparative Examples 8 to 23, it can be seen that in order to obtain a fiber treatment agent that is excellent in water repellency and washing removability, and can impart washable water repellency (water repellency) to fiber articles, For silicone (silicone graft polymer of component A), the molecular weight of the side chain is 800 or more, and the IOB value is about 0.6 is not enough, and it needs to be 0.7 or more used in the examples. In addition, according to the results of the treatment agent removal rate of Comparative Example 24 using a silicone with no silicone bond in the main chain, the removal rate of the treatment agent is 0%, and the cleaning removal performance is not available. It can be seen that the fiber treatment agent using the silicone is provided with cleaning removal performance. , The silicone is required to have a "main chain with siloxane bonds". [Industrial availability]

According to the present invention, there is provided a fiber treatment agent, which prevents defects such as urine or other body fluids from oozing into clothes and visible from the outside, has excellent antibacterial effect, and can be removed by washing. The fiber treatment agent of the present invention is particularly useful for people who suffer from slight urine leakage. For example, the simple operation of spraying the fiber treatment agent to underwear, etc., can solve the above-mentioned urine stains and bacteria proliferation caused by the hygienic state The problem of decline, and because the fiber treatment agent has washing removal properties, the underwear treated with the fiber treatment agent can be restored by washing, thereby being hygienic.

1: shorts 1a: inner surface (skin facing side) 1b: Outer surface (non-skin facing surface) 2: Barrier film 3: outer clothing 50: bacteria 51: Antimicrobial 100: The Male Wearer

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 the wearing state of shorts provided with the fiber treatment agent. Fig. 2(a) is a schematic diagram showing the antibacterial mechanism using the antibacterial agent, and Fig. 2(b) is a schematic diagram showing the antibacterial mechanism using the fiber treatment agent of the present invention.

Claims (7)

A fiber treatment agent containing the following components A, B, and C, and the content of the antibacterial agent of component B is 4 ppm or more, Component A: Silicone graft polymer, which has a main chain containing siloxane bonds and side chains with a molecular weight of 800 or more, and an IOB value of 0.7 or more Ingredient B: Antibacterial agent Component C: organic solvent. The fiber treatment agent of claim 1, wherein the antibacterial agent of component B is piroctone ethanolamine. Such as the fiber treatment agent of 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. Such as the fiber treatment agent of claim 1 or 2, which is a sheet-like solid material. Such as the fiber treatment agent of claim 1 or 2, which is a rod-shaped solid substance. A spray product, which is formed by filling a spray container with the fiber treatment agent of claim 1 or 2. A roll-coated product, which is formed by filling the fiber treatment agent of claim 1 or 2 in a roll-coating container.

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