Liquid detergent composition for fiber products

Abstract

The present invention relates to a liquid detergent composition for fiber products, which contains (a) a surfactant, (b) an alcohol having 10 to 16 carbon atoms, and (c) an antibacterial compound having an aromatic ring (excluding quaternary ammonium salts).

Description

Technical Field

[0001] The present invention relates to a liquid detergent composition for fiber products and a method for cleaning fiber products. Background Art

[0002] In powder detergent compositions for fiber products such as clothing, anionic surfactants or nonionic surfactants are used as cleaning components. As anionic surfactants, anionic surfactants having a sulfonic acid group or its salt represented by alkylbenzene sulfonates, and anionic surfactants having a sulfate group represented by alkyl sulfate salts and polyoxyalkylene alkyl sulfate salts are known. From the viewpoint of the cleaning power against various stains attached to clothing, suppliers of clothing detergents are using a combination of multiple anionic surfactants.

[0003] On the other hand, with the improvement of consumers' hygiene awareness, the attention to the odor or bacteria of clothing has gradually increased. It is known that skin resident bacteria or various bacteria existing in the environment adhere to and multiply on clothing. As a method for inhibiting the proliferation of bacteria attached to clothing, a method of using a quaternary ammonium surfactant is known. In addition, aromatic chlorine-based compounds such as diclosan are also known as compounds having antibacterial or bactericidal properties.

[0004] In Japanese Patent Laid-Open No. 2009-263812, a method for suppressing the odor of undried clothes is disclosed, in which an aqueous composition is brought into contact with a fiber product having a water content (the ratio of the contained water to the total dry mass of the fiber product) of 30 to 120% by mass after the dehydration in the washing step. The aqueous composition contains (a) at least one antibacterial agent selected from cationic organic antibacterial agents, triclosan, and diclosan, (b) at least one surfactant selected from nonionic surfactants and amine oxide type surfactants, and water, and the content of (a) is 0.05 to 10% by mass, and the content of (b) is 0.01 to 10% by mass.

[0005] In Japanese Patent Laid-Open No. 2004-204085, a detergent composition is disclosed, which is characterized by containing surface-coated particles obtained by coating particles of a granulated product containing a clay mineral with a surface coating agent, and the clay mineral carries at least one selected from a substance having an antibacterial effect, a substance having an antioxidant effect, and a substance having a deodorizing effect.

[0006] In Japanese Patent Laid-Open No. 2011-190368, there is disclosed a liquid detergent composition for fabrics, which contains: a copolymer (A) obtained from four ethylene monomers, namely, an ethylene monomer m1 having a tertiary amine structure in the side chain, an ethylene monomer m2 having a lactam structure, an ethylene monomer m3 having a linear or branched carbon chain of 1 to 30, or an alicyclic hydrocarbon or aromatic hydrocarbon group in the side chain, and an ethylene monomer m4 having a polyoxyalkylene group with 2 to 4 carbon atoms in the side chain, and the copolymer is obtained in such a manner that the constituent amounts of the above four monomers are respectively in the ranges of (m1) 10 to 70 mol%, (m2) 10 to 70 mol%, (m3) 1 to 30 mol%, and (m4) 1 to 60 mol% and the total amount is 100 mol%; a functional ingredient (B) having at least one effect among bactericidal, antibacterial, deodorizing, and antioxidant effects; and a surfactant (C). Summary of the Invention

[0007] The present invention provides a liquid detergent composition for fiber products and a method for cleaning fiber products. The liquid detergent composition for fiber products can impart excellent antibacterial properties to fiber products even when used in washing steps such as cleaning and rinsing, has excellent detergency, and is easy to foam.

[0008] The present invention relates to a liquid detergent composition for fiber products, which contains (a) a surfactant [hereinafter referred to as component (a)], (b) an alcohol having 10 to 16 carbon atoms [hereinafter referred to as component (b)], and (c) an antibacterial compound having an aromatic ring [hereinafter referred to as component (c)].

[0009] In addition, the present invention relates to a method for cleaning fiber products, which uses a cleaning liquid obtained by mixing the liquid detergent composition for fiber products of the present invention with water to clean the fiber products, and then rinses the fiber products with water.

[0010] According to the present invention, there is provided a liquid detergent composition for fiber products and a method for cleaning fiber products. The liquid detergent composition for fiber products can impart excellent antibacterial properties to fiber products even when used in washing steps such as cleaning and rinsing, has excellent detergency, and is easy to foam. Detailed Description of the Invention

[0011] [Liquid Detergent Composition for Fiber Products]

[0012] The liquid detergent composition for fiber products of the present invention contains the surfactant as component (a).

[0013] As the component (a), one or more surfactants selected from (a1) anionic surfactants [hereinafter referred to as the component (a1)] and (a2) nonionic surfactants [hereinafter referred to as the component (a2)] can be cited.

[0014] As the component (a1), one or more anionic surfactants selected from internal olefin sulfonates having 10 to 18 carbon atoms, sulfate esters having an alkyl or alkenyl group having 10 to 24 carbon atoms, polyoxyalkylene alkyl or alkenyl ether sulfates having an alkyl or alkenyl group having 10 to 24 carbon atoms, and sulfonates having an alkyl or alkenyl group having 10 to 24 carbon atoms (excluding internal olefin sulfonates having 10 to 18 carbon atoms) can be cited.

[0015] The internal olefin sulfonate having 10 to 18 carbon atoms can be obtained by sulfonating an internal olefin having 10 to 18 carbon atoms. The above internal olefin means an olefin in which a double bond exists more internally than the 2-position. The internal olefin can be obtained, for example, by dehydrating 1-alcohol and isomerizing the obtained 1-olefin. When the internal olefin is sulfonated, β-sultone is quantitatively generated, and a part of the β-sultone becomes γ-sultone and olefin sulfonic acid, and further these are converted into hydroxyalkanesulfonate and olefin sulfonate in the neutralization and hydrolysis steps (for example, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the obtained hydroxyalkanesulfonate is located inside the alkane chain, and the double bond of the olefin sulfonate is located inside the olefin chain. In addition, the obtained product is mainly a mixture of these, and in addition, a trace amount of hydroxyalkanesulfonate having a hydroxy group at the end of the carbon chain or α-olefin sulfonate having a double bond at the end of the carbon chain is contained in a part thereof. In the present specification, these respective products and their mixtures are collectively referred to as internal olefin sulfonates. In addition, the hydroxyalkanesulfonate is referred to as the hydroxy form of the internal olefin sulfonate (hereinafter, also referred to as HAS), and the olefin sulfonate is referred to as the olefin form of the internal olefin sulfonate (hereinafter, also referred to as IOS).

[0016] The internal olefin sulfonate has 10 or more carbon atoms, preferably 14 or more carbon atoms, and 18 or less carbon atoms. From the viewpoints of antibacterial property, detergency, and foaming property, an internal olefin sulfonate having 16 carbon atoms is preferred. The liquid detergent composition for fiber products of the present invention can contain an internal olefin sulfonate having 16 carbon atoms as the component (a1). In addition, the number of carbon atoms of the internal olefin sulfonate does not include the number of carbon atoms of the salt part. That is, the number of carbon atoms of the olefin part is the number of carbon atoms of the internal olefin sulfonate. That is, the number of carbon atoms of the internal olefin sulfonate represents the number of carbon atoms of the internal olefin covalently bonded to the sulfonate.

[0017] Examples of the salt of the internal olefin sulfonate include alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, or organic ammonium salts. Examples of the alkali metal salts include sodium salts and potassium salts. Examples of the organic ammonium salts include alkanolammonium salts having 1 to 6 carbon atoms.

[0018] The internal olefin sulfonate also contains a trace amount of sulfonate at the 1-position of the carbon chain, i.e., so-called alpha olefin sulfonate (hereinafter, also referred to as α-olefin sulfonate). Regarding the content of the α-olefin sulfonate in the internal olefin sulfonate, from the viewpoints of antibacterial property, detergency, and foaming property, the upper limit of the content is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and preferably 0.01% by mass or more.

[0019] For the internal olefin sulfonate, as the main component, it can be obtained by sulfonating an olefin having 10 to 18 carbon atoms with a double bond at the 2-position or higher. When this internal olefin is sulfonated, β-sultone is quantitatively generated, and a part of the β-sultone becomes γ-sultone and olefin sulfonic acid. Further, these are converted into hydroxyalkanesulfonate and olefin sulfonate in the neutralization and hydrolysis steps (for example, J.Am.Oil Chem.Soc. 69, 39 (1992)). Here, the hydroxy group of the obtained hydroxyalkanesulfonate is located inside the alkane chain, and the double bond of the olefin sulfonate is located inside the olefin chain. In addition, the obtained product is mainly a mixture of these, and there is also a case where a trace amount of hydroxyalkanesulfonate having a hydroxy group at the end of the carbon chain or olefin sulfonate having a double bond at the end of the carbon chain is contained in a part thereof.

[0020] In this specification, each of these products and their mixtures are collectively referred to as internal olefin sulfonate. In addition, as described above, hydroxyalkanesulfonate is referred to as the hydroxy form (HAS) of internal olefin sulfonate, and olefin sulfonate is referred to as the olefin form (IOS) of internal olefin sulfonate.

[0021] In addition, the mass ratio of the compounds in the internal olefin sulfonate can be measured by HPLC-MS (High Performance Liquid Chromatography-Mass Spectrometer). Specifically, for example, according to the method of the following examples, the mass ratio can be obtained from the HPLC-MS peak area of the internal olefin sulfonate.

[0022] The above-mentioned internal olefin sulfonates may include a hydroxyl form and an olefin form. The mass ratio (olefin form / hydroxyl form) of the content of the olefin form of the internal olefin sulfonate to the content of the hydroxyl form of the internal olefin sulfonate in the internal olefin sulfonate may be 0 / 100 or more, further 5 / 95 or more, and 50 / 50 or less, further 40 / 60 or less, still further 30 / 70 or less, and even further 25 / 75 or less.

[0023] From the viewpoints of antibacterial property, detergency, and foaming property, the number of carbon atoms of the above-mentioned alkyl or alkenyl group of the sulfate ester salt having an alkyl or alkenyl group with 10 or more and 24 or less carbon atoms is preferably 12 or more, and preferably 20 or less, more preferably 18 or less. The above-mentioned sulfate ester salt preferably has an alkyl group.

[0024] From the viewpoints of antibacterial property, detergency, and foaming property, the number of carbon atoms of the above-mentioned alkyl or alkenyl group of the polyoxyalkylene alkyl or alkenyl ether sulfate ester salt having an alkyl or alkenyl group with 10 or more and 24 or less carbon atoms is preferably 12 or more, and preferably 18 or less, more preferably 16 or less. The above-mentioned ether sulfate ester salt is preferably an ether sulfate ester salt having an alkyl group. As the oxyalkylene group of the above-mentioned ether sulfate ester salt, one or more groups selected from an ethyleneoxy group and a propyleneoxy group can be cited. The oxyalkylene group is preferably an oxyalkylene group containing a propyleneoxy group. More preferably, it is a propyleneoxy group. The average addition mole number of the oxyalkylene group of the above-mentioned ether sulfate ester salt is preferably 1 or more and 5 or less.

[0025] As the sulfonate having an alkyl or alkenyl group with 10 or more and 24 or less carbon atoms (wherein, excluding the internal olefin sulfonate having 10 or more and 18 or less carbon atoms), one or more anionic surfactants selected from an alkylbenzene sulfonate having an alkyl group with 10 or more and 24 or less carbon atoms, an alkenylbenzene sulfonate having an alkenyl group with 10 or more and 24 or less carbon atoms, an alkane sulfonate having an alkyl group with 10 or more and 24 or less carbon atoms, an α-olefin sulfonate having 10 or more and 24 or less carbon atoms in the α-olefin moiety, an α-sulfo fatty acid salt having 10 or more and 24 or less carbon atoms in the fatty acid moiety, and an α-sulfo fatty acid lower alkyl ester salt having 10 or more and 24 or less carbon atoms in the fatty acid moiety and 1 or more and 5 or less carbon atoms in the ester moiety can be cited.

[0026] As the salt of the component (a1), an alkali metal salt, an alkaline earth metal (1 / 2 atom) salt, an ammonium salt, or an organic ammonium salt can be cited. As the alkali metal salt, a sodium salt and a potassium salt can be cited. As the organic ammonium salt, an alkanolammonium salt having 1 or more and 6 or less carbon atoms can be cited. From the viewpoint of easy availability, the salt of the component (a1) is preferably an alkali metal salt or an alkanolammonium salt having 1 or more and 6 or less carbon atoms.

[0027] From the viewpoints of antibacterial property, detergency, and foaming property, the liquid detergent composition for fiber products of the present invention preferably contains an internal olefin sulfonate having 10 or more and 18 or less carbon atoms as the component (a), and further as the component (a1).

[0028] Examples of the component (a2) include alcohol alkoxylates, ester alkoxylates, polyol fatty acid esters that may contain alkylene oxides, alkyl glycosides, polyethylene glycols, polyoxyethylene oxypropylene glycols, polyoxypropylene oxyethylene oxypropylene glycols, etc. Examples of the alcohol alkoxylates include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, etc. Examples of the polyol fatty acid esters that may contain alkylene oxides include glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc.

[0029] Among them, from the viewpoints of antibacterial property, detergency, and foaming property, the component (a2) is preferably a nonionic surfactant selected from alcohol alkoxylates and ester alkoxylates. Examples of the alcohol alkoxylates and ester alkoxylates include nonionic surfactants represented by the following general formula (1).

[0030] R 1 (CO) m O-(AO) n -R 2 (1)

[0031] [In the formula, R 1 is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, R 2 is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, AO is one or more alkylene oxides selected from alkylene oxides having 2 carbon atoms and alkylene oxides having 3 carbon atoms, and AO contains at least an alkylene oxide having 2 carbon atoms. When AO contains an alkylene oxide having 2 carbon atoms and an alkylene oxide having 3 carbon atoms, the alkylene oxide having 2 carbon atoms and the alkylene oxide having 3 carbon atoms may be in a block type bond or a random type bond; n is the average addition mole number and is a number of 1 or more and 50 or less.]

[0032] In formula (1), from the viewpoints of antibacterial property, detergency, and foaming property, the number of carbon atoms of R 1 is preferably 12 or more and preferably 18 or less.

[0033] In formula (1), the aliphatic hydrocarbon group of R 1 may include an alkyl group and an alkenyl group.

[0034] In formula (1), from the viewpoints of antibacterial property, detergency, and foaming property, m is preferably 0.

[0035] In formula (1), AO is one or more alkyleneoxy groups selected from alkyleneoxy groups having 2 carbon atoms and alkyleneoxy groups having 3 carbon atoms, and AO contains at least an alkyleneoxy group having 2 carbon atoms. In AO, from the viewpoints of antibacterial property, detergency, and foaming property, the ratio of the alkyleneoxy group having 2 carbon atoms, i.e., ethyleneoxy group, is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, and is 100 mol% or less, and may be 100 mol%.

[0036] In formula (1), from the viewpoints of antibacterial property, detergency, and foaming property, n is preferably 4 or more, more preferably 6 or more, and is preferably 40 or less, more preferably 30 or less.

[0037] The liquid detergent composition for fiber products of the present invention preferably contains the nonionic surfactant represented by the above general formula (1) as the component (a), and further as the component (a2).

[0038] From the viewpoints of antibacterial property, detergency, and foaming property, the liquid detergent composition for fiber products of the present invention preferably contains the surfactant represented by the following general formula (2) as the component (a), and further as the component (a2).

[0039] R 11 -O-(EO) n1 -(AO) n2 -(EO) n3 -H (2)

[0040] [wherein, R 11 is an alkyl or alkenyl group having 10 or more and 18 or less carbon atoms, EO is an ethyleneoxy group, AO is an alkyleneoxy group having 3 or 4 carbon atoms, n1, n2, and n3 are the average addition mole numbers of EO and AO, n1 is 0 or more and 20 or less, n2 is 1 or more and 10 or less, and n3 is 1 or more and 20 or less.]

[0041] In formula (2), from the viewpoints of antibacterial property, detergency, and foaming property, the carbon atom number of R 11 is preferably 10 or more, and is preferably 15 or less.

[0042] n1, n2, and n3 are the average molar addition numbers of EO and AO. From the viewpoints of antibacterial property, detergency, and foaming property, n1 is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and preferably 15 or less, more preferably 12 or less, further preferably 10 or less. n2 is preferably 1.5 or more, more preferably 2 or more, and preferably 10 or less, more preferably 8 or less. n3 is preferably 2 or more, more preferably 3 or more, and preferably 17 or less, more preferably 15 or less, further preferably 12 or less, and further more preferably 10 or less.

[0043] From the viewpoints of antibacterial property, detergency, and foaming property, the liquid detergent composition for fiber products of the present invention preferably contains an anionic surfactant as the (a1) component and a nonionic surfactant as the (a2) component as the (a) component. In this case, from the viewpoints of antibacterial property and foaming property, the mass ratio of the content of the (a1) component to the total content of the (a1) component and the (a2) component, i.e., (a1) / [(a1)+(a2)], is preferably 0.05 or more, more preferably 0.2 or more, further preferably 0.3 or more, and further more preferably 0.4 or more, and from the viewpoints of detergency and foaming property, it is preferably 0.95 or less, more preferably 0.8 or less, further preferably 0.6 or less.

[0044] From the viewpoints of antibacterial property, detergency, and foaming property, the liquid detergent composition for fiber products of the present invention contains preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less of the (a) component.

[0045] From the viewpoints of antibacterial property, detergency, and foaming property, the liquid detergent composition for fiber products of the present invention contains preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 13% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 27% by mass or less of the (a1) component.

[0046] From the viewpoints of antibacterial property, detergency, and foaming property, the liquid detergent composition for fiber products of the present invention contains preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less of the (a2) component.

[0047] The liquid detergent composition for fiber products of the present invention contains an alcohol having 10 to 16 carbon atoms as the (b) component.

[0048] From the viewpoints of antibacterial property, detergency, and foaming property, the (b) component is preferably a primary alcohol.

[0049] From the viewpoints of antibacterial property, detergency, and foaming property, the component (b) is preferably an aliphatic alcohol.

[0050] From the viewpoints of antibacterial property, detergency, and foaming property, the component (b) is preferably a linear alcohol.

[0051] From the viewpoints of antibacterial property, detergency, and foaming property, the component (b) is preferably a monohydric alcohol.

[0052] From the viewpoints of antibacterial property, detergency, and foaming property, the component (b) is preferably a saturated alcohol.

[0053] From the viewpoints of antibacterial property, detergency, and foaming property, the number of carbon atoms of the component (b) is preferably 12 or more and 14 or less.

[0054] Examples of the component (b) include decanol, dodecanol, tetradecanol, hexadecanol, etc. From the viewpoints of antibacterial property and foaming property, the component (b) is preferably an alcohol selected from 1-decanol, 1-dodecanol, 1-tetradecanol, and 1-hexadecanol, more preferably an alcohol selected from 1-dodecanol and 1-tetradecanol, and still more preferably 1-dodecanol.

[0055] From the viewpoints of antibacterial property, detergency, and foaming property, the liquid detergent composition for fiber products of the present invention contains the component (b) in an amount preferably of 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 8% by mass or less, more preferably 6% by mass or less, still more preferably 4% by mass or less, and still more preferably 2% by mass or less.

[0056] From the viewpoints of antibacterial property and foaming property, the mass ratio of the content of the component (a) to the content of the component (b) in the liquid detergent composition for fiber products of the present invention, i.e., (b) / (a), is preferably 0.010 or more, more preferably 0.020 or more, and from the viewpoints of detergency and foaming property, is preferably 0.1 or less, more preferably 0.075 or less, still more preferably 0.06 or less, and still more preferably 0.05 or less.

[0057] The liquid detergent composition for fiber products of the present invention contains a component (c), which is an antibacterial compound having an aromatic ring (excluding quaternary ammonium salts).

[0058] The component (c) may be, for example, a nonionic antibacterial compound having an aromatic ring.

[0059] Regarding component (c), the antibacterial compound refers to the following compounds: when 1% by mass of the compound is uniformly adhered to cotton lawn #2003, and the antibacterial property test is carried out using this cloth by the method of JIS (Japanese Industrial Standard) L1902 "Test method for antibacterial property of textile products", and an inhibition zone of growth can be found.

[0060] Examples of component (c) include antibacterial compounds having a diphenyl ether skeleton, antibacterial compounds selected from phenolic derivatives, antibacterial compounds selected from benzoic acid derivatives, etc. From the viewpoints of antibacterial property and easy fixation to textile products after cleaning (antibacterial maintenance), antibacterial compounds having a diphenyl ether skeleton are preferred, for example, antibacterial compounds containing a halogen atom and having a diphenyl ether skeleton. As specific compounds, triclosan, triclocarban, benzoic acid, p-hydroxybenzoate, etc. can be mentioned. From the viewpoints of antibacterial property and easy fixation to textile products after cleaning, triclosan and triclocarban are preferred. Further, from the viewpoint of ease of product design of liquid detergents for textile products, triclosan is more preferred.

[0061] From the viewpoints of antibacterial property and economy, the liquid detergent composition for textile products of the present invention contains component (c) preferably in an amount of 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 0.1% by mass or less, more preferably 0.07% by mass or less.

[0062] From the viewpoints of antibacterial property, detergency, foaming property, and deodorizing effect of textile products, the mass ratio of the content of component (b) to the content of component (c) in the liquid detergent composition for textile products of the present invention, i.e., (b) / (c), is preferably 5 or more, more preferably 15 or more, further preferably 20 or more, and preferably 100 or less, more preferably 50 or less, further preferably 30 or less.

[0063] The liquid detergent composition for textile products of the present invention may contain, within the range not impairing the effects of the present invention, an alkali agent, a chelating agent, a recontamination preventing agent, a dispersant, a bleaching agent, a softening agent, an enzyme, a fluorescent dye, an antioxidant, a pigment, an antibacterial preservative, an antifoaming agent, etc. as components other than component (a), component (b), and component (c).

[0064] The liquid detergent composition for textile products of the present invention preferably contains water. Water is used in an amount such that the composition of the composition becomes 100% by mass. The detergent composition of the present invention may contain, for example, 20% by mass or more, further 30% by mass or more, and 99% by mass or less, further 98% by mass or less, still further 90% by mass or less, still further 80% by mass or less of water.

[0065] From the viewpoints of antibacterial property, detergency, and foaming property, the pH value of the liquid detergent composition for fiber products of the present invention at 25°C is preferably 3 or more, more preferably 4 or more, and preferably 10 or less, more preferably 9 or less. The pH value of the composition can be measured by the measurement method described in the examples below.

[0066] From the viewpoints of antibacterial property, detergency, and foaming property, the viscosity of the liquid detergent composition for fiber products of the present invention at 20°C is preferably 10 mPa·s or more, more preferably 50 mPa·s or more, and preferably 250 mPa·s or less, more preferably 200 mPa·s or less. The viscosity of the liquid detergent composition for fiber products of the present invention can be measured, for example, using a known rotary viscometer such as a single cylinder type viscometer after setting the sample at 20°C.

[0067] The fiber constituting the fiber product to be cleaned with the liquid detergent composition of the present invention can be either a hydrophobic fiber or a hydrophilic fiber. Examples of hydrophobic fibers include protein fibers (such as milk protein casein fiber, protein copolymer fiber (Promix), etc.), polyamide fibers (such as nylon), polyester fibers (such as polyester), polyacrylonitrile fibers (such as acrylic fibers), polyvinyl alcohol fibers (such as vinylon), polyvinyl chloride fibers (such as polyvinyl chloride), polyvinylidene chloride fibers (such as vinylidene), polyolefin fibers (such as polyethylene, polypropylene, etc.), polyurethane fibers (such as polyurethane), polyvinyl chloride / polyvinyl alcohol copolymer fibers (such as polyvinyl chloride alcohol fiber (polychlal), etc.). Examples of hydrophilic fibers include seed hair fibers (such as cotton, cotton, kapok, etc.), bast fibers (such as hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (such as Manila hemp, sisal, etc.), coconut fibers, rush, straw, animal hair fibers (such as wool, mohair, cashmere, camel hair, alpaca hair, vicuña hair, angora rabbit hair, etc.), silk fibers (such as domestic silk, wild silk), feathers, cellulose fibers (such as rayon, high wet modulus viscose fiber (polynosic), cuprammonium fiber, acetate fiber, etc.).

[0068] In addition, examples of fiber products include fabrics, knitted fabrics, non-woven fabrics, etc. using the above-mentioned hydrophobic fibers or hydrophilic fibers, and products such as vests, T-shirts, shirts, blouses, casual pants, hats, handkerchiefs, towels, knitted sweaters, socks, underwear, tights, etc. obtained using such fabrics.

[0069] The mechanism by which the effects of the present invention are manifested may not be clear, but it is considered as follows. Although the component (c) of the present invention has antibacterial properties, the antibacterial property against bacteria is enhanced by using it in combination with the component (b). The reason is considered to be that, compared with the case where only the component (c) is absorbed into the bacterial cell, when both the component (c) and the component (b) are absorbed into the bacterial cell, the effect on any metabolic system of the bacteria becomes greater, thereby inhibiting the growth of the bacterial cells. On the other hand, it is considered that when cleaning a fiber product, the component (a) that contributes to the cleanliness of the fiber product is adsorbed onto the surface of the fiber product after cleaning, but the component (c) that becomes a low molecule and has high solubility in water is difficult to be adsorbed onto the surface of the fiber product. In the liquid detergent composition for fiber products of the present invention, by using the component (b) in combination, the molecular aggregation state of the component (a) as a surfactant in the aqueous solution is changed, thereby exhibiting good detergency and foaming properties. Further, it is considered that the component (b) with higher hydrophobicity is easily adsorbed onto the surface of the fiber product, and regarding the adsorption states of the components (a) and (b) on the fiber surface after cleaning, it is considered that gaps are formed at the adsorption sites of the component (a), and the component (c) of the present invention is adsorbed into these gaps, thereby promoting the adsorption of the component (c) near the component (b). It is considered that when the components (a1) and (a2) are used in combination, the relationship between these adsorbed molecules becomes a better state. It is considered that when bacterial cells adhere to the surface of the fiber product cleaned with the composition of the present invention, it is easy to introduce the nearby components (b) and (c), thereby enhancing the antibacterial property. In addition, the present invention is not particularly limited to the above action mechanism.

[0070] [Cleaning method for fiber products]

[0071] The cleaning method of the present invention is a cleaning method for fiber products as follows: cleaning the fiber products with a cleaning liquid obtained by mixing the liquid detergent composition for fiber products of the present invention and water, and then rinsing the fiber products with water.

[0072] That is, the cleaning method of the present invention is a cleaning method for fiber products as follows: cleaning the fiber products with a cleaning liquid obtained by mixing the components (a), (b), (c) and water, and then rinsing the fiber products with water.

[0073] The water mixed with the liquid detergent composition for fiber products of the present invention and the water for rinsing can be respectively selected within the range of 1 °dH or more, further 2 °dH or more, further 3 °dH or more and 30 °dH or less, further 25 °dH or less, further 20 °dH or less, still further 18 °dH or less, and even further 15 °dH or less as measured by a German hardness meter.

[0074] Here, the German hardness (°dH) in this specification refers to the concentration of calcium and magnesium in water expressed as 1 mg / L (ppm) = approximately 0.056 °dH (1 °dH = 17.8 ppm) in terms of the conversion concentration of CaCO3.

[0075] The concentration of calcium and magnesium used to reflect this German hardness is determined by the chelation titration method using disodium ethylenediaminetetraacetate.

[0076] The following shows the specific measurement method of the German hardness of the water in this specification.

[0077] <Measurement Method of German Hardness of Water>

[0078] [Reagents]

[0079] · 0.01 mol / l EDTA·2Na solution: 0.01 mol / l aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH Co., Ltd.)

[0080] · Universal BT indicator (Product name: Universal BT, manufactured by Dojindo Laboratories)

[0081] · Ammonia buffer solution for hardness measurement (solution prepared by dissolving 67.5 g of ammonium chloride in 570 ml of 28 w / v% ammonia water and making the total volume 1000 ml with deionized water)

[0082] [Measurement of Hardness]

[0083] (1) Collect 20 ml of the water as a sample into a conical beaker using a volumetric pipette.

[0084] (2) Add 2 ml of the ammonia buffer solution for hardness measurement.

[0085] (3) Add 0.5 ml of the Universal BT indicator. Confirm that the solution after addition is purplish red.

[0086] (4) While thoroughly shaking the conical beaker, add the 0.01 mol / l EDTA·2Na solution dropwise from the burette, and take the moment when the water as the sample changes color to blue as the end point of the titration.

[0087] (5) The total hardness is obtained from the following calculation formula.

[0088] Hardness (°dH) = T × 0.01 × F × 56.0774 × 100 / A

[0089] T: Titration volume (mL) of the 0.01 mol / l EDTA·2Na solution

[0090] A: Sample volume (20 mL, volume of water that becomes the test sample)

[0091] F: Factor of 0.01 mol / l EDTA·2Na solution

[0092] In the cleaning method of the present invention, the matters described in the liquid detergent composition for fiber products of the present invention can be appropriately applied.

[0093] From the viewpoints of antibacterial property, detergency, and foaming property, the content of component (a) in the above cleaning liquid is preferably 50 mass ppm or more, more preferably 100 mass ppm or more, further preferably 125 mass ppm or more, and preferably 5000 mass ppm or less, more preferably 300 mass ppm or less, further preferably 270 mass ppm or less, and further more preferably 250 mass ppm or less.

[0094] From the viewpoints of antibacterial property, detergency, and foaming property, the content of component (a1) in the above cleaning liquid is preferably 10 mass ppm or more, more preferably 20 mass ppm or more, and preferably 2000 mass ppm or less, more preferably 500 mass ppm or less.

[0095] From the viewpoints of antibacterial property, detergency, and foaming property, the content of component (a2) in the above cleaning liquid is preferably 10 mass ppm or more, more preferably 20 mass ppm or more, and preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less.

[0096] From the viewpoints of antibacterial property and foaming property, the mass ratio of the content of component (a1) to the total content of component (a1) and component (a2) in the above cleaning liquid, i.e., (a1) / [(a1)+(a2)], is preferably 0.05 or more, more preferably 0.2 or more, further preferably 0.4 or more, and from the viewpoints of detergency and foaming property, it is preferably 0.95 or less, more preferably 0.8 or less, further preferably 0.6 or less.

[0097] From the viewpoints of detergency and foaming property, the content of component (b) in the above cleaning liquid is preferably 1 mass ppm or more, more preferably 1.5 mass ppm or more, further preferably 2 mass ppm or more, and preferably 12 mass ppm or less, more preferably 10 mass ppm or less, further preferably 8 mass ppm or less.

[0098] From the viewpoints of antibacterial property and foaming property, the mass ratio of the content of component (a) to the content of component (b) in the above cleaning liquid, i.e., (b) / (a), is preferably 0.010 or more, more preferably 0.020 or more. And from the viewpoints of detergency and foaming property, it is preferably 0.100 or less, more preferably 0.075 or less, further preferably 0.06 or less, and still more preferably 0.05 or less.

[0099] From the viewpoints of antibacterial property and economy, the content of component (c) in the above cleaning liquid is preferably 0.03 mass ppm or more, more preferably 0.05 mass ppm or more, further preferably 0.1 mass ppm or more, and preferably 1.5 mass ppm or less, more preferably 1.3 mass ppm or less, further preferably 1.0 mass ppm or less.

[0100] From the viewpoints of antibacterial property, detergency, foaming property and workability, the temperature of the cleaning liquid is preferably 0 °C or more, more preferably 3 °C or more, further preferably 5 °C or more, and preferably 70 °C or less, more preferably 60 °C or less.

[0101] From the viewpoints of antibacterial property, detergency and foaming property, the pH value of the cleaning liquid at 20 °C is preferably 3 or more, more preferably 4 or more, and preferably 10 or less, more preferably 9 or less. The pH value of the cleaning liquid can be measured by the measurement method described in the examples below.

[0102] In recent years, washing machines have been gradually enlarged, and the value of the bath ratio, which is represented by the ratio of the mass (kg) of the clothing material to the amount of water (liters) of the cleaning liquid, i.e., the amount of water (liters) of the cleaning liquid / the mass (kg) of the clothing material (hereinafter, this ratio may sometimes be referred to as the bath ratio), has a tendency to become smaller. In the cleaning method of the present invention, from the viewpoints of antibacterial property, detergency and foaming property, the bath ratio is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, still more preferably 5 or more, and preferably 45 or less, more preferably 40 or less, further preferably 30 or less, and still more preferably 20 or less.

[0103] In the cleaning method of the present invention, from the viewpoints of workability, antibacterial property, detergency and foaming property, the cleaning time is preferably 1 minute or more, more preferably 2 minutes or more, further preferably 3 minutes or more, and preferably 90 minutes or less, more preferably 60 minutes or less, further preferably 30 minutes or less, and still more preferably 15 minutes or less.

[0104] The cleaning method of the fibers of the present invention is suitable for the following methods: a method of impregnating fibers into a liquid for refining while conveying the fibers by means of rollers or the like; a rotary cleaning method. The rotary cleaning method refers to a cleaning method in which fibers not fixed to a rotating device rotate around a rotation axis together with a cleaning liquid. The rotary cleaning method can be implemented via a rotary washing machine. In the present invention, for example, it is preferable to use a rotary washing machine to clean the fibers. Specifically, as the rotary washing machine, a drum washing machine, a pulsator washing machine, or a stirring washing machine can be cited. These rotary washing machines can use commercially available machines respectively.

[0105] The cleaning method of the present invention uses a specified cleaning liquid to clean a fiber product, and then, the fiber product is rinsed with water. The rinsing can be carried out using water according to a well-known method such as washing of clothing.

[0106] In addition to the above embodiments, the present invention discloses the following forms.

[0107] <1>

[0108] A liquid detergent composition for fiber products, which contains (a) a surfactant [hereinafter referred to as component (a)], (b) an alcohol having 10 to 16 carbon atoms [hereinafter referred to as component (b)], and (c) an antibacterial compound having an aromatic ring (excluding quaternary ammonium salts) [hereinafter referred to as component (c)].

[0109] <2>

[0110] The liquid detergent composition for fiber products as described in <1>, wherein component (a) is one or more surfactants selected from (a1) anionic surfactants and (a2) nonionic surfactants.

[0111] <3>

[0112] The liquid detergent composition for fiber products as described in <1> or <2>, which contains (a1) anionic surfactant [hereinafter referred to as component (a1)] and (a2) nonionic surfactant [hereinafter referred to as component (a2)] as component (a).

[0113] <4>

[0114] The liquid detergent composition for fiber products as described in <3>, wherein the mass ratio of the content of component (a1) to the total content of component (a1) and component (a2), i.e., (a1) / [(a1)+(a2)], is preferably 0.05 or more, more preferably 0.2 or more, further preferably 0.3 or more, further more preferably 0.4 or more, and preferably 0.95 or less, more preferably 0.8 or less, further preferably 0.6 or less.

[0115] <5>

[0116] The liquid detergent composition for fiber products according to any one of <2> to <4>, wherein the component (a2) is a nonionic surfactant selected from alcohol alkoxylates and ester alkoxylates.

[0117] <6>

[0118] The liquid detergent composition for fiber products according to any one of <1> to <5>, wherein the mass ratio of the content of the component (a) to the content of the component (b), i.e., (b) / (a), is preferably 0.010 or more, more preferably 0.020 or more, and preferably 0.1 or less, more preferably 0.075 or less, further preferably 0.06 or less, and further more preferably 0.05 or less.

[0119] <7>

[0120] The liquid detergent composition for fiber products according to any one of <1> to <6>, which contains internal olefin sulfonate having 10 or more and 18 or less carbon atoms as the component (a).

[0121] <8>

[0122] The liquid detergent composition for fiber products according to any one of <1> to <7>, which contains the nonionic surfactant represented by the following general formula (1) as the component (a).

[0123] R 1 (CO) m O-(AO) n -R 2 (1)

[0124] [In the formula, R 1 is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, R 2 is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, AO is one or more alkylene oxides selected from alkylene oxides having 2 carbon atoms and alkylene oxides having 3 carbon atoms, and AO contains at least an alkylene oxide having 2 carbon atoms. When AO contains ethylene oxide and propylene oxide, the ethylene oxide and propylene oxide may be block-bonded or randomly bonded; n is the average addition mole number and is a number of 1 or more and 50 or less.]

[0125] <9>

[0126] The liquid detergent composition for fiber products according to any one of <1> to <8>, which contains the surfactant represented by the following general formula (2) as the component (a).

[0127] R11 -O-(EO) n1 -(AO) n2 -(EO) n3 -H (2)

[0128] [In the formula, R 11 is an alkyl or alkenyl group having 10 or more and 18 or less carbon atoms, EO is ethoxy, AO is an alkyleneoxy group having 3 or 4 carbon atoms, n1, n2, and n3 are the average addition molar numbers of EO and AO, n1 is 1 or more and 15 or less, n2 is 1 or more and 10 or less, and n3 is 1 or more and 15 or less.]

[0129] <10>

[0130] The liquid detergent composition for fiber products according to any one of <1> to <9>, wherein the component (b) is an alcohol selected from decanol, dodecanol, tetradecanol, and hexadecanol, preferably an alcohol selected from 1-decanol, 1-dodecanol, 1-tetradecanol, and 1-hexadecanol, more preferably an alcohol selected from 1-dodecanol and 1-tetradecanol, and further preferably 1-dodecanol.

[0131] <11>

[0132] The liquid detergent composition for fiber products according to any one of <1> to <10>, wherein the component (c) is a nonionic antibacterial compound having an aromatic ring.

[0133] <12>

[0134] The liquid detergent composition for fiber products according to any one of <1> to <11>, wherein the component (c) is an antibacterial compound having a diphenyl ether skeleton.

[0135] <13>

[0136] The liquid detergent composition for fiber products according to any one of <1> to <12>, which contains the component (c) preferably in an amount of 0.01% by mass or more, more preferably 0.02% by mass or more and preferably 0.1% by mass or less, more preferably 0.07% by mass or less.

[0137] <14>

[0138] A method for cleaning a fiber product, which comprises cleaning the fiber product with a cleaning liquid obtained by mixing the liquid detergent composition for fiber products according to any one of <1> to <13> with water, and then rinsing the fiber product with water.

[0139] <15>

[0140] A cleaning method for a fiber product as described in <14>, wherein the water mixed with the liquid detergent composition for the fiber product and the water for rinsing respectively have a hardness selected from the range of 1 °dH or more, further 2 °dH or more, still further 3 °dH or more and 30 °dH or less, further 25 °dH or less, still further 20 °dH or less, even further 18 °dH or less, and further 15 °dH or less as measured by a German hardness meter.

[0141] <16>

[0142] A cleaning method for a fiber product as described in <15>, wherein the above-mentioned German hardness is the hardness measured by the following measuring method.

[0143] <Method for Measuring German Hardness of Water>

[0144] [Reagents]

[0145] · 0.01 mol / l EDTA·2Na solution: 0.01 mol / l aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH)

[0146] · Universal BT indicator (Product name: Universal BT, manufactured by Dojindo Laboratories)

[0147] · Ammonia buffer solution for hardness measurement (solution obtained by dissolving 67.5 g of ammonium chloride in 570 ml of 28 w / v% ammonia water and making the total volume 1000 ml with deionized water)

[0148] [Measurement of Hardness]

[0149] (1) Collect 20 ml of water as a sample into a conical flask using a volumetric pipette.

[0150] (2) Add 2 ml of ammonia buffer solution for hardness measurement.

[0151] (3) Add 0.5 ml of Universal BT indicator. Confirm that the solution after addition is purplish red.

[0152] (4) While shaking the conical flask sufficiently, add 0.01 mol / l EDTA·2Na solution dropwise from a burette, and take the moment when the water as a sample changes color to blue as the end point of titration.

[0153] (5) The total hardness is obtained from the following calculation formula.

[0154] Hardness (°dH) = T × 0.01 × F × 56.0774 × 100 / A

[0155] T: Titration volume (mL) of 0.01 mol / L EDTA·2Na solution

[0156] A: Sample volume (20 mL, volume of water as the test sample)

[0157] F: Factor of 0.01 mol / L EDTA·2Na solution

[0158] <17>

[0159] The cleaning method of the fiber product as described in any one of <14> to <16>, wherein the content of component (a) in the above cleaning solution is preferably 50 mass ppm or more, more preferably 100 mass ppm or more, further preferably 125 mass ppm or more, and preferably 5000 mass ppm or less, more preferably 300 mass ppm or less, further preferably 270 mass ppm or less, and further more preferably 250 mass ppm or less.

[0160] <18>

[0161] The cleaning method of the fiber product as described in any one of <14> to <17>, wherein the content of component (a1) in the above cleaning solution is preferably 10 mass ppm or more, more preferably 20 mass ppm or more, and preferably 2000 mass ppm or less, more preferably 500 mass ppm or less.

[0162] <19>

[0163] The cleaning method of the fiber product as described in any one of <14> to <18>, wherein the content of component (a2) in the above cleaning solution is preferably 10 mass ppm or more, more preferably 20 mass ppm or more, and preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less.

[0164] <20>

[0165] The cleaning method of the fiber product as described in any one of <14> to <19>, wherein the content of component (b) in the above cleaning solution is preferably 1 mass ppm or more, more preferably 1.5 mass ppm or more, further preferably 2 mass ppm or more, and preferably 12 mass ppm or less, more preferably 10 mass ppm or less, further preferably 8 mass ppm or less.

[0166] <21>

[0167] The cleaning method of the fiber product according to any one of <14> to <20>, wherein the content of the component (c) in the above cleaning liquid is preferably 0.03 mass ppm or more, more preferably 0.05 mass ppm or more, still more preferably 0.1 mass ppm or more, and preferably 1.5 mass ppm or less, more preferably 1.3 mass ppm or less, still more preferably 1.0 mass ppm or less.

[0168] Examples

[0169] The components used in the examples and comparative examples are as described below.

[0170] <Blending components>

[0171] (a) component

[0172] (a1) component

[0173] (a1-1): Potassium internal olefin sulfonate with 16 carbon atoms

[0174] (a1-1) is obtained by using internal olefins with 16 carbon atoms and referring to the method described in the production example of Japanese Patent Laid-Open No. 2014-76988. The mass ratio of olefin body (potassium olefin sulfonate) / hydroxy body (potassium hydroxyalkane sulfonate) in the obtained potassium internal olefin sulfonate of (a1-1) is 17 / 83. The mass ratio of the position distribution of the sulfonic acid group of the hydroxy body in (a1-1) is 1st / 2nd / 3rd / 4th / 5th / 6-9th = 2.3% / 23.6% / 18.9% / 17.5% / 13.7% / 11.2% / 6.4% / 6.4% / 0% (total 100 mass%).

[0175] The mass ratio of the position distribution of the sulfonic acid group in the internal olefin sulfonate is measured by high performance liquid chromatography / mass spectrometer (HPLC-MS). Specifically, the hydroxy body combined with the sulfonic acid group is separated by a high performance liquid chromatography device (HPLC), and each hydroxy body combined with the sulfonic acid group is identified by a mass spectrometer (MS). As a result, the ratio of each sulfonic acid group is obtained based on its HPLC-MS peak area. In this specification, the ratio of each sulfonic acid group obtained from the peak area is calculated as the mass ratio.

[0176] In addition, the apparatus and conditions used in the measurement are as follows. HPLC apparatus "LC-20ASXR" (manufactured by Shimadzu Corporation), column "ODS Hypersil (registered trademark)" (4.6×250 mm, particle size: 3 μm, manufactured by ThermoFisher Scientific), sample preparation (diluted 1000-fold with methanol), eluent A (water added with 10 mM ammonium acetate), eluent B (methacrylonitrile / water = 95 / 5 (v / v) solution added with 10 mM ammonium acetate), gradient (0 min (A / B = 60 / 40) → 15.1 - 20 min (30 / 70) → 20.1 - 30 min (60 / 40)), MS apparatus "LCMS-2020" (manufactured by Shimadzu Corporation), ESI (Electrospray Ionization) detection (anion detection, m / z: 321.10 (component (a) with 16 carbon atoms), column temperature (40 °C), flow rate (0.5 mL / min), injection volume (5 μL)

[0177] The mass ratio of the hydroxy form to the olefin form of the internal olefin sulfonate is determined by HPLC-MS. Specifically, the hydroxy form and the olefin form are separated by HPLC, and the hydroxy form and the olefin form are respectively identified using MS. As a result, the respective ratios are obtained based on the HPLC-MS peak areas of the hydroxy form and the olefin form.

[0178] In addition, the apparatus and conditions used in the measurement are as follows. HPLC apparatus (trade name: Agilent Technology 1100, manufactured by Agilent Technologies), column (trade name: L-column ODS 4.6×150 mm, manufactured by Chemicals Evaluation and Research Institute, Japan), sample preparation (diluted 1000-fold with methanol), eluent A (water added with 10 mM ammonium acetate), eluent B (methanol added with 10 mM ammonium acetate), gradient (0 min (A / B = 30 / 70%) → 10 min (30 / 70%) → 55 min (0 / 100%) → 65 min (0 / 100%) → 66 min (30 / 70%) → 75 min (30 / 70%)), MS apparatus (trade name: Agilent Technology 1100MS SL (G1946D)), MS detection (anion detection, m / z 60 - 1600, UV (ultraviolet) 240 nm)

[0179] In addition, an α-olefin sulfonate having an aliphatic hydrocarbon group with 16 carbon atoms is externally added to the component (a1-1) in a specified amount, the peak area of the α-olefin sulfonate is compared with the peak area of the component (a1-1), and the mass of the component (a1-1) is calculated. The number of moles of the component (a1-1) is calculated based on the molecular weight of the component (a1-1). The molecular weight of the component (a1-1) is calculated in acid form. The molecular weight of the olefin body of the internal olefin sulfonate is 304.5, and the molecular weight of the HAS body is 322.6.

[0180] (a1-2): Laurylbenzenesulfonic acid

[0181] (a2) component

[0182] (a2-1): Polyoxyethylene lauryl ether (average number of moles of ethylene oxide added: 10 moles)

[0183] (a2-2): Polyoxyethylene·polyoxypropylene·polyoxyethylene lauryl ether (average number of moles of ethylene oxide added: 9 moles and 9 moles, average number of moles of propylene oxide added: 2 moles)

[0184] (b) component: 1-Dodecanol (manufactured by Kao Corporation, Kalcol 2098)

[0185] (c) component: Triclosan

[0186] (1) Method for measuring pH value

[0187] Connect a combined electrode for pH measurement (manufactured by HORIBA, glass ground sleeve type) to a pH meter (manufactured by HORIBA, pH meter / ion meter F-23), and turn on the power. Use a saturated potassium chloride aqueous solution (3.33 mol / L) as the internal solution of the pH electrode. Then, fill 100 mL beakers with standard solutions of pH 4.01 (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 (borate standard solution) respectively, and immerse them in a constant temperature bath at 25°C for 30 minutes. Immerse the pH measurement electrode in the thermostatically adjusted standard solution for 3 minutes, and perform calibration operations in the order of pH 6.86 → pH 9.18 → pH 4.01. Adjust the sample (liquid detergent composition for fiber products) to be measured to 25°C, immerse the electrode of the above pH meter in the sample, and measure the pH value after 1 minute.

[0188] (2) Preparation of liquid detergent composition for fiber products

[0189] The preparation method of the liquid detergent composition for fiber products shown in Tables 1 and 2 is as follows.

[0190] A stirring piece made of Teflon (registered trademark), with a length of 5 cm, was put into a glass beaker with a capacity of 200 mL, and its mass was measured. Then, 20 g of ion-exchanged water, component (a1), component (a2), component (b), and component (c) were added. While stirring at 100 r / min, monoethanolamine or hydrochloric acid was added so that the pH value of the composition became 8, and ion-exchanged water was added to make the total amount 100 g. After stirring at 100 r / min for 15 minutes, a liquid detergent composition for fiber products was prepared.

[0191] (3) Preparation of fiber products for cleaning rate evaluation

[0192] (3-1) Preparation of fiber products for evaluating the adsorption rate of triclosan

[0193] A 1.7 kg of cotton cloth (Kome 2003 (manufactured by Taniguchi Store)) was subjected to two cumulative washes using the standard program of a fully automatic washing machine (manufactured by National, NA-F702P) (during cleaning, 4.7 g of Emulgen 108 (manufactured by Kao Corporation) and 47 L of water were used, washing for 9 minutes, rinsing twice, and dehydrating for 3 minutes). Then, it was subjected to three cumulative washes only with water (47 L of water, washing for 9 minutes, rinsing twice, and dehydrating for 3 minutes), and dried for 24 hours in an environment of 23°C and 45% RH. Thereafter, it was cut into a size of 6 cm × 6 cm.

[0194] (3-2) Preparation of fiber products for cleaning rate evaluation

[0195] · Preparation of model sebum artificial contaminated cloth

[0196] A model sebum artificial contaminated liquid with the following composition was attached to a cloth (Kome 2003 (manufactured by Taniguchi Store)) to prepare a model sebum artificial contaminated cloth. The attachment of the model sebum artificial contaminated liquid to the cloth was carried out by printing the artificial contaminated liquid onto the cloth using an intaglio roll coater. The step of making the model sebum artificial contaminated liquid by attaching it to the cloth was carried out under the conditions of a unit capacity of the intaglio roll of 58 cm 3 / m 2 , a coating speed of 1.0 m / min, a drying temperature of 100°C, and a drying time of 1 min. Thereafter, it was cut into a size of 6 cm × 6 cm.

[0197] *Composition of the model sebum artificial contamination solution: lauric acid 0.4% by mass, myristic acid 3.1% by mass, pentadecanoic acid 2.3% by mass, palmitic acid 6.2% by mass, heptadecanoic acid 0.4% by mass, stearic acid 1.6% by mass, oleic acid 7.8% by mass, triolein 13.0% by mass, cetyl palmitate 2.2% by mass, squalene 6.5% by mass, protein lecithin liquid crystal 1.9% by mass, Kanuma red clay 8.1% by mass, carbon black 0.01% by mass, and the balance water (total 100% by mass)

[0198] (4) Cleaning test

[0199] (4-1) Cleaning test 1

[0200] The cleaning operation was carried out using a vertical decontamination machine (Terg-O-Tometer, manufactured by Ueshima Seisakusho). The cleaning water used in the cleaning was obtained as follows: Calcium chloride and magnesium chloride were added to ion-exchanged water at a mass ratio of 8:2 to adjust the hardness to 4°dH. The liquid detergent composition for fiber products described in Tables 1 and 2 was mixed with the cleaning water in such a way that the total amount of components (a1) and (a2) in the composition was 150 mg / kg by concentration in the cleaning liquid to obtain a cleaning liquid. 0.6 L of the cleaning liquid and 4 pieces of the fiber products for evaluating the adsorption rate of the above-mentioned triclosan were put into a 1-liter stainless steel beaker for the cleaning test. The bath ratio was adjusted to 20 by the above-mentioned fiber products for evaluating the adsorption rate. The temperature of the cleaning liquid was 20°C. The fiber for cleaning evaluation was cleaned at 85 rpm for 10 minutes using the Terg-O-Tometer. After cleaning, dehydration was carried out, and all the dehydrated fibers were put into 0.6 L of cleaning water and rinsed at 85 rpm for 3 minutes using the Terg-O-Tometer. After rinsing, dehydration was carried out again, and then dried in an environment of 23°C and 45% RH for 24 hours.

[0201] (4-2) Cleaning test 2

[0202] The cleaning operation was carried out using a vertical decontamination machine (Terg-O-Tometer, manufactured by Ueshima Seisakusho). The water used for cleaning was obtained as follows: Calcium chloride and magnesium chloride were added to ion-exchanged water at a mass ratio of 8:2, and the hardness was adjusted to 4°dH to obtain the cleaning water. The cleaning liquid was obtained by mixing the cleaning water with the total amount of components (a1) and (a2) in the liquid detergent composition for fiber products described in Tables 1 and 2 at a concentration of 150 mg / kg in the cleaning liquid. 0.6 L of the cleaning liquid and 5 pieces of the above-mentioned fiber products for evaluating the cleaning rate were put into a 1-liter stainless steel beaker for the cleaning test. The bath ratio was adjusted to 20 using the fiber products for evaluating the adsorption rate of triclosan. The temperature of the cleaning liquid was 20 °C. The fibers for evaluation were cleaned for 10 minutes at 85 rpm using the Terg-O-Tometer. After cleaning, dehydration was carried out, and drying was carried out using a hot press.

[0203] (5) Quantification of the adsorption amount of triclosan on fiber products (evaluation of antibacterial properties)

[0204] The adsorption amount of the antibacterial agent on the fiber product was used as an index of antibacterial properties. The more the adsorption amount of the antibacterial agent, the higher the antibacterial properties, and in addition, the antibacterial properties of the fiber product after cleaning were maintained well.

[0205] Two pieces were taken out from the fiber products for evaluating the adsorption rate of triclosan after the above-mentioned cleaning test 1, and the mass of the cloth was measured while sealing them into a No. 7 screw tube. 20 mL of methanol was added to the tube, and ultrasonic treatment was carried out at 25 °C for 30 minutes using an ultrasonic cleaner to obtain the measurement solution. Next, component (c) (triclosan) was diluted with methanol to prepare calibration curve solutions of 0.01 μg / mL, 0.05 μg / mL, 0.1 μg / mL, 0.5 μg / mL, and 1.0 μg / mL. The amount of triclosan in the measurement solution was quantified by a liquid chromatography-mass spectrometry device (hereinafter, simply referred to as the LCMS device), and the adsorption amount of triclosan on the fiber product was determined from the calibration curve solutions.

[0206] · LCMS device: LCMS2020 manufactured by Shimadzu Corporation

[0207] · Eluent A: An aqueous solution of 10 mmol / L ammonium acetate distilled water was used

[0208] Eluent B: A methanol solution of 10 mmol / L ammonium acetate

[0209] · Gradient conditions: Eluent A / B = 1:1 (0 minutes) → Eluent B (2 - 5 minutes) → Eluent A / Eluent B = 1 / 1 (5.1 minutes to 8 minutes), flow rate: 0.6 mL / min, sample injection volume 5 μL, column temperature 40 °C

[0210] The adsorption rate of triclosan on the textile products was calculated by the following formula. The results are shown in Tables 1 and 2.

[0211] Adsorption rate of triclosan = 100 × {(total mass of triclosan adsorbed by the two textile products used in the measurement of the adsorption amount) × (total mass of the textile products used in Cleaning Test 1) / (mass of the two textile products used in the measurement of the adsorption amount)} / (total mass of triclosan used in the preparation of the cleaning solution)

[0212] (6) Method for evaluating the cleaning rate

[0213] The cleaning rate of the evaluated textile products obtained in the above-mentioned Cleaning Test 2 was measured by the following method, and the average value of 5 textile products was calculated. The results are shown in Tables 1 and 2.

[0214] The reflectance of the original fabric before contamination and at 550 nm before and after cleaning was measured using a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., Z-300A), and the cleaning rate (%) was calculated according to the following formula. In addition, the values in Tables 1 and 2 are the average values of the cleaning rates of 5 textile products.

[0215] Cleaning rate (%) = 100 × [(reflectance after cleaning - reflectance before cleaning) / (reflectance of the original fabric - reflectance before cleaning)]

[0216] (7) Foaming test

[0217] The water used in the foaming test was the foaming test water obtained as follows: Calcium chloride and magnesium chloride were added to deionized water at a mass ratio of 8:2 to adjust the hardness to 4°dH. The textile products described in Tables 1 and 2 were mixed with the foaming test water with the liquid detergent composition so that the total amount of components (a1) and (a2) in the composition was 600 mg / kg by concentration in the cleaning solution to obtain a foaming test solution. 50 g of the foaming test solution was placed in a No. 8 helical tube. The helical tube containing the foaming test solution was subjected to vertical reciprocating vibration treatment at 300 rpm for 5 minutes using a vibrator (Yamato Scientific Co., Ltd., model: SA300). After the treatment, the helical tube was removed from the vibrator, and after standing for 30 minutes, the height from the water surface to the foam surface of the foaming test solution was measured, and this height was taken as the foam height. The foaming test solution with a foam height of 3.5 cm or more was designated as ○, and the foaming test solution with a foam height of less than 3.5 cm was designated as ×.

[0218]

[0219]

Claims

1. A liquid detergent composition for fiber products, wherein, it contains the following components (a), (b) and (c): (a) Surfactant; (b) An alcohol having 10 or more and 16 or less carbon atoms; (c) An antibacterial compound having an aromatic ring other than quaternary ammonium salt, As the component (a), it contains the components (a1) and (a2): (a1) Anionic surfactant; (a2) Nonionic surfactant, The component (a1) is one or more anionic surfactants selected from internal olefin sulfonates having 14 or more and 18 or less carbon atoms and alkylbenzene sulfonates having an alkyl group having 10 or more and 24 or less carbon atoms, The component (a2) contains surfactants represented by the following general formula (1) and the following general formula (2), R 1 (CO) m O-(AO) n -R 2 (1) In general formula (1), R 1 is an aliphatic hydrocarbon group having 12 or more and 18 or less carbon atoms, R 2 is a hydrogen atom, CO is a carbonyl group, m is 0, AO is an alkyleneoxy group having 2 carbon atoms, n is the average number of moles added, and is a number of 6 or more and 10 or less, R 11 -O-(EO) n1 -(AO) n2 -(EO) n3 -H(2) In the general formula (2), R 11 is an alkyl or alkenyl group having 10 or more and 15 or less carbon atoms, EO is an ethyleneoxy group, AO is an alkyleneoxy group having 3 carbon atoms, n1, n2, and n3 are the average addition molar numbers of EO and AO, n1 is 3 or more and 10 or less, n2 is 2 or more and 8 or less, and n3 is 2 or more and 10 or less. (b) The component is 1-dodecanol, (c) The component is an antibacterial compound having a diphenyl ether skeleton, The mass ratio of the content of the component (a1) to the total content of the component (a1) and the component (a2), i.e., (a1) / [(a1)+(a2)], is 0.05 or more and 0.95 or less, The mass ratio of the content of the component (b) to the content of the component (a), i.e., (b) / (a), is 0.010 or more and 0.1 or less, The mass ratio of the content of the component (b) to the content of the component (c), i.e., (b) / (c), is 5 or more and 100 or less.

2. The liquid detergent composition for fiber products according to claim 1, wherein, The mass ratio of the content of the component (a1) to the total content of the component (a1) and the component (a2), i.e., (a1) / [(a1)+(a2)], is 0.2 or more and 0.8 or less.

3. The liquid detergent composition for fiber products according to claim 2, wherein, The mass ratio of the content of the component (a1) to the total content of the component (a1) and the component (a2), i.e., (a1) / [(a1)+(a2)], is 0.4 or more and 0.8 or less.

4. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein, (a1) The component is an anionic surfactant selected from potassium salt of internal olefin sulfonate having 16 carbon atoms and lauryl benzene sulfonic acid.

5. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein, The mass ratio of the content of the component (a) to the content of the component (b), i.e., (b) / (a), is 0.020 or more and 0.075 or less.

6. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein, The mass ratio of the content of the component (a) to the content of the component (b), i.e., (b) / (a), is 0.020 or more and 0.067 or less.

7. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein, (a2) The component is a surfactant selected from polyoxyethylene lauryl ether with an average addition molar number of 10 moles of ethylene oxide groups, and polyoxyethylene·polyoxypropylene·polyoxyethylene lauryl ether with an average addition molar number of 9 moles and 9 moles of ethylene oxide groups and an average addition molar number of 2 moles of propylene oxide groups.

8. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein (c) The component is an antibacterial compound containing a halogen atom and having a diphenyl ether skeleton.

9. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein (c) The component is an antibacterial compound selected from triclosan and triclocarban.

10. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein The content of component (c) is 0.01% by mass or more and 0.1% by mass or less.

11. The liquid detergent composition for fiber products according to any one of claims 1 to 3, wherein The mass ratio of the content of component (b) to the content of component (c), i.e., (b) / (c), is 5 or more and 50 or less.

12. A method for cleaning fiber products, wherein The fiber products are cleaned with a cleaning liquid obtained by mixing the liquid detergent composition for fiber products according to any one of claims 1 to 11 with water, and then the fiber products are rinsed with water.

13. The method for cleaning fiber products according to claim 12, wherein The water mixed with the liquid detergent composition for fiber products and the water for rinsing each have a hardness selected from 1 °dH or more and 30 °dH or less as measured by a German hardness meter.

14. The method for cleaning fiber products according to claim 13, wherein The German hardness is the hardness measured by the following measurement method. Measurement method for the German hardness of water: Reagents: · 0.01 mol / l EDTA·2Na solution: A 0.01 mol / l aqueous solution of disodium ethylenediaminetetraacetate, a titration solution, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH; · Universal BT indicator: Product name: Universal BT, manufactured by Dojindo Laboratories; · Ammonia buffer solution for hardness measurement: A solution obtained by dissolving 67.5 g of ammonium chloride in 570 ml of 28 w / v% ammonia water and making the total volume 1000 ml with deionized water. Measurement of hardness: (1) Collect 20 ml of water as a sample into a conical beaker using a full-volume pipette. (2) Add 2 ml of ammonia buffer solution for hardness measurement. (3) Add 0.5 ml of Universal BT indicator and confirm that the added solution is purple-red. (4) While shaking the conical beaker sufficiently, add 0.01 mol / l EDTA·2Na solution dropwise from a burette, and take the moment when the water as the sample changes color to blue as the end point of titration. (5) The total hardness is calculated by the following formula: Hardness = T × 0.01 × F × 56.0774 × 100 / A wherein the unit of hardness is °dH. T: The titration volume of the 0.01 mol / l EDTA·2Na solution, in mL; A: The sample volume, which is 20 mL and is the volume of water that becomes the test sample; F: The factor of the 0.01 mol / l EDTA·2Na solution.

15. The cleaning method of the fiber product according to any one of claims 12 to 14, wherein the content of component (a) in the cleaning liquid is 50 mass ppm or more and 5000 mass ppm or less.

16. The cleaning method of the fiber product according to any one of claims 12 to 14, wherein the cleaning liquid contains (a1) an anionic surfactant as component (a), and the content of component (a1) in the cleaning liquid is 10 mass ppm or more and 2000 mass ppm or less.

17. The cleaning method of the fiber product according to any one of claims 12 to 14, wherein the cleaning liquid contains (a2) a nonionic surfactant as component (a), and the content of component (a2) in the cleaning liquid is 10 mass ppm or more and 3000 mass ppm or less.

18. The cleaning method of the fiber product according to any one of claims 12 to 14, wherein the content of component (b) in the cleaning liquid is 1 mass ppm or more and 12 mass ppm or less.

19. The cleaning method of the fiber product according to any one of claims 12 to 14, wherein the content of component (c) in the cleaning liquid is 0.03 mass ppm or more and 1.5 mass ppm or less.

Images