WO2023286794A1 - Détergent liquide - Google Patents

Détergent liquide Download PDF

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Publication number
WO2023286794A1
WO2023286794A1 PCT/JP2022/027501 JP2022027501W WO2023286794A1 WO 2023286794 A1 WO2023286794 A1 WO 2023286794A1 JP 2022027501 W JP2022027501 W JP 2022027501W WO 2023286794 A1 WO2023286794 A1 WO 2023286794A1
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WIPO (PCT)
Prior art keywords
component
mass
liquid detergent
acid
salt
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PCT/JP2022/027501
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English (en)
Japanese (ja)
Inventor
敦 大河内
亮太 武井
彰悟 猿渡
聡 大塚
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ライオン株式会社
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Priority to JP2023534828A priority Critical patent/JPWO2023286794A1/ja
Publication of WO2023286794A1 publication Critical patent/WO2023286794A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening

Definitions

  • the present invention relates to liquid detergents.
  • This application claims priority based on Japanese Patent Application No. 2021-115742 filed in Japan on July 13, 2021, the contents of which are incorporated herein.
  • Patent Documents 1 and 2 disclose a liquid detergent containing a fluorescent brightener such as a stilbene type and a surfactant.
  • Patent Literatures 1 and 2 do not necessarily provide sufficient detergency against yellowing caused by oxidation of sebum stains accumulated on textile products such as clothes.
  • An object of the present invention is to provide a liquid detergent having excellent detergency against yellowing of textile products.
  • the present invention has the following aspects.
  • component (D) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 2. to the total mass of the liquid detergent.
  • the component (E) is an alkylene oxide adduct of polyalkyleneimine, polyacrylic acid and its salts, polymaleic acid and its salts, acrylic acid-maleic acid copolymer and its salts, The liquid detergent according to [6] above, containing one or more selected from the group consisting of copolymers of hydrocarbon and maleic acid and salts thereof, acrylic acid-methacrylic acid copolymers and salts thereof.
  • the component (E) contains an alkylene oxide adduct of the polyalkyleneimine, and the content of the alkylene oxide adduct of the polyalkyleneimine is preferably 0 relative to the total mass of the liquid detergent.
  • Component (F) The liquid detergent of any one of the above [1] to [8], further containing a structuring agent.
  • the content of component (F) is preferably 0.02 to 2% by mass, more preferably 0.04 to 1.5% by mass, relative to the total mass of the liquid detergent. , more preferably 0.05 to 1% by mass, the liquid detergent of [9] or [10].
  • Component (A) is 4,4′-bis(2-sulfostyryl)biphenyl disodium salt, 4,4′-bis-(4-chloro-3-sulfostyryl)-biphenyl disodium salt, 4,4′-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2′-disulfonate and 4,4′-bis((4- Any of the above [1] to [11], including one or more selected from the group consisting of toluidino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonates some liquid detergent.
  • the content of component (A) is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, relative to the total mass of the liquid detergent, and further The liquid detergent according to any one of the above [1] to [12], which is preferably 0.1 to 2% by mass, particularly preferably 0.1 to 1% by mass.
  • the nonionic surfactant contains one or more selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). liquid detergent.
  • R 11 O—[(EO) s /(A 11 O) t ]—(EO) u —R 12 (1)
  • R 11 is a straight or branched hydrocarbon group having 8 to 22 carbon atoms
  • R 12 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a is an alkenyl group
  • EO is an oxyethylene group
  • s is a number representing the average repeating number of EO from 3 to 25
  • a 11 O is at least one of PO (oxypropylene group) and BO (oxybutylene group)
  • t is a number from 0 to 6 representing the average number of repetitions of A 11 O.
  • u is a number from 0 to 20 representing the average number of repetitions of EO.
  • R 13 is a hydrocarbon group having 7 to 21 carbon atoms
  • —X— is —COO— or —CONH—
  • R 14 is a hydrogen atom; an alkyl group or an alkenyl group having 2 to 6 carbon atoms
  • EO is an oxyethylene group
  • p is a number from 3 to 25 indicating the average number of repetitions of EO
  • a 12 is PO (oxypropylene group) and BO ( oxybutylene group)
  • q is a number from 0 to 6 representing the average number of repetitions of A 12 O
  • r is a number from 0 to 20 representing the average number of repetitions of EO.
  • the content of the nonionic surfactant is preferably 5 to 60% by mass, more preferably 10 to
  • the non-soap anionic surfactant is linear alkylbenzene sulfonic acid or its salt, ⁇ -olefin sulfonic acid or its salt, linear or branched alkyl sulfate ester or its salt, polyoxyalkylene alkyl
  • the polyoxyalkylene alkyl (alkenyl) ether sulfate ester or salt thereof is a compound represented by the following general formula (3).
  • R 15 O—[(EO) m /(PO) n ]—SO 3 Ma (3)
  • R 15 is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms.
  • EO is is an oxyethylene group
  • PO is an oxypropylene group
  • m is a number of 0.1 or more representing the average number of repetitions of EO
  • n is a number of 0 to 6 representing the average number of repetitions of PO.
  • (EO) m /(PO) n ] indicates that there is no limitation on the arrangement order of EO and PO
  • Ma is a counterion.
  • the content of the non-soap anionic surfactant is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, and still more preferably, based on the total mass of the liquid detergent. is 10 to 30% by mass, particularly preferably 15 to 30% by mass.
  • the mass ratio of the nonionic surfactant to the non-soap anionic surfactant is preferably from 0.1 to 3, more preferably from 0.15 to 2, and even more preferably from 0.15 to 2. 2 to 1.5, particularly preferably 0.25 to 1.3, the liquid detergent according to any one of the above [14] to [20].
  • the water-miscible organic solvent is preferably ethanol, glycerin, 3-methoxy-3-methyl-1-butanol, propylene glycol, polyethylene glycol having a molecular weight of about 200 to 1000, and diethylene glycol monobutyl ether (butyl carbitol).
  • the liquid detergent according to any one of [1] to [22] above, which contains one or more selected from the group consisting of, more preferably one or more selected from the group consisting of ethanol, glycerin, and propylene glycol.
  • the mass ratio of water to the mass of the water-miscible organic solvent is preferably 0.2 to 3, more preferably 0.8 to 2.5, still more preferably 1 to 2.
  • the mass ratio of the component (A) to the mass of the antibacterial agent having a diphenyl structure is preferably 0.1 to 60, more preferably 0.25 to 60, still more preferably 1 to 30. , particularly preferably 1 to 10, most preferably 2 to 10, the liquid detergent of [26] or [27].
  • the liquid detergent of the present invention is a composition containing the following components (A), (B) and (C).
  • the liquid detergent preferably further contains one or more of the following components (D), (E) and (F).
  • the liquid detergent may contain components (optional components) other than (A) component, (B) component, (C) component, (D) component, (E) component, (F) component and water.
  • a numerical range represented by "-" means a numerical range including numerical values before and after "-" as lower and upper limits.
  • new numerical ranges can be obtained by arbitrarily combining the lower and upper limits thereof.
  • Component (A) is a fluorescent brightening agent. If the liquid detergent contains the (A) component, the (A) component adheres to the yellowing of the textile product that could not be removed by the cleaning component, thereby making the textile product look white. As a result, the yellowing of the textile product can be made difficult to see. That is, the detergency against yellowing of textile products can be improved.
  • component (A) examples include stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanine, dibenzothiophene-5-dioxide, azole, and derivatives of five- and six-membered heterocyclic compounds.
  • Particularly suitable examples include 4,4'-bis(2-sulfostyryl)biphenyl disodium salt, 4,4'-bis-(4-chloro-3-sulfostyryl)-biphenyl disodium salt, and the like.
  • Component may be used individually by 1 type, and may be used in combination of 2 or more types.
  • Tinopal registered trademark
  • Tinopal registered trademark
  • Tinopal registered trademark
  • CBS-X Tinopal
  • CBS-CL Tinopal
  • AMS-GX Tinopal
  • Leucophor registered trademark
  • the content of component (A) is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, even more preferably 0.1 to 2% by mass, relative to the total mass of the liquid detergent. 0.1 to 1% by weight is particularly preferred. If the content of the component (A) is at least the above lower limit, the yellowing of the textile product can be made less visible. If the content of component (A) is at most the above upper limit, good liquid appearance can be maintained.
  • Component is a surfactant. If the liquid detergent contains the (B) component, the detergency will increase.
  • Component (B) is not particularly limited as long as it is a surfactant used in conventional liquid detergents. Examples include nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, Semipolar surfactants and the like are included.
  • component (B) one surfactant may be used, or two or more surfactants may be used in combination. From the viewpoint of enhancing detergency, the component (B) preferably contains a nonionic surfactant and a non-soap anionic surfactant.
  • a nonionic surfactant As component (B), a nonionic surfactant, a non-soap anionic surfactant, and one or more of a cationic surfactant, an amphoteric surfactant and a semipolar surfactant may be used in combination.
  • nonionic surfactants include polyoxyalkylene type nonionic surfactants, alkylphenols, alkylene oxide adducts such as fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, Fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, hydrogenated castor oil alkylene oxide adducts, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like.
  • a nonionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more types.
  • nonionic surfactant a polyoxyalkylene type nonionic surfactant is preferable, and among them, in particular, a compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”), the following general formula A compound represented by (2) (hereinafter also referred to as “compound (2)”) is more preferred, and compound (1) is even more preferred.
  • compound (1) a compound represented by the following general formula (1)
  • compound (2) the following general formula A compound represented by (2)
  • compound (1) is even more preferred.
  • R 11 O—[(EO) s /(A 11 O) t ]—(EO) u —R 12 (1)
  • R 11 is a straight or branched hydrocarbon group having 8 to 22 carbon atoms
  • R 12 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a is an alkenyl group
  • EO is an oxyethylene group
  • s is a number representing the average repeating number of EO from 3 to 25
  • a 11 O is at least one of PO (oxypropylene group) and BO (oxybutylene group)
  • t is a number from 0 to 6 representing the average number of repetitions of A 11 O.
  • u is a number from 0 to 20 representing the average number of repetitions of EO.
  • the number of carbon atoms in the hydrocarbon group of R 11 is 8-22, preferably 10-18, more preferably 12-18.
  • R 12 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • s is preferably 4-20, more preferably 5-16, even more preferably 6-10.
  • t is preferably 0 to 4, more preferably 0 to 2, even more preferably 0.
  • u is 1 or more, s is preferably 4-16, more preferably 6-12, even more preferably 8-10.
  • t is preferably 1 to 4, more preferably 2 to 3.
  • u is preferably 4 to 16, more preferably 6 to 12, even more preferably 8 to 10.
  • R 13 —X—[(EO) p /(A 12 O) q ]—(EO) r —R 14 (2)
  • R 13 is a hydrocarbon group having 7 to 21 carbon atoms
  • —X— is —COO— or —CONH—
  • R 14 is a hydrogen atom; an alkyl group or an alkenyl group having 2 to 6 carbon atoms
  • EO is an oxyethylene group
  • p is a number of 3 to 25 indicating the average number of repetitions of EO
  • a 12 is PO (oxypropylene group) and BO ( oxybutylene group)
  • q is a number from 0 to 6 representing the average number of repetitions of A 12 O
  • r is a number from 0 to 20 representing the average number of repetitions of EO.
  • the number of carbon atoms in the hydrocarbon group of R 13 is 7-21, preferably 9-19, more preferably 11-17.
  • -X- is preferably -COO-.
  • R 14 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.
  • p is preferably 6-22, more preferably 9-20, even more preferably 12-18.
  • q is preferably 0 to 4, more preferably 0 to 2, even more preferably 0.
  • p is preferably 4-16, more preferably 6-12, even more preferably 8-10.
  • q is preferably 1 to 4, more preferably 2 to 3.
  • r is preferably 4 to 16, more preferably 6 to 12, even more preferably 8 to 10.
  • q is 1 or more, there is no particular limitation on the distribution (order of arrangement) of EO and PO, EO and BO, or EO, PO and BO in [(EO) p /(A 12 O) q ]. may be arranged in blocks or may be arranged randomly.
  • the content of the nonionic surfactant is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 45% by mass, and 20 to 40% by mass with respect to the total mass of the liquid detergent. Especially preferred. If the content of the nonionic surfactant is at least the above lower limit, the detergency will be enhanced. If the content of the nonionic surfactant is equal to or less than the above upper limit, liquid stability at low temperatures is improved.
  • liquid stability refers to the property that solidification, precipitation, and separation of components are unlikely to occur when the liquid detergent is stored.
  • non-soap anionic surfactants include linear alkylbenzene sulfonic acid or its salt (LAS), ⁇ -olefin sulfonic acid or its salt (AOS), linear or branched alkyl sulfate ester or its salt ( AS), polyoxyalkylene alkyl (alkenyl) ether sulfate or its salt (AES), alkanesulfonic acid having an alkyl group or its salt, ⁇ -sulfo fatty acid ester or its salt, internal olefin sulfonic acid or its salt (IOS) , alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, acylaminocarboxylic acid or its salt, carboxylic acid type anion Surfactants; phosphoric acid ester types such as alkyl phosphates,
  • Non-soap anionic surfactants include, for example, alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). ) and the like.
  • the non-soap anionic surfactants may be used singly or in combination of two or more.
  • LAS, AOS, AS, AES, and IOS are preferable, and LAS, AES, and IOS are more preferable from the viewpoint of further increasing detergency.
  • the liquid detergent contains at least AES, more preferably both LAS and AES.
  • a polyoxyalkylene alkyl (alkenyl) ether sulfate or a salt thereof (AES) is represented by the following general formula (3).
  • R 15 O—[(EO) m /(PO) n ]—SO 3 Ma (3)
  • R 15 is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms.
  • EO is is an oxyethylene group
  • PO is an oxypropylene group
  • m is a number of 0.1 or more representing the average number of repetitions of EO
  • n is a number of 0 to 6 representing the average number of repetitions of PO.
  • (EO) m /(PO) n ] indicates that there is no limitation on the arrangement order of EO and PO
  • Ma is a counterion.
  • Examples of Ma in formula (3) include sodium ion, potassium ion, magnesium ion, and ammonium ion.
  • Ma is a counterion with a valence of 2 or higher
  • Ma is bound to -SO 3 by multiplying the valence by 1. For example, when Ma is a magnesium ion, the number of Ma is 1/2.
  • the internal olefin sulfonic acid or its salt (IOS) is represented by the following general formula (5) and the alkene sulfonic acid represented by the following general formula (4) (hereinafter also referred to as "compound (4)"): It is a mixture with hydroxyalkanesulfonic acid (hereinafter also referred to as “compound (5)").
  • An internal olefin represents an olefin in which a double bond exists inside from the 2-position.
  • R 16 —CH ⁇ CH(CH 2 ) x CH(SO 3 Mb)—R 17 (4)
  • R 16 is an alkyl group
  • R 17 is an alkyl group having 1 to 5 carbon atoms, the total number of carbon atoms is 8 to 24, x is a number of 0 to 4, Mb represents a counterion.
  • the number of carbon atoms in compound (4) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. If the number of carbon atoms is at least the above lower limit, the lipophilicity of IOS increases, and the function as a surfactant increases. If the number of carbon atoms is equal to or less than the above upper limit, the hydrophilicity of IOS increases, and the function as a surfactant increases.
  • R 16 in formula (4) represents an alkyl group.
  • the number of carbon atoms in R 16 is preferably 1-21, more preferably 3-17, even more preferably 7-15.
  • R 17 in formula (4) represents an alkyl group having 1 to 5 carbon atoms.
  • the number of carbon atoms in R 17 is preferably 1-3.
  • x in formula (4) is 0 to 4, preferably 0 to 2. If x is more than the said lower limit, detergency will increase more. If x is below the said upper limit, liquid stability will improve more.
  • Examples of Mb in formula (4) include sodium ion, potassium ion, magnesium ion, and ammonium ion. When Mb is a counterion with a valence of 2 or higher, Mb is bound to -SO 3 by multiplying the valence by 1. For example, if Mb is a magnesium ion, the number of Mb is 1/2.
  • R 18 CH(SO 3 Mc)—R 19 (5)
  • R 18 is an alkyl group
  • R 19 is an alkyl group having 1 to 5 carbon atoms, the total number of carbon atoms is 8 to 24, y is a number of 0 to 4, Mc represents a counterion.
  • Compound (5) is the hydroxy form of compound (4).
  • the number of carbon atoms in compound (5) is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 14 to 18. If the number of carbon atoms is at least the above lower limit, the lipophilicity of IOS increases, and the function as a surfactant increases. If the number of carbon atoms is equal to or less than the above upper limit, the hydrophilicity of IOS increases, and the function as a surfactant increases.
  • R 18 in formula (5) represents an alkyl group.
  • the number of carbon atoms in R 18 is preferably 2-22, more preferably 4-18, even more preferably 8-16.
  • R 19 in formula (5) represents an alkyl group having 1 to 5 carbon atoms.
  • the number of carbon atoms in R 19 is preferably 1-3.
  • y in formula (5) is 0 to 4, preferably 0 to 2. If y is at least the above lower limit, the detergency will be enhanced. When y is equal to or less than the above upper limit value, the liquid stability is further improved.
  • Examples of Mc in formula (5) include sodium ion, potassium ion, magnesium ion, and ammonium ion.
  • Mc is a counter ion having a valence of 2 or more
  • Mc is bound to -SO 3 by a number multiplied by 1/valence.
  • Mc is a magnesium ion
  • the number of Mc is 1/2.
  • the ratio ((IO-2S)/(IO-1S) ratio) is preferably 0.3-5, more preferably 1-3.
  • the (IO-2S)/(IO-1S) ratio is at least the above lower limit, the slipperiness of the object to be washed is further enhanced. If the (IO-2S)/(IO-1S) ratio is equal to or less than the above upper limit, the liquid stability is further enhanced.
  • the (IO-1S) component is an IOS in which R 17 in formula (4) and R 19 in formula (5) have 1 to 3 carbon atoms.
  • the (IO-2S) component is an IOS in which R 17 in formula (4) and R 19 in formula (5) have 4 or more carbon atoms.
  • IOS is obtained by sulfonating an internal olefin.
  • the total number of carbon atoms in the internal olefin is 8 to 24, preferably 10 to 20, more preferably 12 to 18, even more preferably 14 to 18.
  • Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. When the internal olefin is sulfonated, ⁇ -sultone is generated quantitatively, and a part of ⁇ -sultone is converted to ⁇ -sultone and olefin sulfonic acid, which are then converted into compounds ( 4) and compound (5) (eg, J. Am. Oil Chem. Soc. 69, 39 (1992)).
  • the hydroxy group of the resulting compound (5) is inside the alkane chain and the double bond of compound (4) is inside the olefin chain.
  • the resulting product is mainly a mixture of these, and a part thereof includes a hydroxyalkanesulfonate having a hydroxy group at the end of the carbon chain, or a double bond at the end of the carbon chain. A trace amount of ⁇ -olefin sulfonate may also be contained.
  • IOS ⁇ -olefin sulfonate
  • the mass ratio of compound (4) to the mass of compound (5) with respect to 100% by mass of IOS is preferably 1/99 to 50/50, more preferably 1/99 to 30/70, even more preferably 5/95 to 20/80, and particularly preferably 10/90 to 15/85.
  • the compound (4)/compound (5) ratio is at least the above lower limit, the liquid stability is further enhanced. If the compound (4)/compound (5) ratio is equal to or less than the above upper limit, the detergency will be enhanced.
  • the content of the non-soap anionic surfactant is preferably 5 to 40% by mass, more preferably 10 to 40% by mass, even more preferably 10 to 30% by mass, further preferably 15 to 30% by mass, relative to the total mass of the liquid detergent. % by weight is particularly preferred. If the content of the non-soap anionic surfactant is at least the above lower limit, the detergency will be enhanced. In addition, anti-soil redeposition property is improved. When the content of the non-soap anionic surfactant is not more than the above upper limit, the fluidity of the liquid detergent is excellent and the liquid stability at low temperatures is improved.
  • the mass ratio of the nonionic surfactant to the mass of the non-soap anionic surfactant was 0.00. 1 to 3 are preferred, 0.15 to 2 are more preferred, 0.2 to 1.5 are even more preferred, and 0.25 to 1.3 are particularly preferred. If the nonion/anion ratio is within the above range, liquid stability at low temperatures is improved. In addition, the liquid detergent is less prone to gelation, and better fluidity can be maintained. When the liquid detergent contains an enzyme, the enzyme stability may decrease if the liquid detergent contains a non-soap anionic surfactant as the component (B). Enzyme stability can be maintained well.
  • cationic surfactants include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristate dimethylaminopropylamide, palmitate dimethylaminopropylamide, stearic acid dimethylaminopropylamide, Long-chain fatty amidoalkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or their salts; fatty ester alkyl tertiary amines such as palmitate ester propyl dimethylamine and stearate ester propyl dimethylamine or salts thereof; diethanolaminopropylamide palmitate, diethanolaminopropylamide stearate; tetra short chain (alkyl of 1 to 4 carbon atoms) such as tetramethylammonium salt, tetraethylam
  • the content of the cationic surfactant is preferably 0.1-5% by mass, more preferably 0.2-3% by mass, relative to the total mass of the liquid detergent. If the content of the cationic surfactant is within the above range, it is possible to further enhance the softening, antibacterial and deodorizing effects of clothes.
  • amphoteric surfactants examples include alkylbetaine-type, alkylamidobetaine-type, imidazoline-type, alkylaminosulfone-type, alkylaminocarboxylic acid-type, alkylamidocarboxylic acid-type, amideaminoacid-type, and phosphoric acid-type amphoteric surfactants. mentioned.
  • An amphoteric surfactant may be used individually by 1 type, and 2 or more types may be combined and used.
  • semipolar surfactants examples include alkylamine oxides, alkylamidopropyldimethylamine oxides, and the like. Semi-polar surfactants may be used singly or in combination of two or more.
  • the content of component (B) is preferably 15 to 80% by mass, more preferably 15 to 70% by mass, even more preferably 20 to 60% by mass, and 40 to 55% by mass relative to the total mass of the liquid detergent. Especially preferred. (B) If content of a component is more than the said lower limit, detergency will increase more. (B) If content of a component is below the said upper limit, a liquid cleaning agent will be hard to gelatinize, and it can maintain fluidity
  • Component (C) is one or more selected from water and water-miscible organic solvents. If the liquid detergent contains the component (C), it will have good fluidity.
  • Component may be used individually by 1 type, and may be used in combination of 2 or more types.
  • Purified water ion-exchanged water, distilled water, tap water, and the like can be used as water.
  • One type of water may be used alone, or two or more types may be used in combination.
  • the water content is preferably 3 to 30% by mass, preferably 5 to 25% by mass, more preferably 5 to 23% by mass, relative to the total mass of the liquid detergent. . If the content of water is at least the above lower limit, the viscosity suitable as a liquid detergent can be favorably maintained. If the content of water is equal to or less than the above upper limit, the liquid detergent is less likely to gel, and good fluidity can be maintained. In the case of a liquid detergent with a low surfactant concentration, the water content is preferably 60-85% by mass, more preferably 65-83% by mass, even more preferably 70-80% by mass.
  • the content of water is at least the above lower limit, the viscosity of the liquid cleaning agent can be lowered, thereby improving usability and making it less flammable. Furthermore, the compatibility between the components is improved, and the manufacturability and liquid stability are further enhanced. If the content of water is equal to or less than the above upper limit, the detergency and liquid stability will be enhanced.
  • the surfactant concentration is high means that the total content of the surfactant in the liquid cleaning agent is 40% by mass or more with respect to the total mass of the liquid cleaning agent.
  • Low surfactant concentration means that the total content of surfactants in the liquid detergent is less than 40% by mass with respect to the total mass of the liquid detergent.
  • a water-miscible organic solvent refers to an organic solvent that dissolves 50 g or more in 1 L of water at 25°C.
  • Water-miscible organic solvents include alcohols such as ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, 3-methoxy-3-methyl-1-butanol (Solfit, trade name); propylene glycol; (PG), butylene glycol, hexylene glycol and other glycols; diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of about 200 to 1000, dipropylene glycol and other polyglycols; diethylene glycol monomethyl ether, diethylene glycol monoethyl Alkyl ethers such as ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, and the like are included.
  • ethanol, glycerin, 3-methoxy-3-methyl-1-butanol, propylene glycol, and a molecular weight of about 200 to 1000 are preferred from the viewpoints of low odor, availability, fluidity of liquid detergents, and the like.
  • polyethylene glycol and diethylene glycol monobutyl ether (butyl carbitol) are preferred, and ethanol, glycerin and propylene glycol are more preferred.
  • the water-miscible organic solvents may be used singly or in combination of two or more. It is preferable to use propylene glycol and ethanol in combination from the viewpoints of enzyme stability (residual activity), appearance stability, and fluidity of the liquid detergent.
  • the content of the water-miscible organic solvent is preferably 3-40% by mass, more preferably 5-20% by mass, and even more preferably 8-15% by mass, relative to the total mass of the liquid detergent. If the content of the water-miscible organic solvent is at least the above lower limit, the appearance stability and fluidity of the liquid detergent will be good. When the content of the water-miscible organic solvent is equal to or less than the above upper limit, the stability of the enzyme is improved when the liquid detergent contains the enzyme.
  • the mass ratio of water to the mass of the water-miscible organic solvent is preferably 0.2 to 3, and 0.8. ⁇ 2.5 is more preferred, and 1-2 is even more preferred. If the water/organic solvent ratio is within the above range, the fluidity of the liquid cleaning agent is further improved.
  • the content of component (C) is preferably 6 to 60% by mass, more preferably 10 to 50% by mass, even more preferably 20 to 45% by mass, even more preferably 30 to 40% by mass, relative to the total mass of the liquid detergent. Especially preferred. If the content of the component (C) is at least the above lower limit, the appearance stability and fluidity of the liquid detergent will be good. If the content of the component (C) is equal to or less than the above upper limit, the stability of the enzyme is improved when the liquid detergent contains the enzyme.
  • Component is an inorganic alkaline agent.
  • the component (D) is a component that imparts detergency to the liquid detergent, especially detergency against sebum stains (sebum detergency).
  • the inorganic alkaline agent is a component that dissolves in whole or in part in water and exhibits basicity, and the pH of a 1% by mass aqueous solution at 25° C. is 8 or higher.
  • Specific examples of component (D) include sodium carbonate, sodium hydrogen carbonate, double salts of sodium carbonate and sodium hydrogen carbonate (sodium sesquicarbonate), potassium carbonate, carbonates such as potassium hydrogen carbonate; sodium metasilicate, layered silicon and silicates such as sodium phosphate.
  • Component may be used individually by 1 type, and 2 or more types may be combined and used.
  • the component (D) may be dissolved, or at least part of the component (D) may exist in a solid state.
  • the component (D) may be dissolved in the liquid detergent or may exist in a solid state without being dissolved. may be included.
  • component (D1) the component (D) dissolved in the liquid detergent
  • component (D1) the component (D) present in the liquid detergent in a solid state
  • component (D2) component the component (D) present in the liquid detergent in a solid state.
  • the entire amount of component (D) may be blended in the liquid detergent as it is, or an amount not exceeding the solubility of the total amount of component (D) may be blended in the liquid detergent and dissolved. may be incorporated into the liquid detergent.
  • the surface of component (D2) may be modified. If the surface of the component (D2) is modified, the component (D2) does not dissolve and the particle appearance (number of particles, particle size, etc.) can be maintained well, and the appearance stability of the component (D2) is enhanced. . In addition, the component (D2) is less likely to precipitate, improving dispersion stability. Furthermore, the dissolution rate of component (D2) can be controlled.
  • a method for modifying the surface of the component (D2) for example, a method of baking an inorganic alkaline agent can be used.
  • the surface-modified inorganic alkaline agent is also referred to as "modified alkaline agent".
  • sodium carbonate partially containing sodium bicarbonate and sodium sesquicarbonate is also regarded as a modified alkaline agent.
  • the surface of the component (D2) may be coated with a coating agent. That is, a coating layer may be formed on the surface of the component (D2). If the surface of the component (D2) is coated with a coating agent, the component (D2) does not dissolve and the particle appearance (number of particles, particle size, etc.) can be maintained well, and the appearance stability of the component (D2) increases. In addition, the component (D2) is less likely to precipitate, improving dispersion stability. Furthermore, the dissolution rate of component (D2) can be controlled. However, when the liquid detergent of the present invention is used in a washing machine or an automatic dispenser equipped with an automatic detergent dispenser, the surface of component (D2) should be It is preferably not coated with a coating. In this specification, an inorganic alkaline agent whose surface is coated with a coating agent is also referred to as a "coated alkaline agent".
  • Coating agents include, for example, hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or salts thereof, acrylic acid-maleic acid copolymers or salts thereof, acrylic acid-maleic anhydride copolymers or salts thereof.
  • fatty acid or its salt polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, aluminosilicate (zeolite, etc.), titanium oxide, and the like.
  • hydroxypropylmethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer are used from the viewpoint of controlling the solubility in the liquid detergent and maintaining the appearance of the particles.
  • acrylic acid-maleic anhydride copolymer or salt thereof, fatty acid or salt thereof, polyvinyl alcohol, pullulan, xanthan gum, starch, modified starch, sodium sulfate, calcium carbonate, hydroxypropyl methylcellulose, hydroxypropyl cellulose are preferable.
  • methylcellulose, polyacrylic acid or its salt, acrylic acid-maleic acid copolymer or its salt, acrylic acid-maleic anhydride copolymer or its salt, and sodium sulfate are more preferred.
  • a coating agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the coating alkali agent is a fluidized bed granulation method in which a coating agent is sprayed while fluidizing an inorganic alkali agent to granulate and coat.
  • agitating granulation method immersing and agitating an inorganic alkaline agent in a coating agent, distilling off the solvent to obtain granules and coated products, adding a coating agent to an inorganic alkaline agent, and kneading Extrusion granulation method of mixing and extruding this with an extruder, rolling granulation method of granulating and coating by spraying coating agent while rotating inorganic alkaline agent, spraying slurry containing inorganic alkaline agent and coating agent It can be obtained by a spray-drying granulation method or the like.
  • the coating agent may be dissolved or dispersed in any solvent and used in the form of a solution.
  • salt that makes the coating agent sensitive is added to the granules obtained by the above-described method using any machine such as a mixer, granulator, or fluidized bed, and mixed, A coated alkaline agent may be produced.
  • salt that sensitizes the coating material refers to a salt that increases the viscosity of the coating material, causes gelation, or forms a film.
  • Preferred examples of such sensitive salts include polyvalent chlorides such as calcium chloride, magnesium chloride and aluminum chloride; polyvalent sulfates such as magnesium sulfate and aluminum sulfate; polyvalent nitrates such as calcium nitrate and magnesium nitrate; polyvalent organic acid salts such as calcium acetate and calcium citrate; calcium oxide; calcium hydroxide; and sodium tetraborate.
  • polyvalent chlorides such as calcium chloride, magnesium chloride and aluminum chloride
  • polyvalent sulfates such as magnesium sulfate and aluminum sulfate
  • polyvalent nitrates such as calcium nitrate and magnesium nitrate
  • polyvalent organic acid salts such as calcium acetate and calcium citrate
  • calcium oxide calcium hydroxide
  • sodium tetraborate sodium tetraborate.
  • One type of sensitive salt may be used alone, or two or more types may be used in combination.
  • the ratio of the coating layer to 100 parts by mass of component (D2) is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass. If the ratio of the coating layer is at least the above lower limit, the effect of component (D2) covering the surface can be sufficiently obtained. If the ratio of the coating layer is not more than the above upper limit, the coating layer quickly dissolves, swells, disintegrates, or disperses in the washing liquid, and component (D2) can be prevented from being left undissolved. In addition, the amount of component (D2) per unit weight can be increased.
  • the particle size of component (D) is preferably 10 to 2000 ⁇ m, more preferably 100 to 1500 ⁇ m, even more preferably 200 to 1000 ⁇ m.
  • the particle size of component (D) is at least the above lower limit, the dissolution rate can be easily controlled, and the appearance of the particles can be excellent. If the particle size of the component (D) is equal to or less than the above upper limit, the dissolution rate in water is improved.
  • the particle size of component (D) is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the particle size of component (D) whose surface is not coated is preferably less than 200 ⁇ m, more preferably less than 100 ⁇ m.
  • the particle size of the component (D) is equal to or less than the above upper limit, the component (D2) dissolves quickly when the liquid detergent is diluted with water.
  • the solid component (D2) is less likely to remain on the inlet of the washing machine or on the clothes after washing. Therefore, if the particle size of component (D) is 200 ⁇ m or less, it is suitable for use in washing machines and automatic dispensers equipped with an automatic detergent injection function.
  • the particle size of the coated alkaline agent is preferably 10 to 2000 ⁇ m, more preferably 100 to 1500 ⁇ m, even more preferably 200 to 1000 ⁇ m.
  • the particle diameter of the coated alkaline agent is at least the above lower limit, the dissolution rate can be easily controlled, and the appearance of the particles is excellent. If the particle size of the coated alkaline agent is equal to or less than the above upper limit, the dissolution rate in water is improved.
  • the particle size of the coated alkaline agent is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the particle size of the component (D) and the particle size of the coated alkaline agent are measured by a laser diffraction scattering method using a particle size distribution analyzer (for example, manufactured by Beckman Coulter, Inc., product name "LS 13 320"). This is the standard median diameter.
  • the particle size may be measured by a dry method in which the component (D) or the coated alkaline agent is measured as it is, or by a wet method in which the component (D) or the coated alkaline agent is dispersed in a solvent and measured.
  • the content of component (D) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, even more preferably 2.5 to 10% by mass, relative to the total mass of the liquid detergent.
  • content of a component is more than the said lower limit, detergency will increase more.
  • content of a component is below the said upper limit, the fluidity
  • the ratio of the component (D2) is 10 to 80% by mass with respect to the total mass of the component (D). Preferably, 15 to 70% by mass, and even more preferably 20 to 60% by mass. If the ratio of component (D2) to the total mass of component (D) is equal to or less than the above upper limit, fluidity of the liquid detergent and beautiful appearance of particles can be obtained.
  • (E) component is a dispersant. If the liquid detergent contains the (E) component, it is possible to suppress re-adhesion of sebum stains and their decomposition products removed from the textiles during washing to the textiles. Therefore, it is possible to further suppress the occurrence of yellowing of the textile product, and the detergency against the yellowing of the textile product is further enhanced.
  • component (E) include alkylene oxide adducts of polyalkyleneimine, polycarboxylic acid polymers, and salts of polycarboxylic acid polymers.
  • (E) Component may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the polyalkyleneimine of the alkylene oxide adduct of polyalkyleneimine (hereinafter also referred to as "(E1) component”) is represented by, for example, the following general formula (6).
  • R 20 is each independently an alkylene group having 2 to 6 carbon atoms.
  • B represents a hydrogen atom or another branched polyamine chain.
  • g is a number of 1 or more. However, all of the above B are not hydrogen atoms.
  • the polyalkyleneimine represented by the general formula (6) has a branched polyamine chain in its structure.
  • R 20 is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms.
  • R 20 is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 carbon atoms.
  • the polyalkyleneimine is obtained by polymerizing one or more alkyleneimine having 2 to 6 carbon atoms by a conventional method.
  • the alkyleneimine having 2 to 6 carbon atoms includes ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and the like.
  • polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable.
  • PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in its structure.
  • the weight average molecular weight of the polyalkyleneimine is preferably 200-2000, more preferably 300-1500, even more preferably 400-1000, and particularly preferably 500-800.
  • the polyalkyleneimine preferably has 5 to 30 active hydrogens in one molecule, more preferably 7 to 25 active hydrogens, and even more preferably 10 to 20 active hydrogens.
  • the (E1) component is obtained by adding an alkylene oxide to a polyalkyleneimine.
  • an alkylene oxide such as ethylene oxide is added to the polyalkyleneimine starting material at 100 to 180°C. and the like.
  • Alkylene oxides include those having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred.
  • Component (E1) includes ethylene oxide adducts of polyalkyleneimine, propylene oxide adducts of polyalkyleneimine, and ethylene oxide-propylene oxide adducts of polyalkyleneimine.
  • the ethylene oxide-propylene oxide adduct of the polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to the polyalkyleneimine.
  • Component (E1) is preferably an ethylene oxide adduct of polyalkyleneimine or an ethylene oxide-propylene oxide adduct of polyalkyleneimine, more preferably an ethylene oxide adduct of polyalkyleneimine.
  • the component (E1) is preferably one in which an average of 5 to 40 alkylene oxides are added to 1 atom of the active hydrogen of the raw material polyalkyleneimine, and an average of 10 to 30 alkylene oxides are added. is more preferred. That is, it is preferable that an average of 5 to 40 mol of alkylene oxide is added per 1 mol of active hydrogen of the raw material polyalkyleneimine, and that of an average of 10 to 30 mol of alkylene oxide is more preferable.
  • the weight average molecular weight of component (E1) is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, even more preferably from 5,000 to 30,000, and particularly preferably from 10,000 to 20,000.
  • the mass average molecular weight in this specification means the value obtained by gel permeation chromatography using polyethylene glycol as a standard substance.
  • the (E1) component includes, for example, compounds represented by the following general formula (7).
  • each R 22 is independently an alkylene group having 2 to 6 carbon atoms.
  • Each h is independently a number of 1 or more.
  • R 22 is preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms.
  • h is the average repeating number of (R 22 O), each independently preferably 5-40, more preferably 10-30.
  • (E1) component may be used individually by 1 type, and may be used in combination of 2 or more types.
  • As the (E1) component a synthetic product or a commercially available product may be used.
  • the content of component (E1) is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 1 to 3% by mass, relative to the total mass of the liquid detergent. (E1) If the content of the component is at least the above lower limit, the detergency against yellowing will be better. If the content of the component (E1) is equal to or less than the above upper limit value, the appearance stability is improved.
  • polycarboxylic acid-based polymers and salts of polycarboxylic acid-based polymers include, for example, polyacrylic acid and its salts, polymaleic acid and its salts, acrylic acid -maleic acid copolymers and salts thereof, copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and salts thereof, acrylic acid-methacrylic acid copolymers and salts thereof, and the like.
  • the (E2) component is one or more selected from acrylic acid-maleic acid copolymers and salts thereof, and one selected from copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and salts thereof.
  • More than one species is preferable, and one or more species selected from copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and salts thereof are more preferable.
  • the salt may be partly or wholly, and the salt is preferably an alkali metal salt such as sodium or potassium or an organic amine salt such as alkanolamine.
  • the hydrocarbon having 4 to 12 carbon atoms in the component (E2) may be any one that can be copolymerized with maleic acid. Hydrocarbons of ⁇ 10 are more preferred, hydrocarbons of 4 to 9 carbon atoms are more preferred, hydrocarbons of 5 to 9 carbon atoms are particularly preferred, and hydrocarbons of 8 carbon atoms are most preferred. Such hydrocarbons include, for example, unsaturated chain hydrocarbons having double bonds.
  • the molar ratio of copolymerization of acrylic acid and maleic acid is preferably 50:50 to 80:20, more preferably 50:50 to 70:30. More preferably, 55:45 to 65:35 is even more preferable.
  • Higher proportions of acrylic acid are more soluble in liquid detergents.
  • the polymerizability is enhanced and the production of the copolymer is facilitated.
  • a higher proportion of maleic acid increases the ability to break down the insolubilized modified starch-calcium complex, resulting in higher detergency.
  • the (E2) component may be a crosslinked polymer or a non-crosslinked polymer.
  • the crosslinked polymer include a crosslinked polymer crosslinked by a crosslinking agent.
  • the cross-linking agent include allyl ether compounds.
  • the allyl ether compound include allyl ether, allyl ether of sugar, allyl ether of sugar alcohol, and the like.
  • the sugar include sucrose and the like.
  • Examples of the sugar alcohol include pentaerythritol.
  • the weight average molecular weight of component (E2) is preferably 1,000 to 100,000, more preferably 3,000 to 100,000, even more preferably 5,000 to 80,000, and particularly preferably 5,000 to 50,000. If the mass average molecular weight of the component (E2) is at least the above lower limit, the coating and washing properties of the liquid detergent will be improved. (E2) If the mass average molecular weight of the component is at most the above upper limit, the liquid stability of the liquid detergent will be improved.
  • the weight average molecular weight of a copolymer of a hydrocarbon having 4 to 12 carbon atoms and maleic acid is preferably 1,000 to 100,000, more preferably 3,000 to 50,000.
  • the copolymer of acrylic acid and maleic acid preferably has a mass average molecular weight of 5,000 to 100,000, more preferably 5,000 to 50,000.
  • the weight-average molecular weight is at least the above lower limit, it becomes easy to take out the laundry after washing from the washing machine. If the weight average molecular weight is equal to or less than the above upper limit, the liquid stability of the liquid detergent is improved.
  • (E2) component may be used individually by 1 type, and may be used in combination of 2 or more types.
  • As the (E2) component a synthetic product or a commercially available product may be used.
  • Commercially available products of component (E2) include, for example, one or more selected from copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and salts thereof.
  • the content of component (E2) is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 1 to 3% by mass, relative to the total mass of the liquid detergent. (E2) If the content of the component is at least the above lower limit, the detergency against yellowing will be better. (E2) If the content of the component is equal to or less than the above upper limit, the fluidity of the liquid detergent will be good.
  • the (E) component is preferably the (E1) component from the viewpoint of particularly excellent cleaning performance against yellowing and fluidity of the liquid detergent.
  • the ethylene oxide adduct of polyethyleneimine represented by the general formula (7) is particularly preferred.
  • the content of component (E) is preferably 0.02 to 10% by mass, more preferably 0.2 to 8% by mass, and even more preferably 1 to 6% by mass, relative to the total mass of the liquid detergent. (E) If the content of the component is at least the above lower limit, the detergency against yellowing will be better. (E) If content of a component is below the said upper limit, the fluidity
  • the total content of components (A) and (E) is preferably 0.07 to 15% by mass, more preferably 0.3 to 10% by mass, more preferably 1.1 to 1.1%, based on the total mass of the liquid detergent. 7% by mass is more preferred, and 2 to 5% by mass is particularly preferred. If the total content of the component (A) and the component (E) is at least the above lower limit, the detergency against yellowing will be better. If the total content of the component (A) and the component (E) is equal to or less than the above upper limit, the appearance stability of the liquid detergent will be good.
  • the mass ratio of component (A) to the mass of component (E), that is, the mass ratio (A/E ratio) represented by component (A)/component (E) is preferably 0.005 to 50, and 0.005 to 50.
  • 05 to 20 are more preferred, 0.1 to 10 are more preferred, 0.1 to 5 are particularly preferred, and 0.1 to 1 are most preferred. If the A/E ratio is at least the above lower limit, the detergency against yellowing will be better. If the A/E ratio is equal to or less than the above upper limit, the fluidity of the liquid detergent will be good.
  • Component is a structuring agent.
  • the liquid detergent is structured by containing the component (F). Therefore, when the liquid detergent contains insoluble particles (for example, the above-described component (D2)), the dispersion stability of the insoluble particles can be enhanced, the insoluble particles can be uniformly dispersed in the liquid detergent, and the state can be maintained satisfactorily. can.
  • the term “structured” refers to a state in which the viscosity changes before and after force is applied.
  • Structuring agents include, for example, bacterial cellulose, non-bacterial cellulose, and the following compound (8).
  • a structuring agent may be used individually by 1 type, and may be used in combination of 2 or more types.
  • Bacterial cellulose is cellulose produced by fermentation of bacteria of the genus Acetobacter.
  • Examples of bacterial cellulose include so-called mesh-like bacterial cellulose, in which water-insoluble fibers are branched into a network and mesh with each other to form a network.
  • At least part of the bacterial cellulose may be coated or mixed with a thickening agent.
  • Thickeners include, for example, carboxymethylcellulose (CMC), modified CMC, xanthan products, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, Examples include tamarind gum and locust bean gum.
  • a thickener may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Non-bacterial cellulose is cellulose obtained from vegetables, fruits, and wood, and is also called cellulose fiber.
  • non-bacterial cellulose commercially available products can be used, for example, the trade name "Avicel (registered trademark)” manufactured by FMC, the trade name “Citri-Fi” manufactured by Fiberstar, the trade name "Betafib” manufactured by Cosun, etc. mentioned.
  • the compound (8) is a compound (triglyceride component) represented by the following general formula (8).
  • Z 1 to Z 3 are each independently a hydrogen atom, a hydroxy group, or a carboxy group.
  • Z 1 to Z 3 may be the same or different.
  • the volume of the hydrophobic group portion becomes sufficiently bulky, and the coating detergency becomes high.
  • the risk of solidification due to bulkiness of the hydrophobic group portion is reduced.
  • Examples of compound (8) include compound (8-1) in which Z 1 to Z 3 are hydroxy groups, compound (8-2) in which Z 1 to Z 3 are hydrogen atoms, and the like.
  • Hydrogenated castor oil is particularly preferred as compound (8-1), and hydrogenated palm oil is particularly preferred as compound (8-2).
  • Hydrogenated castor oils may include glycerides, especially triglycerides, containing alkyl or alkenyl moieties with 10 to 22 carbon atoms incorporating hydroxyl groups, specifically trihydroxystearin, dihydroxystearin, and the like. Hydrogenated castor oil is obtained by hydrogenating castor oil to convert double bonds that may be present as ricinoleyl moieties in the starting oil.
  • Hydrogenated castor oil can be processed in any suitable starting form, including, but not limited to, which can be used in the solid state, the melt state, or mixtures thereof.
  • hydrogenated castor oil commercially available products can be used, for example, Rheox, Inc.; product name “THIXCIN (registered trademark)” manufactured by NOF Corporation, and product name “Caster Wax A Flake” manufactured by NOF Corporation.
  • Rheox, Inc. product name "THIXCIN (registered trademark)” manufactured by NOF Corporation
  • product name "Caster Wax A Flake” manufactured by NOF Corporation commercially available products can be used.
  • bacterial cellulose and non-bacterial cellulose are preferable because even a small amount thereof can sufficiently exhibit the effect of enhancing the dispersion stability of insoluble particles such as the component (D2), and a highly transparent liquid appearance can be easily obtained. , bacterial cellulose is more preferred.
  • the content of component (F) is preferably 0.02 to 2% by mass, more preferably 0.04 to 1.5% by mass, and further preferably 0.05 to 1% by mass, relative to the total mass of the liquid detergent. preferable.
  • the content of the component (F) is the actual content of the product. , preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 2.5 to 7% by mass, relative to the total mass of the liquid detergent.
  • the "content of the product as it is” means the content of the product itself, including the water contained in the product.
  • the content of the component (F) is at least the above lower limit, the dispersion stability of the insoluble particles such as the component (D2) is enhanced. If the content of the component (F) is equal to or less than the above upper limit, the viscosity of the liquid detergent becomes lower, and usability and liquid stability are further enhanced.
  • Optional components include builder components other than component (D), chelating agents, pH adjusters, viscosity reducers and solubilizers, enzymes, antibacterial agents, thickeners other than component (F), and Alkali agent, higher fatty acid or its salt, preservative, antioxidant, inorganic reducing agent, enzyme stabilizer, texture improver, dye transfer inhibitor, anti-soil redeposition agent other than component (E), coloring agent, emulsion agents, flavoring agents, anti-tarnishing agents, hydrotropic agents, bleaching agents, pearl agents, extracts of natural products, and the like.
  • Optional components may be used singly or in combination of two or more.
  • Builder components other than component (D) include, for example, sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium sulfite, potassium sulfite, sodium hydrogensulfite, ammonium chloride, ammonium sulfate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, sodium hydroxide, potassium hydroxide, aluminosilicates (eg, zeolite, etc.);
  • Other builder components may be used singly or in combination of two or more.
  • Other builder components may be dissolved in the liquid detergent or present in solid form.
  • the content of other builder components is preferably 20% by mass or less, more preferably 0.5 to 10% by mass, based on the total mass of the liquid detergent.
  • a chelating agent having a tri- or tetravalent carboxylic acid group or a salt thereof is preferred.
  • Specific examples include citric acid or its salts, aminocarboxylic acid-based chelating agents or its salts.
  • Aminocarboxylic acid refers to a compound containing at least one primary to tertiary amino group and at least one carboxyl group in one molecule, and an aminocarboxylic acid-based chelating agent is a chelating agent that is an aminocarboxylic acid.
  • Aminocarboxylic acid-based chelating agents that are known in the field of detergents can be used.
  • MGDA methylglycine diacetate
  • GLDA L-glutamic acid diacetic acid
  • DTPA diethylenetriamine pentaacetic acid
  • EDDS ethylenediamine succinate
  • HIDS 3-hydroxy-2,2'-iminodisuccinic acid
  • ASDA 3-hydroxy-2,2'-iminodisuccinate
  • L-aspartic acid-N,N-2 acetic acid ASDA
  • a chelating agent may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the content of the chelating agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the total mass of the liquid detergent. 0.1% by mass or more is more preferable. If the content of the chelating agent is at least the above lower limit, the detergency improving effect, liquid stability improving effect, and discoloration preventing effect can be sufficiently obtained.
  • pH adjusters examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine and lysine; ammonia; acid agents such as sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid. .
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • basic amino acids such as arginine and lysine
  • ammonia acid agents
  • sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid .
  • sodium hydroxide, sulfuric acid and hydrochloric acid are preferred.
  • the pH adjusters may be used singly or in combination of two or more.
  • the amount of the pH adjuster to be added may be appropriately set so as to adjust the pH of the liquid detergent to a predetermined value.
  • Viscosity reducers and solubilizers include, for example, aromatic sulfonic acids or salts thereof. Specific examples include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and salts thereof. Salts of aromatic sulfonic acids include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, alkanolamine salts, and the like.
  • the viscosity reducers and solubilizers may be used singly or in combination of two or more. The content of the viscosity reducer and the solubilizer is preferably 0.1 to 15% by weight with respect to the total weight of the liquid detergent.
  • the enzyme means an enzyme preparation.
  • a liquid enzyme preparation may be used, or a solid (granular) enzyme preparation may be used.
  • a solid enzyme preparation it is preferred that a part or the whole of it is present in the liquid detergent in a solid state from the viewpoint of enzyme stability.
  • enzymes examples include protease, amylase, lipase, cellulase, mannanase and the like.
  • protease trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 5L, Alcalase 5L, 2L, Alcalase, 2L, Alcalase, 2L, 2L, Alcalase, 16XL, Savinase Evity 16L, Savinase Ultra 16XL, Savinase Evity 16L, and Alcalase are available as protease preparations from Novozymes.
  • lipase include Lipex 100L, Lipolase 100L, Lipex 100T (trade names) available from Novozymes as lipase preparations.
  • Examples of cellulase include Endolase 5000L, Celluzyme 0.4L, Carezyme 4500L and Celluclean 4500T available from Novozymes as cellulase preparations, and REVITALENTZ 2000 available from DuPont.
  • Examples of mannanase include Mannaway 4L, Mannaway 4.0T and the like available from Novozymes as mannanase preparations.
  • the content of the enzyme is preferably 0.1-5% by mass, more preferably 0.3-3% by mass, and even more preferably 0.4-2.5% by mass, relative to the total mass of the liquid detergent. If the content of the enzyme is within the above range, the detergency will be enhanced and it will be economically advantageous.
  • Antibacterial agents include, for example, diclosan, triclosan, isopropylmethylphenol, polylysine, polyhexamethylenebiguanide, and the like. Among these, antibacterial agents having a diphenyl structure are preferred, and diclosan and triclosan are more preferred.
  • One type of antibacterial agent may be used alone, or two or more types may be used in combination.
  • the content of the antibacterial agent is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, even more preferably 0.03 to 2% by mass, relative to the total mass of the liquid detergent.
  • a liquid detergent contains an antibacterial agent having a diphenyl structure such as diclosan or triclosan
  • the liquid detergent tends to be colored when exposed to light, especially when the pH of the liquid detergent is high.
  • the liquid detergent contains the component (A)
  • the component (A) absorbs the light that hits the liquid detergent, thereby suppressing the reaction occurring between the phenyl groups and improving the stability against light. It is believed that the coloration of the liquid detergent when exposed to light can be suppressed.
  • the mass ratio of component (A) to the mass of the antibacterial agent having a diphenyl structure that is, the mass ratio represented by component (A)/antibacterial agent having a diphenyl structure (hereinafter also referred to as "A/antibacterial agent ratio"). is preferably 0.1 to 60, more preferably 0.25 to 60, more preferably 1 to 30, particularly preferably 1 to 10, most preferably 1 to 5. If there is, the stability of the liquid detergent against light is further improved, and coloration when exposed to light can be further suppressed. If the A/antibacterial agent ratio is equal to or less than the above upper limit, a sufficient antibacterial effect is likely to be obtained.
  • thickeners other than component (F) include acrylic polymers, xanthan gum, and galageenan.
  • examples of commercially available acrylic polymers include the Carbopol (registered trademark) series manufactured by Lubrizol.
  • the Carbopol series includes, for example, Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez20, Carbopol Ultrez21, Carbopol Aqua 30 and the like.
  • Other thickeners may be used singly or in combination of two or more.
  • the content of other thickening agents is preferably 6% by mass or less, more preferably 0.2 to 4% by mass, relative to the total mass of the liquid detergent.
  • alkaline agents other than component (D) examples include monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino Alkanolamine such as 2-methyl-1,3-propanediol, isopropanolamine and diisopropanolamine.
  • monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and diisopropanolamine are preferred.
  • Other alkaline agents may be used singly or in combination of two or more.
  • the content of the other alkaline agents is preferably 3-8% by mass, more preferably 4-6% by mass, relative to the total mass of the liquid detergent.
  • the antifoaming property refers to the property of suppressing foaming when washing with a liquid detergent, specifically when the liquid detergent is diluted with tap water or the like.
  • Higher fatty acids or salts thereof include single fatty acids or salts thereof such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, behenic acid; Fatty acids, mixed fatty acids such as beef tallow fatty acids, salts thereof, and the like are included.
  • Preferred higher fatty acids are lauric acid, myristic acid, palmitic acid and coconut oil fatty acid, and more preferred is coconut oil fatty acid.
  • Salt forms of higher fatty acids include, for example, alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). .
  • Higher fatty acids or salts thereof may be used singly or in combination of two or more.
  • the content of the higher fatty acid or its salt is preferably 0.5 to 10% by mass, more preferably 2 to 8% by mass, still more preferably 3 to 5% by mass, relative to the total mass of the liquid detergent. If the content of the higher fatty acid or salt thereof is at least the above lower limit, antifoaming properties are enhanced. If the content of the higher fatty acid or salt thereof is equal to or less than the above upper limit, liquid stability at low temperatures is improved.
  • antiseptics examples include 2-bromo-2-nitropropane-1,3-diol, 3-iodopropynylbutylcarbamate, zinc pyrithione, sodium pyrithione, octylisothiazolin-3-one, 1,2-benzisothiazolin-3-one.
  • BIT 5-chloro-2-methylisothiazolin-3-one
  • CMIT 2-methylisothiazolin-3-one
  • MIT 2-methylisothiazolin-3-one
  • ethoxylated cocoamine octanediol
  • benzyl alcohol phenoxyethanol
  • sodium benzoate sodium benzoate
  • the liquid detergent contains an antioxidant, oxygen absorption in the headspace of the container containing the liquid detergent can be suppressed. In addition, fading and discoloration due to light and heat can be suppressed.
  • antioxidants include monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenolic antioxidants such as 2,2′-methylenebis(4-methyl-6-t-butylphenol; dl- ⁇ -polymeric phenolic antioxidants such as tocopherol, etc.
  • monophenolic antioxidants and polymeric antioxidants are preferable.
  • the monophenolic antioxidants dibutylhydroxytoluene
  • polymeric phenolic antioxidants dl- ⁇ -tocopherol is particularly preferred.
  • An antioxidant may be used individually by 1 type, and 2 or more types may be combined and used.
  • the content of the antioxidant is preferably 0.01-2% by mass with respect to the total mass of the liquid detergent.
  • the liquid detergent contains an inorganic reducing agent, fading and discoloration due to light or heat can be suppressed.
  • the inorganic reducing agent include sulfites such as sodium sulfite and potassium sulfite; pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite; and bisulfites such as sodium hydrogensulfite and potassium hydrogensulfite.
  • sodium sulfite is preferable from the viewpoint of excellent liquid stability.
  • An inorganic reducing agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the inorganic reducing agent is preferably 0.01 to 3% by mass, more preferably 0.02 to 1% by mass, and even more preferably 0.05 to 0.5% by mass, relative to the total mass of the liquid detergent. . If the content of the inorganic reducing agent is at least the above lower limit, the effect of suppressing coloration due to light can be sufficiently obtained, and if it is at most the above upper limit, the liquid stability is enhanced.
  • Enzyme stabilizers include, for example, boric acid, borax, formic acid or salts thereof, lactic acid or salts thereof, calcium salts such as calcium chloride and calcium sulfate.
  • An enzyme stabilizer may be used individually by 1 type, and may be used in combination of 2 or more types. The content of the enzyme stabilizer is preferably 2% by mass or less with respect to the total mass of the liquid detergent.
  • the texture improver examples include silicones such as dimethylsilicone, polyether-modified silicone and amino-modified silicone.
  • the texture improver may be used singly or in combination of two or more.
  • the content of the texture improver is preferably 5% by mass or less with respect to the total mass of the liquid detergent.
  • dye transfer inhibitors examples include polyvinylpyrrolidone, carboxymethylcellulose, and polyalkyleneamine.
  • the dye transfer inhibitor may be used singly or in combination of two or more.
  • the content of the dye transfer inhibitor is preferably 3% by mass or less with respect to the total mass of the liquid detergent.
  • anti-soil redeposition agent other than the component (E) for example, at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units and , and at least one repeating unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units.
  • water-soluble polymers include the trade name “TexCare SRN-100” (manufactured by Clariant, weight average molecular weight 2000 to 3000), the trade name “TexCare SRN-300” (manufactured by Clariant, weight average molecular weight 7000), trade name “Repel-O-Tex Crystal” (manufactured by Rhodia), trade name “Repel-O-Tex QC” (manufactured by Rhodia), and the like.
  • TexCare SRN-100 is preferred because of its high solubility in water and excellent liquid stability.
  • TexCare SRN-170 manufactured by Clariant Co., Ltd.
  • Clariant Co., Ltd. which is commercially available as a 70% aqueous solution of TexCare SRN-100
  • Other anti-soil redeposition agents may be used singly or in combination of two or more.
  • the content of other anti-soil redeposition agents is preferably 0.01 to 5% by mass with respect to the total mass of the liquid detergent.
  • the coloring agent is not particularly limited, and examples thereof include dyes described in "Legal Dyes Handbook" (Japan Cosmetic Industry Association) and those chemically modified with a water-soluble polymer or the like at the end of the chromophore structure. be done. Specifically, C.I. I. Acid Red 138, C.I. I. Acid Red 260, C.I. I. Acid Red 106, Acid Yellow 203 (Yellow No. 203), Acid Blue 9, Blue No. 1, Blue No. 205, Green No.
  • Liquitint® BLUE SE Liquitint® Blue SE
  • Liquitint® BLUE HP Liquitint® Blue HP
  • Liquitint® BLUE MC Liquitint® Blue MC
  • Liquitint® VIOLET CT Liquitint® Violet CT
  • Liquitint® VIOLET LS Liquitint® Violet LS
  • Liquitint® VIOLET DD Liquitint® Violet DD
  • Liquitint® ) GREEN SA Liquitint (Registered Trademark) Green SA
  • Liquitint (Registered Trademark) Bright Yellow Liquitint (Registered Trademark) Bright Yellow
  • Liquitint (Registered Trademark) YELLOW SY Liquitint (Registered Trademark) Yellow SY
  • Liquitint (Registered Trademark) Trademark) YELLOW LP Liquitint (registered
  • colorants may be used singly or in combination of two or more.
  • the content of the colorant is preferably 0.00005 to 1.0% by mass, more preferably 0.00005 to 0.01% by mass, relative to the total mass of the liquid detergent. If the content of the coloring agent is at least the above lower limit value, the liquid detergent can be sufficiently colored, and if it is at most the above upper limit value, pigmentation on the object to be washed is less likely to occur, resulting in excellent dispersion stability. It becomes easy to obtain a liquid detergent.
  • emulsifying agents examples include polystyrene emulsions and polyvinyl acetate emulsions, and usually emulsions having a solid content of 30 to 50% by mass are preferably used. Specific examples include polystyrene emulsion (trade name: Saibinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.), Opulyn 301, Acusol OP 301, and the like.
  • the emulsifying agents may be used singly or in combination of two or more.
  • the content of the emulsifying agent is preferably 0.001-0.5% by mass with respect to the total mass of the liquid detergent.
  • flavoring agent for example, Kagaku Kogyo Nippousha, 1996, Genichi Indo, "Synthetic Perfume, Chemistry and Product Knowledge”; Montclair, 1969; J. published by STEFFEN ARCTANDER, "Perfume and Flavor Chemicals”. More specific examples include synthetic fragrances, natural fragrances derived from animals or plants, mixed fragrances containing natural and/or synthetic fragrances, and fragrance ingredients described in, for example, JP-A-2002-146399.
  • the flavoring agent may be formulated as a capsule fragrance encased in a capsule formed of a polymer compound. Flavoring agents may be used singly or in combination of two or more.
  • the content of the flavoring agent is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent. In addition, the total amount of all components constituting the liquid detergent does not exceed 100% by mass.
  • the pH of the liquid detergent at 25° C. is 9 or higher, preferably 9-12, more preferably 9-11, and even more preferably 9-10. If the pH of the liquid detergent is equal to or higher than the above lower limit, sebum stains, which are the cause of yellowing on textiles, are hydrolyzed and easily removed from the textiles, increasing the detergency against yellowing of textiles. If the pH of the liquid detergent is equal to or less than the above upper limit, damage to textile products such as clothes can be prevented.
  • the pH of the liquid detergent can be adjusted by adding a pH adjuster, if necessary.
  • the pH of the liquid detergent is a value measured with a pH meter (manufactured by Toa DKK Co., Ltd., product name "HM-30G”) at 25°C.
  • the method for producing the liquid detergent is not particularly limited, and the liquid detergent can be produced according to a conventional method.
  • the liquid detergent may contain the components (A), (B), and part of (C), and if necessary, components (D), (E), (F), and pH It can be produced by mixing one or more optional components other than the adjuster, adjusting the pH to a predetermined value using a pH adjuster as necessary, and then mixing the remaining component (C).
  • Liquid detergents can be used, for example, by putting the liquid detergent into the liquid detergent inlet of the washing machine and then running the washing machine, or by putting the liquid detergent into the water together with the object to be washed during washing. a method of immersing the object to be washed in a cleaning liquid prepared by previously dissolving a liquid detergent in water; a method of directly applying the liquid detergent to the object to be washed and leaving it for, for example, 3 minutes to 24 hours; and the like.
  • An automatic detergent dispenser is a device that automatically injects liquid detergent from a tank containing liquid detergent into the washing tub via a filter for dust removal provided at the bottom of the tank and an injection pipe. is.
  • a metering means such as a syringe pump is provided in the middle of the loading pipe so that a fixed amount set according to the amount of laundry can be transferred from the tank to the washing tub.
  • an automatic dispenser that can automatically dispense a predetermined amount of liquid. Even when an automatic dispenser is used, even a small amount of the liquid detergent can be measured accurately, so it is easy to exhibit sufficient detergency and waste due to overuse can be avoided, which is preferable.
  • Some automatic dispensers on the market use an infrared sensor or the like to automatically dispense without touching a switch or the like. If such an automatic dispenser is used, the amount of liquid detergent can be measured simply by holding out the container held in one hand, which greatly reduces the burden on the user.
  • the material of the soft container that can be thrown into the washing machine as it is include silicone resin, polyvinyl chloride, elastomer, soft polyester, soft polypropylene, and polyurethane.
  • Examples of articles to be washed include clothing (clothes), cloths, towels, sheets, and textile products such as curtains.
  • the material of the textile product is not particularly limited, and may be any of natural fibers such as cotton, silk and wool, and chemical fibers such as polyester and polyamide.
  • the liquid detergent is used by dissolving it in water, it is preferable to dilute it, for example, 5 to 6000 times (by volume).
  • the bath ratio mass of washing liquid during washing/mass of clothes
  • the bath ratio mass of washing liquid during washing/mass of clothes
  • Liquid detergents are suitable as detergents for textiles.
  • the washing machine or automatic washing machine equipped with an automatic detergent injection function can be used. Suitable for use in dispensers.
  • the liquid detergent of the present invention described above contains the components (A), (B) and (C), and has a pH of 9 or more at 25°C, so it has detergency against yellowing of textile products. Excellent for In particular, when the liquid detergent contains component (E), the detergency against yellowing of textiles is further enhanced. Moreover, if the liquid cleansing agent contains the (D) component, the detergency against sebum stains is further enhanced.
  • Raw materials used The compound shown below was used as a component.
  • ⁇ A-1 4,4′-bis(2-sulfostyryl)biphenyl disodium salt (manufactured by BASF, trade name “Tinopal (registered trademark) CBS-X”).
  • ⁇ A-2 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate (manufactured by ARCHROMA, trade name "Leucophor® DMA-X Conc").
  • B-2 A straight-chain alkylbenzenesulfonic acid having an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Lipon (registered trademark) LH-200”).
  • ⁇ B-4 IOS. The content of sodium internal olefin sulfonate and hydroxy form synthesized by the following synthesis method is 85% by mass. Synthesized by the synthesis method described below.
  • a nonionic surfactant obtained by block addition in the order of B-1 and B-5 are nonionic surfactants, and B-2 to B-4 are non-soap anionic surfactants.
  • a glass thin-film sulfonation apparatus with an inner diameter of 6 mm ⁇ and a length of 1.2 m was used to convert the reactor temperature to 10 with nitrogen - diluted SO gas (SO concentration: 5 % by volume). ° C. and a SO 3 /internal olefin molar ratio of 1.1, a sulfonation reaction was carried out in a conventional manner to obtain an internal olefin sulfonic acid.
  • the resulting reaction product internal olefinsulfonic acid
  • a neutralization reaction was carried out by stirring to obtain a neutralized product.
  • the neutralized product was then heated in an autoclave at 160° C. for 40 minutes and hydrolyzed to give B-4.
  • (C) The compound shown below was used as a component.
  • ⁇ C-1 Ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”).
  • ⁇ C-2 Propylene glycol (manufactured by Dow Chemical Company, trade name “propylene glycol”).
  • ⁇ C-3 water (ion-exchanged water).
  • ⁇ C-4 glycerin (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., trade name “glycerin”).
  • E The compound shown below was used as a component.
  • E-1 Alkylene oxide adduct of polyalkyleneimine (manufactured by BASF, trade name “Sokalan HP20”, compound in which R 22 is ethylene group and h is 20 in general formula (7)).
  • E-2 Copolymer sodium salt of olefin and maleic acid (manufactured by BASF, trade name "Sokalan CP9", weight average molecular weight 12000).
  • F-1 Bacterial cellulose (manufactured by CPKelco US, trade name “CELLULON (registered trademark) R27”, water content 80% by mass). The moisture content of F-1 was measured using an automatic moisture measuring device (manufactured by Hiranuma Sangyo Co., Ltd., product name "AQUACOUNTER AQV-2200").
  • a Terg-O-Tometer manufactured by UNITED STATES TESTING was used as a cleaning tester.
  • the cleaning liquid was prepared by adding the liquid cleaning composition of each example to 900 mL of tap water (15° C., 3° DH) so as to make 333 ppm by mass, and stirring for 30 seconds.
  • Detergency against yellowing was calculated for 10 soiled cloths, and the average value was used for evaluation based on the following evaluation criteria. ⁇ , ⁇ , and ⁇ were regarded as passed. "Evaluation criteria" A: Detergency against yellowing is 4.1 or more (no yellowing was observed). ⁇ : Detergency against yellowing is 4.0 or more and less than 4.1 (slight yellowing was observed). ⁇ : Detergency against yellowing is 3.9 or more and less than 4.0 (clear yellowing was observed). x: Detergency against yellowing is less than 3.9 (remarkable yellowing was observed).
  • Examples 1 to 12, Comparative Examples 1 and 2 In a 500 mL beaker, according to the formulations in Tables 1 and 2, (A) component, (B) component, C-1, C-2 and C-4, part of C-3, (E) The ingredients and optional ingredients other than the enzyme were added and sufficiently stirred with a three-one motor stirrer (manufactured by AS ONE Co., Ltd.) to obtain a mixture.
  • a three-one motor stirrer manufactured by AS ONE Co., Ltd.
  • the sum of the amount of C-3 used for preparing the mixture and the amount of water contained in F-1 is indicated as the amount of C-3 (% by mass) in Tables 1 and 2. .
  • the input amount of C-3 here is the amount obtained by subtracting the amount of water contained in F-1 from the blending amount of C-3 described in Tables 1 and 2.
  • the component (F) was added to the mixture and thoroughly stirred, and then the component (D) was added and thoroughly stirred.
  • the enzyme was added, and the remaining C-3 was added so that the total amount was 100% by mass to obtain a liquid detergent.
  • part of the component (D) existed in a solid state.
  • the pH of the obtained liquid detergent at 25° C. was measured using a pH meter (manufactured by Toa DKK Co., Ltd., product name “HM-30G”). Detergency against yellowing was evaluated for the obtained liquid detergent.
  • Nonionic/anionic ratio is the weight ratio of nonionic surfactant to weight of non-soap anionic surfactant.
  • A/E ratio is the weight ratio of component (A) to the weight of component (E).
  • A+E is the total content (% by mass) of the components (A) and (E) relative to the total mass of the liquid detergent.
  • the liquid detergent obtained in each example was excellent in detergency against yellowing.
  • the liquid detergents obtained in Examples 1 to 7 and 12 were excellent in detergency against yellowing.
  • the liquid detergent obtained in Comparative Example 1 having a pH of 7 and the liquid detergent obtained in Comparative Example 2 containing no component (A) were inferior in detergency against yellowing.
  • the liquid detergent of the present invention has excellent detergency against yellowing of textile products, and is useful as a detergent for textile products.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Ce détergent liquide contient un composant (A) qui est un agent azurant fluorescent, un composant (B) qui est un tensioactif et un composant (C) qui est au moins une substance choisie parmi l'eau et les solvants organiques miscibles à l'eau. Le détergent liquide a un pH supérieur ou égal à 9 à 25 °C. De préférence, le détergent liquide contient en outre un composant (D) qui est un agent alcalin inorganique et/ou un composant (E) qui est un dispersant.
PCT/JP2022/027501 2021-07-13 2022-07-13 Détergent liquide WO2023286794A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023199913A1 (fr) * 2022-04-13 2023-10-19 花王株式会社 Composition d'agent nettoyant liquide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001254100A (ja) * 2000-03-09 2001-09-18 Kao Corp 液体洗浄剤組成物
JP2008138070A (ja) * 2006-12-01 2008-06-19 Momentive Performance Materials Japan Kk 液体洗浄剤組成物
JP2009138057A (ja) * 2007-12-04 2009-06-25 Kao Corp 液体洗浄剤組成物
JP2012503091A (ja) * 2008-09-30 2012-02-02 ザ プロクター アンド ギャンブル カンパニー ２色又は多色効果を示す液体洗剤組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001254100A (ja) * 2000-03-09 2001-09-18 Kao Corp 液体洗浄剤組成物
JP2008138070A (ja) * 2006-12-01 2008-06-19 Momentive Performance Materials Japan Kk 液体洗浄剤組成物
JP2009138057A (ja) * 2007-12-04 2009-06-25 Kao Corp 液体洗浄剤組成物
JP2012503091A (ja) * 2008-09-30 2012-02-02 ザ プロクター アンド ギャンブル カンパニー ２色又は多色効果を示す液体洗剤組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023199913A1 (fr) * 2022-04-13 2023-10-19 花王株式会社 Composition d'agent nettoyant liquide

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