Methods for maintaining the antibacterial effect of textile products after they have been worn or used for the first time.

Abstract

To provide a method for maintaining the antibacterial effect of textile products after they have been worn or put into use. [Solution] A method for maintaining the antibacterial effect of a textile product after it has been worn or used, comprising the following steps 1 to 3: Step 1: A step of treating a textile product by contacting it with a treatment solution containing 2 mg / kg to 70 mg / kg of a dioctyl ammonium salt of a specific structure, 50 mg / kg to 1000 mg / kg of a nonionic surfactant of a specific structure, and water; Step 2: A step of drying the textile product obtained in Step 1; Step 3: A step of wearing or using the textile product obtained in Step 2.

Description

Technical Field

[0001] The present invention relates to a method for maintaining the antibacterial effect of a textile product after the start of wearing or use.

Background Art

[0002] With the increasing awareness of personal hygiene among consumers, there has been a growing concern about the odor and bacteria on clothing. It is known that various bacteria existing in the skin commensal flora and the environment adhere to and proliferate on clothing. It is considered that as the bacteria grow, the amount of metabolites discharged increases, making it easier to generate odors.

[0003] Techniques for suppressing the odor generated from clothing by washing the clothing with a detergent composition containing a cationic surfactant have been disclosed.

[0004] For example, Patent Document 1 discloses a liquid detergent composition for clothing that can impart an excellent anti-odor effect to clothing. Here, a liquid detergent composition for clothing containing at least one surfactant selected from a specific nonionic surfactant and at least one of two specific anionic surfactants, and at least one compound selected from two specific quaternary ammonium salts as a cationic surfactant is described.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Regarding textile products after the start of wearing or use, since they will be rewashed anyway, whether such textile products maintain an antibacterial effect has not been noticed in the first place. However, due to the recent diversification of lifestyles, it has become common to repeatedly use textile products or to wash them after a certain amount has accumulated after wearing or use. The present invention relates to a method for maintaining the antibacterial effect of a textile product after starting to wear or use it.

Means for Solving the Problems

[0007] The present invention relates to the following [1] to [5]. 〔1〕 A method for maintaining the antibacterial effect of a textile product after starting to wear or use it, including the following steps 1 to 3. Step 1: A step of treating by bringing a treatment liquid containing 2 mg / kg or more and 70 mg / kg or less of the following component (b), 50 mg / kg or more and 1000 mg / kg or less of the following component (c), and water into contact with the textile product Step 2: A step of drying the textile product obtained in Step 1 Step 3: A step of wearing or using the textile product obtained in Step 2 (b) component: A compound represented by the following general formula (1)

Chemical formula

[0008] According to the present invention, it is possible to provide a method for maintaining the antibacterial effect of textile products after they have been worn or put into use. [Modes for carrying out the invention]

[0009] As a result of the inventors' investigations, they unexpectedly discovered that treating textile products after the first wear or use with a treatment solution containing a specific cationic surfactant and a specific nonionic surfactant could sustain the antibacterial effect of the textile products after the first wear or use, thus completing the present invention. According to the present invention, textile products can be worn or used repeatedly after wear or use, or washed after a certain amount of worn or used textile products have accumulated, thereby improving the convenience of clothing.

[0010] The mechanism by which such effects are achieved is that antibacterial effects on textile products can generally be obtained by treating them with quaternary ammonium salts. However, when dirt and bacteria adhere to the treated textile product, the quaternary ammonium salt also acts on the dirt, making it difficult for it to act on the bacteria, and thus the antibacterial effect is not fully exerted. However, by treating the textile product with a quaternary ammonium salt having two C8 alkyl groups and a compound having an aliphatic hydrocarbon group and a polyoxyalkylene group, it is presumed that the compound having the aliphatic hydrocarbon group and polyoxyalkylene group modifies the dirt, making it easier for the specific quaternary ammonium salt of the present invention to act on bacteria.

[0011] [Methods to prolong antibacterial effects] The present invention provides a method for maintaining the antibacterial effect of a textile product after it has been worn or used, and comprises the following steps 1 to 3. Step 1: A process in which textile products are brought into contact with a treatment solution containing the following components: (b) at a concentration of 2 mg / kg to 70 mg / kg, (c) at a concentration of 50 mg / kg to 1000 mg / kg, and water. Step 2: A process to dry the textile product obtained in Step 1. Step 3: The process of wearing or using the textile product obtained in Step 2.

[0012] In this specification, "sustained antibacterial effect" means that the antibacterial effect persists for a long period of time, for example, from the start of wearing or using a textile product through the period after wearing or using it until the next washing. Whether or not the antibacterial effect persists is determined by the evaluation method described in the examples below.

[0013] <Process 1> Step 1 is a process in which the textile product is brought into contact with a treatment solution containing the following components: (b) at a concentration of 2 mg / kg to 70 mg / kg, (c) at a concentration of 50 mg / kg to 1000 mg / kg, and water. The content or amount of each component in the treatment solution is given per 1 kg of treatment solution.

[0014] (Processing solution) The processing solution used in step 1 contains the following component (b) at a concentration of 2 mg / kg to 70 mg / kg, the following component (c) at a concentration of 50 mg / kg to 1000 mg / kg, and water.

[0015] (b) The component is the compound represented by the following general formula (1).

[0016] [ka]

[0017] [In the formula, R 1 and R 2 Each of these is an alkyl group having 8 carbon atoms, and R 3 and R 4 Each of these is a group independently selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X - It is a monovalent anion.

[0018] In general formula (1), R 1 and R 2 Each of these is an alkyl group having 8 carbon atoms. Examples of alkyl groups include linear or branched alkyl groups, preferably linear alkyl groups, and more preferably saturated linear hydrocarbon groups having 8 carbon atoms, i.e., octyl groups. 1 and R 2 While it may be an alkyl group with 8 carbon atoms other than an octyl group, from the viewpoint of prolonging the antibacterial effect, R 1 and R 2 It is even more preferable that both are octyl groups.

[0019] In general formula (1), R 3 and R 4Each of these groups is independently selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms. Specific examples of alkyl groups having 1 to 3 carbon atoms include the methyl group, ethyl group, and propyl group. Specific examples of hydroxyalkyl groups having 1 to 3 carbon atoms include the hydroxymethyl group, hydroxyethyl group, and hydroxypropyl group. 3 and R 4 From the viewpoint of sustaining the antibacterial effect for a longer period of time, the alkyl group is preferably one or more carbon atoms with 3 or fewer carbon atoms, and more preferably a group selected from methyl and ethyl groups.

[0020] In general formula (1), X - It is a monovalent anion. As the monovalent anion, a monovalent anion selected from the group consisting of halide ions and alkyl sulfate ions having 1 to 3 carbon atoms is preferred. Specific examples of halide ions are chloride ions and bromide ions, with chloride ions preferred from the viewpoint of sustaining the antibacterial effect for a longer period of time. Specific examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions, with methyl sulfate ions and ethyl sulfate ions preferred from the viewpoint of sustaining the antibacterial effect for a longer period of time.

[0021] The content of component (b) in the treatment solution is 2 mg / kg or more, preferably 5 mg / kg or more, and more preferably 8 mg / kg or more, from the viewpoint of prolonging the antibacterial effect. On the other hand, from the viewpoint of reducing the amount of waste released into the environment, the content is 70 mg / kg or less, preferably 50 mg / kg or less, and more preferably 30 mg / kg or less.

[0022] (c) Component is a compound represented by the following general formula (c1-1). R 5 -(CO) m -O-(AO) n -R 6 (c1-1) [In the formula, R 5 R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, 6is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is a number between 0 and 1. AO is an alkylene oxy group with 2 to 4 carbon atoms. n is the average number of moles added, and is a number between 1 and 30.

[0023] In general formula (c1-1), R 5 The number of carbon atoms is 8 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, from the viewpoint of sustaining the antibacterial effect for a longer period of time.

[0024] R 5 R is an aliphatic hydrocarbon group, and from the viewpoint of sustaining the antibacterial effect for a longer period of time, it is preferably a group selected from alkyl groups and alkenyl groups, and more preferably an alkyl group. 5 The aliphatic hydrocarbon group may be a straight-chain aliphatic hydrocarbon group or a branched-chain aliphatic hydrocarbon group. The straight-chain aliphatic hydrocarbon group may be a straight-chain primary aliphatic hydrocarbon group or a straight-chain secondary aliphatic hydrocarbon group. 5 Preferred specific groups include one or more groups selected from primary or secondary octyl groups, decyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, tetradecenyl groups, hexadecenyl groups, and octadecenyl groups.

[0025] In general formula (c1-1), the AO group is an alkylene oxy group having 2 to 4 carbon atoms, preferably an alkylene oxy group having 2 to 3 carbon atoms, and more preferably an alkylene oxy group selected from an ethylene oxy group and a propylene oxy group. When a nonionic surfactant having the structure represented by general formula (c1-1) contains multiple AO groups, the multiple AO groups may be ethylene oxy groups, or alkylene oxy groups containing an ethylene oxy group and another alkylene oxy group, such as an alkylene oxy group having 3 or 4 carbon atoms. For example, an alkylene oxy group containing an ethylene oxy group and a propylene oxy group is also possible. The other alkylene oxy group is preferably a propylene oxy group. When the multiple AO groups contain an ethylene oxy group and an alkylene oxy group having 3 or 4 carbon atoms, the ethylene oxy group and the alkylene oxy group having 3 or 4 carbon atoms may be bonded in a block-type or random-type bond. If the material contains both an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be linked in a block or random manner.

[0026] In the general formula (c1-1), m is a number of 0 or 1, and is preferably 0 from the viewpoint of prolonging the antibacterial effect for a longer period of time.

[0027] In general formula (c1-1), n ​​is the average number of moles of AO groups added, and is a number between 1 and 30. In general formula (c1-1), n ​​is preferably 3 or more, more preferably 5 or more, even more preferably 7 or more, and 30 or less, from the viewpoint of sustaining the antibacterial effect for a longer period of time, and from the same viewpoint, preferably 25 or less, more preferably 20 or less, even more preferably 16 or less, even more preferably 14 or less, even more preferably 12 or less, and even more preferably 10 or less. n is the raw material for the production of general formula (c1-1) R 5 (CO) m The number of moles of alkylene oxide with 2 to 4 carbon atoms added to 1 mole of OH may be one mole, or it may be the average number of moles of alkylene oxide with 2 to 4 carbon atoms added after the addition reaction.

[0028] In general formula (c1-1), R 5This is either a hydrogen atom or a methyl group, and from the viewpoint of prolonging the antibacterial effect, a hydrogen atom is preferred.

[0029] The content of component (c) in the treatment solution is 50 mg / kg or more, preferably 70 mg / kg or more, more preferably 80 mg / kg or more, and even more preferably 90 mg / kg or more, from the viewpoint of sustaining the antibacterial effect for a longer period of time. From a similar viewpoint, the content is 1000 mg / kg or less, preferably 500 mg / kg or less, and more preferably 300 mg / kg or less.

[0030] The water used in the treatment solution can be deionized water (sometimes called ion-exchanged water) or water to which sodium hypochlorite has been added at a rate of 1 mg / kg to 5 mg / kg. Tap water can also be used.

[0031] The water content in the processing solution may be the remainder after excluding essential components such as component (b) and other optional components.

[0032] In step 1, the bath ratio, which is expressed as the ratio of the mass of the textile product (kg) to the volume of the treatment solution (liters), i.e., the volume of the treatment solution (liters) / mass of the textile product (kg), is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more, from the viewpoint of sustaining the antibacterial effect for a longer period of time. Similarly, it is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.

[0033] The contact time between the textile product and the treatment solution in step 1 is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more, from the viewpoint of prolonging the antibacterial effect, and preferably 60 minutes or less, more preferably 40 minutes or less, and even more preferably 20 minutes or less, from the viewpoint of economic efficiency.

[0034] The temperature of the treatment solution in step 1 is preferably 0°C or higher, more preferably 4°C or higher, and even more preferably 10°C or higher, from the viewpoint of sustaining the antibacterial effect for a longer period of time. On the other hand, from the viewpoint of reducing the energy required for the treatment, it is preferably 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower.

[0035] As an optional step, step 1 may include a step to reduce the amount of processing liquid adhering to the textile product after it has come into contact with the processing liquid. Examples of steps to reduce the amount of processing liquid include centrifugal dewatering of the textile product, compressing it with rollers, or squeezing it by hand.

[0036] <Optional ingredients> The processing solution used in step 1 of the present invention may contain components other than (b), (c), and water.

[0037] <(d) component> In this invention, component (d) is an anionic surfactant. By using component (d) in combination with components (b) and (c) described above, the effect of prolonging the antibacterial effect can be further enhanced.

[0038] (d) The component more preferably contains one or more anionic surfactants selected from the group consisting of the following components (d1), (d2), (d3), and (d4). (d1) Components: Alkyl or alkenyl sulfates or salts thereof (d2) Components: Polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkylene oxy group or salts thereof (d3) Components: Alkylbenzenesulfonic acid, olefin sulfonic acid, alkanesulfonic acid or salts thereof (d4) Components: fatty acids or salts thereof

[0039] More specifically, component (d1) includes one or more anionic surfactants selected from alkyl sulfate esters with an alkyl group having 10 to 18 carbon atoms, and alkenyl sulfate esters with an alkenyl group having 10 to 18 carbon atoms, or salts thereof. From the viewpoint of further enhancing the effect of prolonging the antibacterial effect, component (d1) is preferably one or more anionic surfactants selected from alkyl sulfate esters with an alkyl group having 12 to 14 carbon atoms, or salts thereof.

[0040] Examples of salts of component (d1) include alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0041] (d2) As for the component, an anionic surfactant represented by the following general formula (2) is preferred. R 5 O-(AO)n-SO3Y (2) [In formula (2), R 5 is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, AO is an alkylene oxy group having 2 to 4 carbon atoms, n is the average number of moles of AO groups added, which is between 0.5 and 10, and Y is a counter salt that dissociates in water to become a cation, Y + These include hydrogen ions, alkali metal ions, alkaline earth metal ions (half an atom), ammonium ions, or organic ammonium ions.

[0042] Regarding component (d2), R 5 The carbon group is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, and from the viewpoint of further enhancing the effect of prolonging the antibacterial effect of the composition, the carbon number is preferably 12 or more. On the other hand, from the same viewpoint, the carbon number is preferably 14 or less.

[0043] Therefore, R 5Preferred aliphatic hydrocarbon groups include one or more aliphatic hydrocarbon groups selected from primary or secondary decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, and hexadecyl groups. Furthermore, from the viewpoint of enhancing the effect of prolonging the antibacterial effect, R 5 When the mass of preferred aliphatic hydrocarbon groups is taken as 100% by mass, the proportion of carbon atoms in the aliphatic hydrocarbon group having 16 carbon atoms is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0044] In general formula (2), the AO group is an alkylene oxy group having 2 to 4 carbon atoms. The alkylene oxy group having 2 to 4 carbon atoms is selected from the group consisting of an ethylene oxy group, a propylene oxy group, and a butylene oxy group. When the (AO)n group contains an ethylene oxy group and a propylene oxy group, the ethylene oxy group and the propylene oxy group may be bonded in a block type or a random type. In the present invention, the (AO)n group being a polyoxyalkylene group containing a propylene oxy group means R in general formula (2) above. 5 It may be understood that the compound is obtained by an addition reaction in which propylene oxide is always used when adding an alkylene oxide with 2 to 4 carbon atoms to an OH group.

[0045] In general formula (2), n is the average number of moles of AO groups added, and is a number between 0.5 and 10. In general formula (2), n is preferably 0.6 or more, more preferably 2 or more, from the viewpoint of further enhancing the effect of prolonging the antibacterial effect, and also preferably 6 or less, and more preferably 5 or less, from the same viewpoint. The ratio n1 / n2, which is the ratio of the average number of moles of ethyleneoxy groups added (n1) to the average number of moles of propyleneoxy groups added (n2), is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, even more preferably 1 or less, even more preferably 0.8 or less, even more preferably 0.6 or less, even more preferably 0.4 or less, even more preferably 0.2 or less, and from the same viewpoint, 0 or more. n1 / n2 may also be 0. Note that the average number of moles of AO groups added is R in general formula (2) above. 5 The number of moles of alkylene oxide with 2 to 4 carbon atoms per mole of OH may be the number of moles of OH that react with and add.

[0046] In general formula (2), Y is the counter salt that dissociates in water to become a cation, and Y + Examples of alkali metal ions include alkali metal ions, alkaline earth metal (half-atom) ions, ammonium ions, or organic ammonium ions. Examples of alkali metal ions include sodium ions and potassium ions. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0047] (d3) More specifically, the component may include one or more anionic surfactants selected from alkylbenzene sulfonates with 10 to 18 carbon atoms in the alkyl group, alkenylbenzene sulfonates with 10 to 18 carbon atoms in the alkenyl group, alkane sulfonates with 10 to 18 carbon atoms in the alkyl group, α-olefin sulfonates with 10 to 18 carbon atoms in the α-olefin portion, α-sulfo fatty acid salts with 10 to 18 carbon atoms in the fatty acid portion, α-sulfo fatty acid lower alkyl ester salts with 10 to 18 carbon atoms in the fatty acid portion and 1 to 5 carbon atoms in the ester portion, and internal olefin sulfonates with 14 to 18 carbon atoms.

[0048] Internal olefin sulfonates, which have 16 to 18 carbon atoms, can be obtained by sulfonating internal olefins, which have 16 to 18 carbon atoms. The internal olefin refers to an olefin in which the double bond is located internally from the 2nd position. Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. Sulfonation of internal olefins quantitatively generates β-sartone, and a portion of the β-sartone is converted to γ-sartone and olefin sulfonic acid. These are further converted to hydroxyalkane sulfonates and olefin sulfonates in the neutralization and hydrolysis steps (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)).

[0049] Here, the hydroxyl group of the resulting hydroxyalkanesulfonate is located inside the alkane chain, and the double bond of the olefin sulfonate is located inside the olefin chain. Furthermore, the resulting product is mainly a mixture of these, and may also contain trace amounts of hydroxyalkanesulfonates having a hydroxyl group at the end of the carbon chain, or α-olefin sulfonates having a double bond at the end of the carbon chain. In this specification, these individual products and mixtures thereof are collectively referred to as internal olefin sulfonates. Hydroxyalkanesulfonates are also referred to as the hydroxy derivative of internal olefin sulfonates (hereinafter also referred to as HAS), and olefin sulfonates are also referred to as the olefin derivative of internal olefin sulfonates (hereinafter also referred to as IOS).

[0050] From the viewpoint of further enhancing the effect of prolonging the antibacterial effect, internal olefin sulfonates with 16 or 18 carbon atoms are preferred. From the viewpoint of further enhancing the effect of prolonging the antibacterial effect, the (d3) component is preferably one or more anionic surfactants selected from α-olefin sulfonates with 10 to 18 carbon atoms in the α-olefin portion, and internal olefin sulfonates with 14 to 18 carbon atoms.

[0051] (d3) Examples of salts of component (d3) include alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0052] (d4) The fatty acid or salt thereof of component (d4) is preferably a fatty acid or salt thereof having 12 to 24 carbon atoms. A fatty acid or salt thereof having 12 to 24 carbon atoms is a compound having an aliphatic hydrocarbon group with 11 to 23 carbon atoms as a hydrophobic group and a carboxylic acid or salt thereof as a hydrophilic group. More specifically, examples include lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, or salts thereof. Component (d4) may be contained as an acid or as a salt. The content of component (d4) shall be expressed as the content converted to the acid form.

[0053] (d3) Examples of salts of component (d3) include alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0054] From the viewpoint of enhancing the effect of prolonging the antibacterial effect, the content of component (d) in the treatment solution is preferably 1 mg / kg or more, more preferably 3 mg / kg or more, even more preferably 10 mg / kg or more, even more preferably 20 mg / kg or more, and even more preferably 30 mg / kg or more. From a similar viewpoint, it is preferably 150 mg / kg or less, more preferably 100 mg / kg or less, and even more preferably 70 mg / kg or less.

[0055] In the processed solution, the mass ratio of component (d) to component (b) (component (d) / component (b)) is: From the viewpoint of further enhancing the effect of prolonging the antibacterial effect, the ratio is preferably 0.1 or higher, more preferably 0.3 or higher, even more preferably 0.5 or higher, even more preferably 0.7 or higher, even more preferably 0.9 or higher, and even more preferably 1.1 or higher. On the other hand, from the same viewpoint, the mass ratio is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0056] Examples of other optional components include components used in treating agents for textile products, such as cationic surfactants other than component (b), nonionic surfactants other than component (c), foaming agents, enzymes, pH adjusters, stabilizers, fluorescent dyes, fragrances, pigments, preservatives, solvents, and other such components. Examples of pH adjusters include alkaline agents and acid agents. Examples of alkaline agents include alkanolamines such as monoethanolamine, and further alkanolamines having 1 to 5 carbon atoms. Examples of acid agents include organic acids such as citric acid. The pH adjuster is preferably used so that the pH of the composition according to the present invention falls within the range described below. Among the pH adjusters, as the alkaline agent, from the viewpoints of detergency and stability, alkanolamines such as monoethanolamine are preferable. Among the pH adjusters, as the acid agent, from the viewpoints of detergency and stability, organic acids such as citric acid are preferable.

[0057] 〔pH of the treatment liquid〕 From the viewpoint of further enhancing the effect of maintaining the antibacterial effect for a longer time, the pH (25 °C) of the treatment liquid is preferably 5 or more, more preferably 6 or more, still more preferably 6.5 or more, even more preferably 7 or more, and from the same viewpoint, preferably 10 or less, more preferably 9.5 or less, still more preferably 9 or less, and even more preferably 8.5 or less. The pH of the composition can be measured according to the following <pH measurement method>.

[0058] <pH measurement method> Connect a pH measuring composite electrode (HORIBA glass ground-joint sleeve type) to a pH meter (HORIBA pH / ion meter F-23) and turn on the power. Use saturated potassium chloride aqueous solution (3.33 mol / L) as the internal solution for the pH electrode. Next, fill 100 mL beakers with pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), and immerse them in a 25°C constant temperature bath for 30 minutes. Immerse the pH measuring electrode in the standard solutions adjusted to constant temperature for 3 minutes and perform calibration in the order of pH 6.86 → pH 9.18 → pH 4.01. Adjust the sample to be measured to 25°C, immerse the electrode of the pH meter in the sample, and measure the pH after 1 minute.

[0059] (Textile products) The textile products to be treated in this invention include clothing and non-clothing products. Specifically, these include denim pants and jackets, batik, undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, and other textile products. The invention is particularly useful in embodiments where textile products with color transfer properties are to be treated. The fibers that make up the textile products include hydrophobic fibers such as acrylic, polyester, and nylon, and hydrophilic fibers such as cotton.

[0060] <Process 2> Step 2 is the process of drying the textile product obtained in Step 1. The drying process is a process that reduces the amount of water present in the textile product. Drying can be done either by natural drying or by heating using a drying machine.

[0061] <Process 3> Step 3 is the step of wearing or using the textile product obtained in Step 2. In this invention, "wearing a textile product" means wearing a textile product, specifically clothing, and "using a textile product" means using a textile product, specifically products other than clothing.

[0062] <Optional steps> The method for sustaining the antibacterial effect of the present invention may include any optional steps. An example of an optional step is step 4 below.

[0063] <Step 4> Step 4: Storage process for storing the textile products obtained in Step 3 after initial wear or use until rewashing.

[0064] In this specification, "re-washing of textile products" means washing the product obtained through steps 1 to 3 of the present invention again. The washing during re-washing may be carried out by the operation of step 1 of the present invention, or by an operation other than step 1 of the present invention. An operation other than step 1 of the present invention may be, for example, a process in which component (b) is removed from the processing solution of step 1 and a processing solution containing any component (d) is used.

[0065] The storage time for the textile product in step 4 is preferably 1 hour or more, more preferably 3 hours or more, and even more preferably 10 hours or more, from the viewpoint of further enhancing the convenience of clothing use. On the other hand, from the viewpoint of prolonging the antibacterial effect, it is preferably 7 days or less, more preferably 5 days or less, and even more preferably 2 days or less.

[0066] In step 4, the textile products are preferably stored in a container. Examples of containers include a washing machine tub, a laundry basket, various boxes such as cardboard boxes, bags, etc.

[0067] The storage temperature of the textile product in step 4 is not particularly limited, but is preferably in the range of 5°C to 35°C.

[0068] The humidity during storage of the textile product in step 4 is not particularly limited, but is preferably in the range of 20%RH to 90%RH. Alternatively, the textile product in step 4 may be partially or completely immersed in water or a treatment solution.

[0069] The cleaning agent composition according to the present invention has a bactericidal effect. For example, the cleaning agent composition according to the present invention can kill bacteria present in water. As for bacteria, for example, it can impart a better bactericidal effect to the target object against Moraxella species described in Japanese Patent Publication No. 2013-18971, Escherichia coli, Staphylococcus aureus, Micrococcus species, Pseudomonas species, or Acinetobacter species. One or more bacteria selected from Moraxella osloensis and Moraxella sp. are more preferred as targets of the present invention.

[0070] [Liquid treatment agent composition for textile products] Another aspect of the present invention is a liquid treatment composition for textile products containing the above-mentioned components (b), (c), and water. Such a composition of the present invention is for sustaining the antibacterial effect on textile products during wear or use and / or after the start of wear or use. Since the liquid treatment composition for textile products of the present invention contains component (c), which can wash away dirt adhering to fibers, it can be used as a cleaning agent composition for textile products.

[0071] <Composition, etc.> The content of component (b) in the liquid treatment agent composition for textile products of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of maintaining the antibacterial effect. On the other hand, from the viewpoint of reducing the amount of waste discharged into the environment, it is preferably 6% by mass or less, more preferably 5% by mass or less, and even more preferably 4% by mass or less.

[0072] The content of component (c) in the composition of the present invention is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of maintaining the antibacterial effect. On the other hand, from the viewpoint of reducing the amount of waste released into the environment, it is preferably 30% by mass or less, more preferably 28% by mass or less, and even more preferably 25% by mass or less.

[0073] If the composition of the present invention contains component (d), the content of component (d) in the composition of the present invention is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of improving processing performance. On the other hand, from the viewpoint of reducing the amount of waste discharged to the environment, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0074] The treatment solution in step 1 may be prepared by mixing the liquid treatment agent composition for textile products with water. The ratio of the liquid treatment agent composition for textile products to water, which is the mixing ratio of the liquid treatment agent composition for textile products (g) / water (liter), is preferably 1g / 30L or more, more preferably 5g / 30L or more, even more preferably 7g / 30L or more, and even more preferably 10g / 30L or more. From a similar viewpoint, it is preferably 50g / 30L, 40g / 30L, or 30g / 30L. [Examples]

[0075] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and do not imply any limitation.

[0076] <Composition ingredients> The following ingredients were used in the examples and comparative examples. Note that the amounts of each ingredient in the table represent the amount of the active ingredient, not the amount of the product. [(b) component] (b-1): Dioctyldimethylammonium chloride (85% by mass aqueous dispersion) (b-2): Dioctylethylmethylammonium ethyl sulfate (85% by mass ethanol solution) (b-3): Dioctyldimethylammonium methyl sulfate (85% by mass ethanol solution)

[0077] [(b') component] (b'-1): Didecylethylmethylammonium ethyl sulfate (85% by mass ethanol solution)

[0078] [(c) component] (c-1): In the above general formula (c1-1), R 5 is a mixed alkyl group (lauryl group / myristyl group = 7 / 3 (mass ratio)), m is 0, (AO) n However, to an alcohol with a mixed alkyl group as the hydrocarbon group, 4 moles of propyleneoxy were added, followed by 17 moles of ethyleneoxy groups (n=21), R 6 It is a compound of H. (c-2): In the above general formula (c1-1), R 5 (A) is a lauryl group, m is 0, (AO) is an ethylene oxy group, n is 10, R 6 It is a compound of H. (c-3): In the above general formula (c1-1), R 5 (A) is a lauryl group, m is 0, (AO) is an ethyleneoxy group, n is 6.5, R 6 It is a compound of H.

[0079] [(d) component] (d-1): In the above general formula (2), R 5 is a dodecyl group, n is 0, Y + A compound in which sodium ions are present. (d-2): In the above general formula (2), R 5 (A) is a dodecyl group, and (AO)n is a compound obtained by adding a propylene oxide group to dodecyl alcohol at a ratio of 0.6 moles per mole, then esterifying with sulfuric acid, and neutralizing with sodium hydroxide (n=0.6). + A compound in which sodium ions are present. (d-3): In the above general formula (2), R 5 (A) is a dodecyl group, and (AO)n is a compound obtained by adding a propylene oxide group to dodecyl alcohol at a ratio of 0.6 moles per mole, then esterifying with sulfuric acid, and neutralizing with sodium hydroxide (n=0.6). + A compound in which sodium ions are present. (d-4): Potassium C16 internal olefin sulfonate obtained by the following manufacturing method) • Production of C16 internal olefin a1 Internal olefin a1 with 16 carbon atoms, which is the raw material for component (d-4) above, was produced according to the method described below. The internal olefin with 16 carbon atoms was produced in accordance with production example C of Japanese Patent Application Publication No. 2014-76988. The double bond distribution of the internal olefin is as follows. In internal olefin a1, the mass percentage of internal olefins with double bonds at the following positions was 1st / 2nd / 3rd / 4th / 5th / 6th / 7th / 8th = 2.3% / 23.6% / 18.9% / 17.5% / 13.7% / 11.2% / 6.4% / 6.4% (total 100 mass%).

[0080] The double bond distribution of the internal olefin a1 was measured by gas chromatography (hereinafter abbreviated as GC). Specifically, the internal olefin was reacted with dimethyl disulfide to form a dithiolated derivative, and then each component was separated by GC. As a result, the proportion of the double bond distribution of the internal olefin was determined from the peak area of ​​each component, and this proportion was taken as the mass proportion. Note that in olefins with 16 carbon atoms, internal olefins with a double bond at position 7 and internal olefins with a double bond at position 8 are structurally indistinguishable, but they become distinguishable when sulfonated. For convenience, the amount of internal olefin with a double bond at position 7 was divided by 2 and shown in each column. The apparatus and analytical conditions used for the measurement are as follows. GC system "HP6890" (manufactured by Hewlett Packard), column "Ultra-Alloy-1HT capillary column" (30m x 250μm x 0.15μm, manufactured by Frontier Labs Co., Ltd.), detector (flame ion detector (FID)), injection temperature 300℃, detector temperature 350℃, He flow rate 4.6mL / min

[0081] Manufacturing of (d-4) The aforementioned internal olefin a1 was subjected to a sulfonation reaction using a thin-film sulfonation reactor with an external jacket, by passing sulfur trioxide gas and cooling water at 20°C through the reactor's external jacket. The molar ratio of SO3 to internal olefin during the sulfonation reaction was set to 1.09. The obtained sulfonate was added to an alkaline aqueous solution prepared with 1.5 molar times the theoretical acid value of potassium hydroxide, and neutralized at 30°C for 1 hour with stirring. The neutralized product was hydrolyzed by heating in an autoclave at 160°C for 1 hour to obtain a crude potassium sulfonate product of the C16 internal olefin. 300 g of the crude product was transferred to a separatory funnel, 300 mL of ethanol was added, and then 300 mL of petroleum ether was added in each step to extract and remove oil-soluble impurities. At this time, inorganic compounds (mainly potassium sulfate) precipitated at the oil-water interface due to the addition of ethanol were also separated and removed from the aqueous phase by oil-water separation. This extraction and removal operation was performed three times. Potassium olefin sulfonate was obtained by evaporating the aqueous phase to dryness. (d-5): Potassium C18 internal olefin sulfonate obtained by the following manufacturing method • Production of C18 internal olefin a2 Internal olefin a2 with 18 carbon atoms, which is the raw material for component (d-5) above, was produced according to the method described below. The internal olefin with 18 carbon atoms was produced in accordance with production example D of Japanese Patent Application Publication No. 2014-76988. The double bond distribution of the internal olefin is as follows. In internal olefin a2, the mass percentage of internal olefins with double bonds at the following positions was 1st / 2nd / 3rd / 4th / 5th / 6th / 7th / 8th / 9th = 0.5% / 25.0% / 22.8% / 19.1% / 14.0% / 7.4% / 5.4% / 2.5% / 2.5% (total 100 mass%).

[0082] The double bond distribution of the internal olefin a2 was measured by gas chromatography (hereinafter abbreviated as GC). Specifically, the internal olefin was reacted with dimethyl disulfide to form a dithiolated derivative, and then each component was separated by GC. As a result, the proportion of the double bond distribution of the internal olefin was determined from the peak area of ​​each component, and this proportion was taken as the mass proportion. Note that in olefins with 18 carbon atoms, internal olefins with a double bond at position 8 and internal olefins with a double bond at position 9 are structurally indistinguishable, but they become distinguishable after sulfonation. For convenience, the amount of internal olefin with a double bond at position 8 was divided by 2 and shown in each column. The apparatus and analytical conditions used for the measurement are as follows. GC system "HP6890" (manufactured by Hewlett Packard), column "Ultra-Alloy-1HT capillary column" (30m x 250μm x 0.15μm, manufactured by Frontier Labs Co., Ltd.), detector (flame ion detector (FID)), injection temperature 300℃, detector temperature 350℃, He flow rate 4.6mL / min

[0083] • Manufacturing of (d-5) The aforementioned internal olefin a2 was subjected to a sulfonation reaction using a thin-film sulfonation reactor with an external jacket, by passing sulfur trioxide gas and cooling water at 20°C through the reactor's external jacket. The molar ratio of SO3 to internal olefin during the sulfonation reaction was set to 1.09. The obtained sulfonate was added to an alkaline aqueous solution prepared with 1.5 molar times the theoretical acid value of potassium hydroxide, and neutralized at 30°C for 1 hour with stirring. The neutralized product was hydrolyzed by heating in an autoclave at 160°C for 1 hour to obtain a crude potassium sulfonate product of the C18 internal olefin. 300 g of the crude product was transferred to a separatory funnel, 300 mL of ethanol was added, and then 300 mL of petroleum ether was added in each step to extract and remove oil-soluble impurities. At this time, inorganic compounds (mainly potassium sulfate) precipitated at the oil-water interface due to the addition of ethanol were also separated and removed from the aqueous phase by oil-water separation. This extraction and removal operation was performed three times. Potassium olefin sulfonate was obtained by evaporating the aqueous phase to dryness.

[0084] (d-6): Sodium dodecylbenzenesulfonate (d-7): Lauric acid (d-8): Myristic acid (d-9): Palmitic acid

[0085] Examples 1-25 and Comparative Examples 1-6 <Preparation of liquid treatment agent compositions for textile products> The above-mentioned components were mixed to prepare the textile treatment agents shown in Tables 1 to 4 below.

[0086] [Method for evaluating the duration of antibacterial effects in textile products] Test Example 1 (Evaluation of fatty acid contamination) <Processing> For evaluation purposes, we used plain weave cotton fabric (Cotton 2003, purchased from Tanigashira Shoten). A 6 x 6 cm cotton plain weave fabric was treated with the various liquid treatment agent compositions listed in Tables 1 to 3 as described below to prepare a test fabric for antibacterial effect. Treatment solutions were prepared by diluting various treatment agent compositions with tap water from Wakayama City, Wakayama Prefecture, Japan, to a concentration of 1 g / L. 30g of the cotton plain weave fabric and 600mL of the processing solution were placed in a Turgotometer (manufactured by Ueshima Seisakusho), processed at 85rpm, 20℃ for 10 minutes, and then dewatered for 1 minute using a small dehydrator, Dry-Cyclone BDS-3.0 SBP (manufactured by Beecam Co., Ltd.).

[0087] <Drying> The dewatered test cloth was placed in 600 mL of tap water and rinsed with the turgotometer at 85 rpm, 20°C, and for 3 minutes. It was then dewatered for 1 minute in the small spin dryer and allowed to air dry.

[0088] <To wear or use> As a model of a textile product after human wear or use, a test cloth was prepared by attaching fatty acids and bacteria to the aforementioned naturally dried test cloth. A methanol solution of 14-methylhexadecanoic acid (manufactured by Larodan AB) was added dropwise to 1 g of test cloth so that the amount of 14-methylhexadecanoic acid was approximately 400 μg, and the cloth was allowed to air dry to obtain the treated cloth.

[0089] Moraxella sp. bacteria isolated from used human textile products were streaked onto plates of nutrient agar (Becton Dickinson) and cultured at 37°C for approximately 24 hours. The cultured samples were scraped off with a platinum loop and placed in 10 mL of nutrient agar (Becton Dickinson), and pre-cultured at 37°C and 110 rpm for approximately 20 hours. The bacterial concentration of the pre-cultured culture solution was estimated by absorbance, and the bacterial concentration was estimated to be approximately 1 × 10⁻⁶. 8 The solution was adjusted to CFU / mL, and 0.2 mL of it was added to 10 mL of nutrient medium and incubated for a further 3 hours at 37°C and 110 rpm. The bacterial concentration in the culture medium was estimated by absorbance, and the bacterial count was 1.0 × 10⁶ using a 10-fold diluted nutrient medium. 5 The bacterial solution was adjusted to CFU / mL. 0.2 mL of this bacterial solution was inoculated onto 0.4 g of the treated cloth.

[0090] <Storage> The storage process involved allowing the treated cloth to be incubated at 37°C for approximately 20 hours after inoculation.

[0091] <Bacterial count measurement> After the storage process, 20 mL of LP diluent (manufactured by Shioya MS Co., Ltd.) at 25°C was added to each treated cloth and mixed for 10 seconds. Then, ultrasound was applied for 10 minutes to extract the bacteria. The extract was serially diluted with LP diluent, poured onto SCD agar plate (manufactured by Shioya MS Co., Ltd.), and incubated overnight at 37°C.

[0092] On the other hand, a 6 x 6 cm cotton plain weave cloth was treated and dried without applying fatty acids and bacteria in the same manner as described above. The cloth was then stored in the same manner, and bacterial extraction was performed in the same manner. The cloth was then incubated overnight at 37°C.

[0093] The number of colonies obtained from each fabric was measured, and the antibacterial activity value (Δlog10) was calculated by subtracting the common logarithm of the number of viable bacteria in each example or comparative example from the common logarithm of the number of viable bacteria in the untreated and undried fabric. In this evaluation, a higher antibacterial activity value indicates a superior antibacterial effect. The results are shown in Tables 1 to 3.

[0094] [Table 1]

[0095] [Table 2]

[0096] [Table 3]

[0097] Tables 1 to 3 show that the method of the present invention maintained high antibacterial properties even after 20 hours of storage for fabrics stained with fatty acids.

[0098] Test Example 2 (Evaluation of Protein Contamination) The evaluation was carried out in the same manner as in Test Example 1 above, except that horse serum (Horse Serum, heat inactivated, New Zealand origin, manufactured by Thermo Fisher Scientific K.K.) was used instead of 14-methylhexadecanoic acid. The results are shown in Table 4.

[0099] [Table 4]

[0100] Table 4 shows that the method of the present invention maintained high antibacterial properties even after 20 hours of storage, even on cloths with protein stains.

Claims

1. A method for maintaining the antibacterial effect of a textile product after it has been worn or used, including steps 1 to 3 below. Step 1: A process of treating textile products by bringing them into contact with a treatment solution containing the following components: (b) at a concentration of 2 mg / kg to 70 mg / kg, (c) at a concentration of 50 mg / kg to 1000 mg / kg, and water. Step 2: A process to dry the textile product obtained in Step 1. Step 3: The process of wearing or using the textile product obtained in Step 2. (b) Component: Compound represented by the following general formula (1) 【Chemistry 1】 [In the formula, R １ and R ２ Each of these is an alkyl group having 8 carbon atoms, and R ３ and R ４ Each of these is independently selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X － It is a monovalent anion. (c) Component: Compound represented by the following general formula (c1-1) R ５ -(A) ｍ -O-(AO) ｎ -R ６ (c--1) [In the formula, R ５ R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, ６ is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is a number, either 0 or 1. The AO group is an alkylene oxy group having 2 to 4 carbon atoms. n is the average number of moles added, and is a number between 1 and 30.

2. A method for sustaining the antibacterial effect according to claim 1, further comprising step 4 below. Step 4: Storage process for storing the textile products obtained in Step 3 after the start of wear or use until they are ready for rewashing.

3. The method for sustaining the antibacterial effect according to claim 2, wherein the storage time of the textile product in step 4 is 10 hours or more.

4. A method for maintaining the antibacterial effect according to claim 2, wherein the textile product in step 4 is stored in a container.

5. A liquid treatment agent composition for textile products, comprising the following components (b), (c), and water, for sustaining the antibacterial effect on textile products after the start of wear or use. (b) Component: Compound represented by the following general formula (1) 【Chemistry 2】 [In the formula, R １ and R ２ Each of these is an alkyl group having 8 carbon atoms, and R ３ and R ４ Each of these is independently selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X － It is a monovalent anion. (c) Component: Compound represented by the following general formula (c1-1) R ５ -(A) ｍ -O-(AO) ｎ -R ６ (c--1) [In the formula, R ５ R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, ６ is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is a number, either 0 or 1. The AO group is an alkylene oxy group having 2 to 4 carbon atoms. n is the average number of moles added, and is a number between 1 and 30.

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