WO2012144438A1 - Détergent liquide - Google Patents

Détergent liquide Download PDF

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Publication number
WO2012144438A1
WO2012144438A1 PCT/JP2012/060133 JP2012060133W WO2012144438A1 WO 2012144438 A1 WO2012144438 A1 WO 2012144438A1 JP 2012060133 W JP2012060133 W JP 2012060133W WO 2012144438 A1 WO2012144438 A1 WO 2012144438A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
group
liquid detergent
carbon atoms
Prior art date
Application number
PCT/JP2012/060133
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English (en)
Japanese (ja)
Inventor
岳 瀧沢
剛 寺林
禎 飯原
知佳 小林
Original Assignee
ライオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to JP2013510977A priority Critical patent/JP5793563B2/ja
Priority to KR1020137022624A priority patent/KR101913880B1/ko
Publication of WO2012144438A1 publication Critical patent/WO2012144438A1/fr

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Classifications

    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to a liquid cleaning agent.
  • This application is filed in Japanese Patent Application No. 2011-092214 filed in Japan on April 18, 2011, Japanese Patent Application No. 2011-092215 filed in Japan on April 18, 2011, and in Japan on April 18, 2011. Claimed priority based on Japanese Patent Application No. 2011-092216 filed and Japanese Patent Application No. 2011-092217 filed in Japan on April 18, 2011, the contents of which are incorporated herein by reference.
  • the liquid detergent needs to ensure liquid stability (transparency uniformity, stability over time, etc.) as well as high detergency.
  • concentration of the surfactant is increased, viscosity increase or gelation occurs in the composition itself, resulting in poor liquid fluidity.
  • it becomes difficult to ensure a transparent and uniform appearance such as turbidity and precipitation.
  • a water-miscible organic solvent As a method for reducing the viscosity of a liquid detergent, a water-miscible organic solvent has been conventionally used.
  • certain non-ionic surfactants such as polyoxyethylene or polyoxyalkylene ethers, anionic surfactants (linear alkylbenzene sulfonates or polyoxyethylene alkyl ether sulfates) and water-miscible organics
  • a liquid detergent containing a solvent at a specific blending ratio is disclosed (see Patent Document 1). According to this liquid detergent, the composition itself is hardly gelled or increased in viscosity.
  • liquid detergent containing 50 to 70% by mass of a specific alkylene oxide adduct, 1 to 10% by mass of a non-soap anionic surfactant, and a water-miscible organic solvent (patent) Reference 2). According to this liquid detergent, it is said that it has a uniform appearance and is less likely to gel with time.
  • liquid detergents do not have the detergency (application washing power) necessary to remove protein stains by directly applying the liquid detergent to foods and other items to which protein stains adhere. It is enough. Furthermore, re-contamination of clothes is likely to occur during washing due to bulk washing in a large-capacity washing machine represented by a drum type washing machine and a decrease in bath ratio accompanying water-saving washing. In particular, re-contamination is likely to occur in hydrophobic chemical fibers such as polyester.
  • washing has been performed under conditions of a low bath ratio with less water.
  • many clothes and the like are often packed in a washing machine and washed.
  • re-contamination is likely to occur in which dirt once removed during washing adheres to clothing and the like again.
  • the objects to be washed in the washing tub are rubbed against each other, the fibers are damaged, the fiber surface is fluffed, and the part is whitened due to irregular reflection of light. It tends to cause a problem that it can be seen or the texture (comfort) after drying is deteriorated.
  • a method of imparting flexibility to an object to be washed by blending a cationic component is useful.
  • a liquid detergent containing a linear alkylbenzene sulfonate or polyoxyethylene alkyl ether sulfate as an anionic surfactant if the cationic component is blended, precipitation and precipitation are likely to occur, and the liquid stability It is difficult to secure.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent having good liquid flowability and liquid stability and having a high detergency against various stains.
  • an object of the present invention is to provide a liquid cleaning agent that is excellent in odor removal properties and coating detergency necessary for removing dirt by applying directly to an object to be washed
  • a liquid cleaning agent that is excellent in odor removal properties and coating detergency necessary for removing dirt by applying directly to an object to be washed
  • Another object of the present invention is to provide a liquid detergent that has good liquid flowability and liquid stability, has high detergency against various stains, and is excellent in recontamination prevention performance. .
  • Another object of the present invention is to provide a liquid cleaning agent that has good liquid flowability and liquid stability, has a high detergency against various types of dirt, and has an excellent flexibility imparting effect. .
  • the present invention also provides a liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in deodorizing performance and recontamination prevention performance. Is an issue.
  • a cationic component when added to a liquid detergent containing a linear alkylbenzene sulfonate or polyoxyethylene alkyl ether sulfate as an anionic surfactant, the cationic component and the anionic surfactant Precipitation and precipitation are likely to occur due to electrostatic interaction with the.
  • a composition having a high surfactant concentration it has been difficult to stably mix the cationic component and the anionic surfactant.
  • a method for the deodorization of odors generated from clothes after washing as described above, a method is conceivable in which a cationic compound having antibacterial properties is blended and caused to act on microorganisms such as microorganisms to exert a deodorizing effect.
  • a method of blending a linear alkylbenzene sulfonate as an anionic surfactant can be considered.
  • a cationic compound as an antibacterial or deodorant component and a linear alkylbenzene sulfonate as a component for preventing recontamination are blended in a composition having a high surfactant concentration, the respective performances are not fully exhibited. Also, it has been difficult to ensure liquid stability as a liquid preparation.
  • fatty acid alkyl ester sulfonates which are surfactants that are generally used in granular detergents and are not normally used in liquid detergents, and fatty acid alkyl ester alkoxylates at a specific blending ratio. It has been found that the above-mentioned problems can be solved by using in combination with a water-miscible organic solvent at a specific blending ratio, and the present invention has been completed.
  • a fatty acid alkyl ester sulfonate, a fatty acid alkyl ester alkoxylate which is a surfactant that is generally used in granular detergents and is not usually used in liquid detergents, and water-miscible. It has been found that the above problems can be solved by blending a specific polymer and a fatty acid or a salt thereof in a mixed system in which an organic solvent is used in combination at a specific blending ratio, and the present invention has been completed.
  • a fatty acid alkyl ester sulfonate, a fatty acid alkyl ester alkoxylate which is a surfactant that is generally used in granular detergents and is not usually used in liquid detergents, and water-miscible. It has been found that the above problems can be solved by blending a tertiary amine in a mixed system in which an organic solvent is used in a specific blending ratio, and the present invention has been completed.
  • a fatty acid alkyl ester sulfonate, a fatty acid alkyl ester alkoxylate which is a surfactant that is generally used in granular detergents and is not usually used in liquid detergents, and water-miscible. It has been found that the above problems can be solved by blending a cationic surfactant into a mixed system in which an organic solvent is used in combination at a specific blending ratio, and the present invention has been completed.
  • the present invention relates to a liquid detergent having a mass ratio represented by [(A) component + (B) component] / (C) component of 23 or less.
  • R 1 is a hydrocarbon group having 8 to 18 carbon atoms
  • R 2 is an alkyl group having 1 to 3 carbon atoms
  • M is a counter ion.
  • R 3 is a hydrocarbon group having 9 to 13 carbon atoms
  • R 4 is an alkylene group having 2 to 4 carbon atoms
  • R 5 is an alkyl group having 1 to 4 carbon atoms.
  • m represents the average number of repetitions of OR 4 and is an integer of 5 to 25.
  • R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group
  • R 8 is an alkylene group having 2 to 4 carbon atoms.
  • n represents an average number of repetitions of OR 8 and is an integer of 1 to 5.
  • R 6 is a hydrocarbon group having 10 to 20 carbon atoms.
  • EO is an oxyethylene group and PO is an oxypropylene group.
  • s represents the average number of repetitions of EO and is an integer of 5 to 20, and
  • t represents the average number of repetitions of PO and is an integer of 1 to 4.
  • R 1 , R 2 , M, R 3 , R 4 , R 5 , m, R 7 , R 8 and n have the same meaning as described above.
  • the liquid detergent may contain at least one silicone compound (G) selected from the group consisting of an amino-modified silicone compound, a carboxy-modified silicone compound, and a polyether-modified silicone compound. preferable.
  • an anionic surfactant (A) represented by the following general formula (a-1) and any one of the following general formula (b-1) and general formula (b-2) A group consisting of at least one nonionic surfactant (B) selected from the group consisting of the compounds represented by formula (1), an alcohol having 2 to 4 carbon atoms and a compound represented by the following general formula (c-1): At least one organic solvent (C) selected from the above and a cationic surfactant (H), and the total of the component (A) and the component (B) is 40% by mass or more,
  • the mass ratio represented by the components is 10 or less, and the mass ratio represented by the components (A) / (H) is 1 to 15.
  • a liquid detergent A liquid detergent.
  • a liquid detergent comprising at least one organic solvent (C) wherein the total of the component (A) and the component (B) is 40% by mass or more based on the total mass of the liquid detergent.
  • the liquid cleaning agent according to (1) which is ⁇ 15.
  • the liquid detergent according to (4) further comprising at least one silicone compound (G) selected from the group consisting of amino-modified silicone compounds, carboxy-modified silicone compounds, and polyether-modified silicone compounds.
  • the mass ratio represented by the [(A) component + (B) component] / (C) component is 10 or less, and the mass ratio represented by the (A) component / (D) component is The liquid detergent according to (1), which is 1 to 15.
  • the present invention it is possible to provide a liquid detergent having good liquid flowability and liquid stability and having a high detergency against various types of dirt.
  • the liquid cleaning agent in addition to liquid fluidity and liquid stability, is excellent in odor removability and coating detergency necessary for directly applying to the object to be washed to remove dirt. Can be provided.
  • liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in anti-recontamination performance.
  • liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various stains, and has an excellent flexibility imparting effect.
  • a liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various types of dirt, and is excellent in deodorization performance and recontamination prevention performance. can do.
  • the liquid detergent according to the first aspect of the present invention includes an anionic surfactant (A) represented by the general formula (a-1), the general formula (b-1) and the general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, alcohol having 2 to 4 carbon atoms, and the general formula (c-1) And at least one organic solvent (C) selected from the group consisting of the above compounds.
  • A anionic surfactant represented by the general formula (a-1), the general formula (b-1) and the general formula (b-2).
  • organic solvent (C) selected from the group consisting of the above compounds.
  • the liquid detergent according to the second aspect of the present invention includes an anionic surfactant (A) represented by the general formula (a-1) and a nonionic interface represented by the general formula (b-1).
  • the liquid detergent according to the third aspect of the present invention includes the anionic surfactant (A) represented by the general formula (a-1), the general formula (b-1) and the general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, alcohol having 2 to 4 carbon atoms, and the general formula (c-1) At least one organic solvent (C) selected from the group consisting of the above compounds, at least one repeating unit (d1) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and oxyalkylene units (d2). And a polymer (D) having a fatty acid or a salt thereof (E).
  • A anionic surfactant represented by the general formula (a-1), the general formula (b-1) and the general formula (b-2).
  • the liquid detergent according to the fourth aspect of the present invention includes the anionic surfactant (A) represented by the general formula (a-1), the general formula (b-1) and the general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, alcohol having 2 to 4 carbon atoms, and the general formula (c-1) And at least one organic solvent (C) selected from the group consisting of the above compounds and a tertiary amine (F).
  • A anionic surfactant represented by the general formula (a-1), the general formula (b-1) and the general formula (b-2).
  • organic solvent (C) selected from the group consisting of the above compounds and a tertiary amine (F).
  • the liquid detergent according to the fifth aspect of the present invention includes the anionic surfactant (A) represented by the general formula (a-1), the general formula (b-1) and the general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, alcohol having 2 to 4 carbon atoms, and the general formula (c-1) At least one organic solvent (C) selected from the group consisting of the above compounds and a cationic surfactant (H).
  • these components are also referred to as (A) component, (B) component, (C) component, (D) component, (E) component, (F) component, and (H) component, respectively.
  • the liquid detergent of the present invention can be used for household or industrial use, and can be suitably used for household use, and is a liquid of a concentrated type (composition having a high surfactant concentration) for clothing. Particularly suitable as a cleaning agent.
  • the hydrocarbon group for R 1 may be linear or branched, or may contain a cyclic structure.
  • the hydrocarbon group for R 1 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
  • R 1 has 8 to 18 carbon atoms, and preferably 10 to 16 carbon atoms. When the carbon number of R 1 is 8 or more, the detergency is improved, and in particular, odor removal is enhanced. On the other hand, when the carbon number of R 1 is 18 or less, the liquid stability is improved, and in particular, precipitation during gelation or low-temperature storage is suppressed.
  • R 2 is an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. An ethyl group is preferred.
  • the carbon number of R 2 is 1 or more, precipitation during low-temperature storage is easily suppressed.
  • the carbon number of R 2 is 3 or less, the solubility of the liquid detergent in water under low temperature conditions increases.
  • M is a counter ion and may be any one that can form a water-soluble salt with R 1 CH (COOR 2 ) SO 3 — , and may be an alkali metal, alkaline earth metal, proton An amine or ammonium that has been converted into an ammonium salt.
  • alkali metal include sodium or potassium.
  • alkaline earth metal include calcium and magnesium.
  • the amine may be any one of primary to tertiary, and preferably has a total carbon number of 1 to 6. The amine may or may not have a hydroxy group, but it has a hydroxy group because the solubility of the liquid detergent in water under low temperature conditions is increased. Is preferred.
  • Examples of such protonated amines include alkanolamines, and the alkanol group preferably has 1 to 3 carbon atoms.
  • Specific examples of the alkanolamine include monoethanolamine, diethanolamine, or triethanolamine.
  • M an alkali metal or a protonated amine is preferable, and sodium, potassium, or alkanolamine is more preferable, and sodium, monoethanolamine, or triethanolamine is more preferable.
  • a component can be manufactured by a well-known method.
  • ⁇ -sulfo fatty acid alkyl ester (acid type) is obtained by bringing a raw material fatty acid ester into contact with sulfuric anhydride or the like and sulfonating and esterifying by a conventional method using a tank reactor equipped with a stirrer. Get.
  • an alkali such as sodium hydroxide
  • a salt is formed at the sulfonic acid portion to obtain an ⁇ -sulfo fatty acid alkyl ester salt paste.
  • the paste of ⁇ -sulfo fatty acid alkyl ester salt obtained by the above reaction is usually an ⁇ -sulfo fatty acid di-salt (also referred to as ⁇ -sulfo fatty acid disodium salt).
  • ⁇ -sulfo fatty acid di-salt also referred to as ⁇ -sulfo fatty acid disodium salt.
  • by-products such as methyl sulfate (also referred to as sodium methyl sulfate), methanol, water, or unreacted starting fatty acid methyl ester.
  • a component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
  • ⁇ -sulfo fatty acid methyl ester salts are more preferable.
  • C 10 H 21 —CH (SO 3 Na) —COOCH 3 C 12 H 25 —CH (SO 3 Na) —COOCH 3 , C 14 H 29 —CH (SO 3 Na) —COOCH 3
  • a compound represented by the formula of C 16 H 33 —CH (SO 3 Na) —COOCH 3 can be given.
  • the blending amount of component (A) in the liquid detergent is preferably 2 to 42% by mass, more preferably 4.2, based on the total mass of the liquid detergent. Is 33% by mass, particularly preferably 7.5-26% by mass.
  • the blending amount of the component (A) in the liquid detergent is preferably 2 to 35% by mass, more preferably 4.5% with respect to the total mass of the liquid detergent. It is -29 mass%, Most preferably, it is 7.5-26 mass%.
  • the amount of component (A) in the liquid detergent is preferably 2 to 26% by mass, more preferably 4.2, based on the total mass of the liquid detergent. It is ⁇ 22 mass%, particularly preferably 6.8 to 18 mass%.
  • the amount of component (A) in the liquid detergent is preferably 2 to 28% by mass, more preferably 4.5%, based on the total mass of the liquid detergent. It is ⁇ 23 mass%, particularly preferably 7.5 to 20 mass%.
  • Nonionic surfactant (B) In the liquid detergent of the present invention, a compound represented by the following general formula (b-1) (hereinafter this compound is also referred to as “component (B1)”) and a general formula (b-2) It contains at least one nonionic surfactant (B) selected from the group consisting of compounds (hereinafter this compound is also referred to as “component (B2)”). This mainly provides cleaning performance.
  • the hydrocarbon group of R 3 may be linear or branched. Or a ring structure.
  • the hydrocarbon group for R 3 is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
  • R 3 has 9 to 13 carbon atoms, preferably 10 to 13 carbon atoms, and more preferably 11 to 13 carbon atoms. When the carbon number of R 3 is 9 or more, the detergency increases. On the other hand, when the carbon number of R 3 is 13 or less, the liquid stability is improved, and particularly gelation is suppressed.
  • R 4 is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group.
  • Two or more R 4 s in the formula may be the same as or different from each other. That is, the alkylene group for R 4 may be one kind alone, or two or more kinds may be combined.
  • m OR 4 in the formula is all oxyethylene groups or oxyethylene groups and oxypropylene groups are mixed. preferable.
  • the addition method of OR 4 is not particularly limited.
  • the addition method in the case where oxyethylene group and oxypropylene group are mixed includes random addition. There may be a block addition.
  • Examples of the block addition method include a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, or a method of adding propylene oxide after adding ethylene oxide and further adding ethylene oxide, etc. Is mentioned.
  • R 5 is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
  • R 5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
  • the carbon number of R 5 is 1 or more, precipitation during low-temperature storage is easily suppressed.
  • the carbon number of R 5 is 4 or less, the solubility of the liquid detergent in water under low temperature conditions is increased.
  • m represents an average number of repetitions of OR 4 and is an integer of 5 to 25.
  • m is 5 or more, the detergency, particularly the detergency against sebum dirt is improved.
  • m is 25 or less, the solubility of the liquid detergent in water is improved.
  • m is preferably an integer of 5 to 20, and more preferably an integer of 12 to 18.
  • OR 4 is a mixture of an oxyethylene group and an oxypropylene group
  • m is particularly preferably an integer of 12 to 21.
  • the average number of repeating oxypropylene groups is preferably an integer of 5 or less, more preferably an integer of 4 or less, and even more preferably an integer of 3 or less. If the average number of repeating oxypropylene groups exceeds 5, the cleaning power and liquid stability (transparency uniformity, stability over time, etc.) as a liquid cleaning agent may be deteriorated.
  • the narrow ratio indicating the distribution ratio of the compounds having different OR 4 repeat numbers is preferably 20% by mass or more. It is preferable that the upper limit of the narrow ratio is substantially 80% by mass or less.
  • the range of the narrow ratio is preferably 20 to 80% by mass, more preferably 20 to 50% by mass, and the liquid stability and the solubility in water are further improved. More preferably.
  • the higher the narrow rate the easier it is to obtain good detergency.
  • the said narrow rate becomes like this.
  • it is 20 mass% or more, Most preferably, it is 30 mass% or more, It becomes easy to obtain the liquid detergent composition with few raw material odors derived from (B1) component.
  • the “narrow ratio” refers to a value represented by the following formula (S), which indicates a distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.
  • m max represents the number of added moles of alkylene oxide of the alkylene oxide adduct that is most abundant in the whole component represented by the formula (b-1).
  • i represents the number of added moles of alkylene oxide.
  • Yi represents the proportion (mass%) of an alkylene oxide adduct having an added mole number of alkylene oxide present in the whole component represented by the formula (b-1).
  • the narrow rate can be controlled by, for example, the method for producing the component (B1).
  • the production method of the component (B1) is not particularly limited.
  • a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst JP 2000-2000A). 144194179)
  • Specific examples of such a surface-modified composite metal oxide catalyst include, specifically, metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 1) that have been surface-modified with a metal hydroxide or the like.
  • a composite metal oxide catalyst such as magnesium oxide, and a hydrotalcite fired product whose surface has been modified with a metal hydroxide and / or a metal alkoxide, etc. It is a catalyst.
  • the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide.
  • the ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.
  • a component may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
  • the hydrocarbon group for R 6 may be linear or branched. Or a ring structure.
  • the hydrocarbon group for R 6 is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
  • the hydrocarbon group of R 6 has 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms. When the carbon number of R 6 is 10 or more, the detergency increases. On the other hand, when the carbon number of R 6 is 20 or less, the liquid stability is improved, and particularly gelation is suppressed.
  • the component (B2) may be a single chain length mixture or a mixture of two or more chain lengths.
  • R 6 is derived from raw material alcohol (R 6 —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef tallow, and synthetic alcohols derived from petroleum.
  • s represents an average number of repetitions of EO (oxyethylene group), is an integer of 5 to 20, and is preferably an integer of 5 to 18.
  • t represents an average number of repetitions of PO (oxypropylene group), and is an integer of 1 to 4, and preferably an integer of 1 to 3.
  • EO and PO may be added in a block shape or may be added in a random shape.
  • the addition method includes adding ethylene oxide and then adding propylene oxide, adding propylene oxide and then adding ethylene oxide, or adding ethylene oxide and propylene.
  • examples thereof include a method of adding an oxide and further adding ethylene oxide.
  • a method in which ethylene oxide is added and then propylene oxide is added to further add ethylene oxide (the terminal is —O—CH 2 CH 2 O—H). Is preferred).
  • the addition mole number distribution of the alkylene oxide is not particularly limited, and the addition mole number distribution can be controlled by the production method of the component (B2).
  • a general alkali catalyst such as sodium hydroxide or potassium hydroxide
  • specific oxides such as magnesium oxide added with metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , or Mn 2+ described in Japanese Patent Publication No. 6-15038
  • an alkylene oxide is added to a hydrophobic raw material using an alkoxylation catalyst, a relatively narrow addition mole number distribution tends to be obtained.
  • a component may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
  • the component (B1) it is preferable to use the component (B1) because the combined use with the component (A) increases the cleaning power (especially odor removal).
  • the amount of component (B) in the liquid detergent is preferably 16 to 67% by mass, more preferably 23 to 59%, based on the total mass of the liquid detergent. % By mass, particularly preferably 30 to 55% by mass.
  • the blending amount of the component (B) (total of the components (B1) and (B2)) in the liquid detergent is 20 to 67 with respect to the total mass of the liquid detergent.
  • the mass is preferably 25% by mass, more preferably 25 to 59% by mass, and particularly preferably 30 to 55% by mass.
  • the blending amount of the component (B) (total of the components (B1) and (B2)) in the liquid detergent is 24 to 62 with respect to the total mass of the liquid detergent.
  • the content is preferably mass%, more preferably 27 to 57 mass%, and particularly preferably 32 to 51 mass%.
  • the blending amount of the component (B) (total of the components (B1) and (B2)) in the liquid detergent is 24 to 67 with respect to the total mass of the liquid detergent.
  • the mass is preferably 29% by mass, more preferably 29 to 59% by mass, and particularly preferably 35 to 55% by mass.
  • the sum of the (B1) component and the (B2) component with respect to the total of the nonionic surfactants blended in the liquid detergent of the present invention is [(B1) component + (B2) component] / nonionic interface.
  • the mass ratio represented by the activator is preferably 0.5 or more and 1.0 or less, more preferably 0.7 or more and 1.0 or less, and 0.85 or more and 1.0 or less. More preferably.
  • the mass ratio represented by [(B1) component + (B2) component] / nonionic surfactant is 0.5 or more and 1.0 or less, the detergency (especially odor removal property) is likely to be improved. In addition, usability as a liquid cleaning agent is improved.
  • the sum of the component (A) and the component (B) is 40% by mass or more based on the total mass of the liquid detergent. And preferably 40 to 70% by mass, more preferably 45 to 65% by mass, and still more preferably 50 to 65% by mass with respect to the total mass of the liquid detergent.
  • the total of the component (A) and the component (B) is 40% by mass or more based on the total mass of the liquid detergent, and the liquid detergent The total mass is preferably 40 to 65% by mass, more preferably 42 to 63% by mass, and still more preferably 45 to 60% by mass.
  • the effect of this invention is notably exhibited as the sum total of (A) component and (B) component is 40 mass% or more with respect to the total mass of the said liquid detergent. Further, high cleaning performance is imparted to the liquid cleaning agent. On the other hand, when the sum of the component (A) and the component (B) exceeds the preferable upper limit value, gelation hardly occurs and the liquid stability of the liquid detergent does not deteriorate.
  • component (A) / component (B) represents the ratio (mass ratio) of the content of component (A) to the content of component (B) in the liquid detergent.
  • Organic solvent (C) contains at least one organic solvent (C) selected from the group consisting of alcohols having 2 to 4 carbon atoms and a compound represented by the following general formula (c-1).
  • examples of the monohydric alcohol include ethanol, 1-propanol, 2-propanol, and 1-butanol.
  • examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, and glycerin.
  • R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group
  • R 8 is an alkylene group having 2 to 4 carbon atoms.
  • n represents an average number of repetitions of OR 8 and is an integer of 1 to 5.
  • Examples of the compound represented by the formula (c-1) include glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, or diethylene glycol monobutyl ether. System solvents and the like.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
  • the components (C) ethanol, propylene glycol, or diethylene glycol monobutyl ether is preferable from the viewpoint of easy improvement of the liquid flowability of the liquid detergent, mild odor, or easy availability of raw materials.
  • the amount of component (C) is preferably 3 to 20% by mass, more preferably 4 to 18% by mass, based on the total mass of the liquid detergent. Particularly preferred is 5 to 15% by mass.
  • the blending amount of the component (C) is preferably 5 to 30% by mass, more preferably 5 to 25% by mass with respect to the total mass of the liquid detergent.
  • the amount of component (C) is preferably 7 to 30% by mass, more preferably 7 to 25% by mass, based on the total mass of the liquid detergent. More preferably, it is 8 to 23% by mass, and particularly preferably 9 to 21% by mass.
  • the blending amount of the component (C) is at least the lower limit value, the liquid flowability of the liquid detergent becomes good, the gel does not gel, and it is easy to use as a liquid detergent. On the other hand, even if blending more than the upper limit, it is difficult to obtain the effect of improving the liquid fluidity corresponding to it, which is economically disadvantageous.
  • “[(A) component + (B) component] / (C) component” means the sum of the (A) component and the (B) component with respect to the content of the (C) component in the liquid detergent.
  • the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component.
  • the expressed mass ratio is 23 or less, preferably 2 to 23, more preferably 2.5 to 16.3, and still more preferably 3.3 to 13.
  • the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component.
  • the expressed mass ratio is 14 or less, preferably 2 to 14, more preferably 2 to 13, and still more preferably 2.4 to 9.3.
  • the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component.
  • the expressed mass ratio is 13 or less, preferably 1.6 to 13, more preferably 1.8 to 10.5, and still more preferably 2.1 to 8.6.
  • the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component.
  • the expressed mass ratio is 10 or less, preferably from 1.6 to 10, more preferably from 2 to 8.1, still more preferably from 2.4 to 7.2.
  • the mass ratio represented by [(A) component + (B) component] / (C) component exceeds the upper limit (the ratio of (A) component + (B) component is too high)
  • the viscosity of the liquid detergent Becomes higher (may cause gelation), the liquid fluidity of the liquid detergent tends to be lowered.
  • the usability as a liquid cleaning agent may worsen.
  • the mass ratio is less than the lower limit (the ratio of the component (C) is too high)
  • the viscosity of the liquid cleaning agent becomes too low, making it difficult to apply to the object to be cleaned, usability and application cleaning power. Tends to decrease.
  • the liquid detergent according to the third aspect of the present invention is a polymer (D) having at least one repeating unit (d1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (d2). Containing.
  • d1 repeating unit selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (d2). Containing.
  • d1 repeating unit selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (d2). Containing.
  • repeating unit (d1) selected from alkylene terephthalate units and alkylene isophthalate units
  • alkylene terephthalate unit hereinafter, this repeating unit is also referred to as “repeating unit (d11)”
  • repeating unit (d11) include repeating units represented by the following general formula (d1-1).
  • R 21 represents an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group of R 21 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
  • the repeating unit (d11) include an ethylene terephthalate unit, an n-propylene terephthalate unit, an isopropylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit, or a tert-butylene terephthalate unit.
  • isopropylene terephthalate units are preferred.
  • repeating unit (d12) examples include repeating units represented by the following general formula (d1-2).
  • R 22 represents an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group of R 22 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
  • the repeating unit (d12) include an ethylene isophthalate unit, a propylene isophthalate unit, an n-butylene isophthalate unit, a sec-butylene isophthalate unit, and a tert-butylene isophthalate unit. Of these, propylene isophthalate units are preferred.
  • a repeating unit (d1) may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate. That is, the component (D) may have only an alkylene terephthalate unit as a repeating unit (d1) in one molecule, may have only an alkylene isophthalate unit, You may have both an alkylene isophthalate unit.
  • the number of repeating units (d1) in one molecule in component (D) is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, and an integer of 2 to 4. Is more preferable. When the number of repeating units (d1) is 1 or more, the recontamination preventing performance is further improved, and when it is 10 or less, the liquid stability is further improved.
  • Oxyalkylene units (d2) examples of the oxyalkylene unit (hereinafter, this repeating unit is also referred to as “repeating unit (d2)”) include repeating units represented by the following general formula (d2-1).
  • R 23 represents an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group of R 23 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and particularly preferably 2 or 3 (R 23 O is an oxyethylene group or an oxypropylene group). Group).
  • a repeating unit (d2) may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate. That is, the component (D) may have, for example, only an oxyethylene unit, only an oxypropylene unit, or only an oxyethylene unit as a repeating unit (d2) in one molecule. And an oxypropylene unit.
  • the number of repeating units (d2) in one molecule in component (D) is preferably an integer of 1 to 100, more preferably an integer of 1 to 80, and an integer of 1 to 50. Is more preferable. When the repeating number of the repeating unit (d2) is 1 or more, the liquid stability is further improved. On the other hand, when it is 100 or less, the effect of preventing recontamination is more easily obtained.
  • the component (D) may have only an oxyalkylene group (when the number of repetitions is 1) as a repeating unit (d2) in one molecule, and a polyoxyalkylene unit (the number of repetitions is 2 or more). In the case of ()), it may have both an oxyalkylene group and a polyoxyalkylene unit.
  • the component (D) is preferably a polymer in which the repeating unit (d1) and the repeating unit (d2) are polymerized in a block shape or a random shape, and more preferably a polymer polymerized in a block shape.
  • the component (D) may have other units other than the repeating unit (d1) and the repeating unit (d2). Examples of the other unit include a unit derived from a polymerization initiator or a polymerization terminator, or a repeating unit derived from a monomer copolymerizable with a monomer that provides the repeating unit (d1) or the repeating unit (d2). .
  • the total of the repeating unit (d1) and the repeating unit (d2) is 80 mol% or more and 100 mol% with respect to all the units constituting the component (D). Or less, more preferably 90 mol% or more and 100 mol% or less.
  • the total of the repeating unit (d1) and the repeating unit (d2) is 80 mol% or more and 100 mol% or less, the anti-contamination performance of clothing is further enhanced.
  • the total of the repeating unit (d1) and the repeating unit (d2) is less than 80 mol%, the recontamination preventing performance is deteriorated.
  • the component (D) is preferably a water-soluble polymer from the viewpoint of its own solubility and the liquid stability of the liquid detergent.
  • water-soluble polymer as used herein means that 10 g of a polymer is added to 1000 g of water at 40 ° C. in a 1 liter beaker and stirred for 12 hours (200 rpm) with a stirrer (thickness 8 mm, length 50 mm). The one that completely dissolves.
  • the weight average molecular weight of the component (D) is preferably from 500 to 8000, more preferably from 800 to 7000, and particularly preferably from 1000 to 6000, because dissolution and dispersibility in water increases.
  • the “weight average molecular weight” here refers to a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent by a calibration curve in PEG (polyethylene glycol).
  • a 5% by mass aqueous solution having a pH (measured at 20 ° C.) of 3 to 7 is preferable.
  • This pH indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.
  • the component (D) preferably has a viscosity (measured at 50 ° C.) of 100 to 1000 mPa ⁇ s. This viscosity is a value measured using a No. 2 rotor in a Brookfield viscometer.
  • (D) What can be easily obtained in a market can be used for a component. Synthesis methods disclosed in the literature, such as Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948); Journal of Polymer Science, Vol. 8, pages 1 to 22 (1951); It can be produced by the method described in JP-A-61-218699.
  • suitable component (D) include polymers each containing a polymer represented by the following general formula (d-1) or a polymer represented by the general formula (d-2).
  • a and B are each independently a hydrogen atom or a methyl group, and R 24 to R 29 are each independently an alkylene group having 2 to 4 carbon atoms.
  • x1 and x2 are each independently an integer of 1 to 10.
  • y1, y2, z1 and z2 are each independently an integer of 1 to 100.
  • a and B are each preferably a methyl group, more preferably a methyl group.
  • R 24 , R 25 and R 26 are each preferably an alkylene group having 2 carbon atoms or an alkylene group having 3 carbon atoms.
  • x1 is an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 2 to 4.
  • y1 and z1 are each an integer of 1 to 100, preferably an integer of 1 to 80, more preferably an integer of 1 to 50, still more preferably an integer of 10 to 50, particularly preferably. It is an integer from 20 to 30.
  • A, B, x2, y2 and z2 are the same as A, B, x1, y1 and z1 in the formula (d-1), respectively.
  • R 27 , R 28 and R 29 are each preferably an alkylene group having 2 carbon atoms or an alkylene group having 3 carbon atoms.
  • ratio of x and y (x: y) and the ratio of x and z (x: z) are respectively The ratio is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18.
  • ratio (x: y) and the ratio (x: z) are in such a range, the anti-recontamination performance is sufficiently exhibited and the solubility in water is further improved.
  • ratio (x: y) means x1: y1 in the polymer represented by formula (d-1), and x2: y2 in the polymer represented by formula (d-2).
  • “Ratio (x: z)” means x1: z1 in the polymer represented by the formula (d-1), and x2: z2 in the polymer represented by the formula (d-2).
  • TexCare SRN-100 manufactured by Clariant, weight average molecular weight 2000 to 3000
  • TexCare SRN-300 manufactured by Clariant, weight average molecular weight 7000
  • TexCare SRN-100 having high solubility in water and little deterioration in washing performance after storage is preferable, and is a 70% by mass aqueous solution of TexCare SRN-100, which is trade name TexCare SRN-170 (Clariant).
  • a component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
  • the blending amount of the component (D) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the total mass of the liquid detergent.
  • the amount is particularly preferably 0.5 to 3% by mass.
  • a chain monocarboxylic acid having 8 to 18 carbon atoms is preferable.
  • R 9 is an aliphatic hydrocarbon group having 7 to 17 carbon atoms.
  • the compound represented by this is mentioned.
  • the aliphatic hydrocarbon group for R 9 may be linear or branched, linear or branched alkyl group, or linear or branched Alkenyl groups are preferred.
  • the aliphatic hydrocarbon group for R 9 has 7 to 17 carbon atoms, preferably 11 to 17 carbon atoms.
  • the aliphatic hydrocarbon group for R 9 is preferably derived from coconut oil.
  • alkali metal salt As a form of the salt in a component, alkali metal salt, alkaline-earth metal salt, amine salt, or ammonium salt etc. are mentioned.
  • alkali metal salt include sodium salt and potassium salt.
  • alkaline earth metal salts include calcium salts and magnesium salts.
  • the amine salt include alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate. Further, the component (E) may be a single chain length mixture or a mixture of two or more chain lengths.
  • the amount of the component (E) is preferably 0.05 to 5% by mass, more preferably 0.05 to 4% by mass, based on the total mass of the liquid detergent. Particularly preferred is 0.1 to 3% by mass.
  • the compounding quantity of a component is 0.05 mass% or more with respect to the total mass of the said liquid detergent, favorable rinse property is easy to be obtained and the recontamination prevention effect improves more. Further, the cleaning power is further improved. On the other hand, when it is 5% by mass or less, the liquid stability of the liquid detergent is further improved.
  • (D) component / (E) component represents the ratio (mass ratio) of the content of (D) component to the content of (E) component in the liquid detergent.
  • tertiary amine means a compound in which three hydrogen atoms of ammonia (NH 3 ) are substituted with a hydrocarbon group (the hydrocarbon group may have a substituent or a linking group). Is included.
  • the substituent that the hydrocarbon group may have include a hydroxy group and an amino group.
  • the linking group that the hydrocarbon group may have include an amide group, an ester group, and an ether group.
  • a preferable compound among the components (F) includes a compound represented by the following general formula (f-1).
  • R 11 and R 12 are each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or an oxyethylene group or an integer of 2 to 25 polyoxyethylene repeats] It is a group.
  • R 13 is a hydrocarbon group having 7 to 27 carbon atoms which may have a substituent or a linking group.
  • R 13 is a hydrocarbon group having 7 to 27 carbon atoms which may have a substituent or a linking group.
  • the hydrocarbon group for R 13 may be linear or branched, may contain a cyclic structure, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. May be.
  • R 13 has 7 to 27 carbon atoms, and preferably 7 to 25 carbon atoms. When the carbon number of R 13 is 7 or more, the effect of imparting flexibility to the article to be washed is enhanced.
  • the solubility of the component (F) in water increases.
  • “carbon number of R 13 ” does not include carbon in the substituent or linking group.
  • the hydrocarbon group for R 13 may have a hydroxy group or the like as a substituent, and may have an amide group, an ester group, an ether group or the like as a linking group in the hydrocarbon chain. .
  • the compounds represented by the formula (f-1) are particularly preferable. .
  • R 11 and R 12 are each the same as R 11 and R 12 in the formula (f-1).
  • R 14 is a hydrocarbon group having 7 to 23 carbon atoms
  • R 15 is a hydrocarbon group having 1 to 4 carbon atoms.
  • R 16 is a hydrocarbon group having 11 to 23 carbon atoms
  • R 17 is a hydrocarbon group having 1 to 4 carbon atoms.
  • the hydrocarbon group for R 14 may be linear or branched, or may contain a cyclic structure, and may be a saturated hydrocarbon group. Or an unsaturated hydrocarbon group.
  • the hydrocarbon group R 14 is preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
  • R 14 has 7 to 23 carbon atoms, and preferably 7 to 21 carbon atoms.
  • the hydrocarbon group for R 15 is preferably a linear alkylene group or a branched alkylene group.
  • the hydrocarbon group for R 16 may be linear or branched, or may contain a cyclic structure, and may be a saturated hydrocarbon group. Or an unsaturated hydrocarbon group.
  • the hydrocarbon group for R 16 is preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
  • R 16 has 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms.
  • the hydrocarbon group for R 17 is preferably a linear alkylene group or a branched alkylene group.
  • component (F) examples include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropyl.
  • Long-chain aliphatic amide dialkyl tertiary amines such as amide, behenic acid dimethylaminopropylamide, or oleic acid dimethylaminopropylamide (compound represented by the formula (f-1-1)); palmitic acid diethanolaminopropylamide Or a long-chain aliphatic amide dialkanol tertiary amine such as stearic acid diethanolaminopropylamide (compound represented by the above formula (f-1-1)); palmitate ester propyldimethylamine Or aliphatic ester dialkyl tertiary amines such as stearate ester propyldimethylamine (compound represented by the above formula (f-1-2)); or lauryl dimethylamine, myristyl dimethylamine, coconut alkyl dimethylamine, pal Methyl dimethylamine, beef tallow alkyl dimethylamine, hardened beef tallow alkyl dimethylamine, stearyl di
  • the long chain aliphatic amide dialkyl tertiary amine is a fatty acid or a fatty acid derivative (fatty acid lower alkyl ester, animal or plant). Oily fats and the like) and a dialkyl (or alkanol) aminoalkylamine are subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is distilled off under reduced pressure or nitrogen blowing.
  • fatty acid or fatty acid derivative examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, vegetable oil such as olive oil fatty acid and the like, or methyl ester, ethyl ester or glyceride thereof.
  • Dialkyl (or alkanol) aminoalkylamine refers to dialkylaminoalkylamine or dialkanolaminoalkylamine. Specific examples of the “dialkyl (or alkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is particularly preferable.
  • the amount of the dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidodialkyl tertiary amine is preferably 0.9 to 2.0 times the molar amount of the fatty acid or derivative thereof, 1.0 to A 1.5-fold mole is particularly preferred.
  • the reaction temperature for producing the long-chain aliphatic amidodialkyl tertiary amine is usually 100 to 220 ° C., preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction becomes too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored.
  • the production conditions other than those described above for the long-chain aliphatic amidodialkyl tertiary amine can be appropriately changed, and the pressure during the reaction may be normal pressure or reduced pressure, and is introduced by blowing an inert gas such as nitrogen during the reaction. It is also possible.
  • an acid catalyst such as sulfuric acid or p-toluenesulfonic acid, or when using a fatty acid derivative, an alkali catalyst such as sodium methylate, caustic potash, or caustic soda can be used at a low reaction temperature. The reaction can proceed efficiently in a short time.
  • the resulting tertiary amine is a long-chain amine having a high melting point
  • it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
  • a long-chain aliphatic amide dialkyl tertiary amine is particularly preferable because the effect of imparting flexibility to an object to be washed and liquid stability are both better.
  • Specific examples of commercially available long-chain aliphatic amidodialkyl tertiary amines include Kachinal MPAS-R (trade name) manufactured by Toho Chemical Co., Ltd.
  • the blending amount of the component (F) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the total mass of the liquid detergent. Particularly preferred is 1 to 5% by mass.
  • the blending amount of the component (F) is 0.1% by mass or more with respect to the total mass of the liquid cleaning agent, an effect of imparting flexibility to the object to be cleaned is easily obtained.
  • even if blending more than 10% by mass it is difficult to obtain an effect of imparting flexibility to the object to be washed, which is disadvantageous economically.
  • component (A) / component (F) represents the ratio (mass ratio) of the content of component (A) to the content of component (F) in the liquid detergent.
  • the mixing ratio of the component (A) to the component (F) is such that the mass ratio represented by the component (A) / component (F) is 1 to 15, and 1.5 to 10 Preferably, it is preferably 2-8.
  • the mass ratio represented by (A) component / (F) component is less than 1 (the ratio of (F) component is too high), the liquid stability of the liquid detergent may be lowered.
  • the mass ratio exceeds 15 the ratio of the component (A) is too high), it is difficult to obtain the blending effect of the component (F) (the effect of imparting flexibility to the object to be washed).
  • a quaternary ammonium salt type cationic surfactant is preferable.
  • the compound represented by the following general formula (h-1) since the liquid stability and deodorizing effect of the liquid detergent are better, the compound represented by the following general formula (h-1), the compound represented by the general formula (h-2) Or a compound represented by formula (h-3) is more preferable.
  • R 411 to R 414 is a hydrocarbon group having 8 to 22 carbon atoms, and the remaining two or more are each independently an alkyl group or carbon having 1 to 3 carbon atoms.
  • the hydrocarbon group in R 411 to R 414 has 8 to 22 carbon atoms and is linear. May be branched or may contain a cyclic structure.
  • the hydrocarbon group in R 411 to R 414 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group. Can be mentioned.
  • Z ⁇ is a counter ion, and examples thereof include a halogen ion and an alkyl sulfate ion.
  • Z ⁇ is a halogen ion
  • examples of Z constituting the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a chlorine atom is preferable.
  • Z - is when it is alkyl sulfate ion, as the Z constituting the alkyl sulfate ion, preferably those having an alkyl group having 1 to 3 carbon atoms.
  • Z ⁇ is preferably a halogen ion.
  • R 411 is a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched alkenyl group having 8 to 22 carbon atoms, and R 412 to R 414 are independent of each other.
  • a compound (H11) which is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms (hereinafter referred to as “component (H11)”);
  • R 411 and R 412 are each independently a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched alkenyl group having 8 to 22 carbon atoms, and
  • R 413 And R 414 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms (hereinafter referred to as “component (H12)”) Etc.
  • the alkyl group and alkenyl group of R 411 have 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms, and more preferably 16 to 18 carbon atoms.
  • R 411 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • R 412 to R 414 are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group.
  • R 411 and the alkyl group or alkenyl group of R 412 each have 8 to 22 carbon atoms, preferably 8 to 12 carbon atoms, and more preferably 8 to 10 carbon atoms.
  • R 411 and R 412 are each preferably a linear or branched alkyl group, more preferably a linear alkyl group, and both are linear alkyl groups. It is particularly preferred.
  • R 413 and R 414 are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group.
  • R 415 is a hydrocarbon group having 10 to 18 carbon atoms
  • R 416 is an aromatic hydrocarbon group which may have a substituent or an alkyl group having 1 to 3 carbon atoms.
  • x and y both represent the average number of repetitions of (CH 2 CH 2 O), each independently an integer of 0 or more, and x + y is an integer of 10 or more.
  • Z ⁇ is a counter ion.
  • the hydrocarbon group for R 415 is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
  • Examples of the aromatic hydrocarbon group for R 416 include a phenyl group and a naphthyl group.
  • R 416 include a methyl group, an ethyl group, a phenyl group, or a tolyl group.
  • x + y is an integer of 10 or more, preferably an integer of 10 to 50. If x + y is less than 10, the solubility of the compound itself in water tends to decrease, and the liquid stability of the liquid detergent may be deteriorated.
  • Z - is, Z in formula (h-1) - is the same as.
  • R 417 is a hydrocarbon group having 8 to 22 carbon atoms
  • R 418 and R 419 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
  • R 420 is an alkylene group having 1 to 3 carbon atoms.
  • Z ⁇ is a counter ion.
  • the hydrocarbon group in R 417 has 8 to 22 carbon atoms, and even if it is linear, it is branched. Or may include an annular structure.
  • the hydrocarbon group for R 417 is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
  • R 417 preferably a linear or branched alkyl group, more preferably a linear alkyl group.
  • the hydrocarbon group for R 417 has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms.
  • R 418 and R 419 are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group.
  • R 420 is preferably a methylene group.
  • Z - is, Z in formula (h-1) - is the same as.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
  • the compound represented by the above general formula (h-1), or the general formula is excellent in the deodorizing effect and easy to ensure the liquid stability of the liquid detergent.
  • the compound represented by (h-3) is preferable, and the compound represented by the general formula (h-1) is particularly preferable.
  • suitable component (H) include alkyltrimethylammonium chloride (for example, trade name “Arcard T-800” manufactured by Lion Akzo Co., Ltd .; component (H11)), didecyldimethylammonium chloride (for example, , Trade name “Arcade 210”, manufactured by Lion Akzo Co., Ltd .; (H12) component), or coconut alkyldimethylbenzylammonium chloride (for example, trade name “Arcade CB-50” manufactured by Lion Akzo Co., Ltd.), etc. it can.
  • alkyltrimethylammonium chloride for example, trade name “Arcard T-800” manufactured by Lion Akzo Co., Ltd .
  • component (H11) didecyldimethylammonium chloride
  • (H12) component) for example, Trade name “Arcade 210”, manufactured by Lion Akzo Co., Ltd .
  • coconut alkyldimethylbenzylammonium chloride for example, trade name
  • the amount of the component (H) is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass with respect to the total mass of the liquid detergent. Particularly preferred is 1 to 5% by mass.
  • the blending amount of the component (H) is 0.1% by mass or more with respect to the total mass of the liquid detergent, the deodorizing effect of odors (such as room-dried odors) generated from clothes after washing is further improved. To do.
  • the content is 10% by mass or less, transfer to the object to be washed, recontamination, and the like are suppressed.
  • effects such as suppression of coloring in the liquid cleaning agent, prevention of viscosity reduction, and stabilization of aroma are further improved. Furthermore, it becomes economically advantageous.
  • component (A) / component (H) represents the ratio (mass ratio) of the content of component (A) to the content of component (H) in the liquid detergent.
  • the blending ratio of the component (A) and the component (H) is such that the mass ratio represented by the component (A) / the component (H) is 1 to 15, and 1.5 to 10 Preferably, it is preferably 2-8.
  • the mass ratio represented by the component (A) / component (H) is less than 1 (the ratio of the component (A) is too low), it is difficult to sufficiently obtain the effect of preventing recontamination by blending the component (A). Moreover, there is a possibility that stable blending becomes difficult as a liquid detergent. On the other hand, if the mass ratio exceeds 15 (the ratio of the component (H) is too low), the effect of imparting antibacterial properties due to the blending of the component (H) is low, and sufficient deodorizing performance is difficult to be imparted.
  • the liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, liquid stability, and the like.
  • the blending amount of water in the liquid detergent according to the second to fourth aspects of the present invention is preferably 5 to 55% by mass, more preferably 5 to 45% by mass with respect to the total mass of the liquid detergent. It is more preferably 45% by mass, and particularly preferably 10 to 40% by mass.
  • the blending amount of water in the liquid detergent of the fifth aspect of the present invention is preferably 5 to 53% by mass, more preferably 5 to 50% by mass with respect to the total mass of the liquid detergent. Is more preferable. If the blending amount of water is 5% by mass or more, the liquid stability of the liquid detergent with time will be better, and if it is not more than the upper limit, the liquid viscosity will be moderately low and good from the viewpoint of usability. Become.
  • liquid cleaning agent of the present invention other components other than the components described above may be blended as desired within a range not impairing the effects of the present invention.
  • the other components are not particularly limited, and components usually used in a liquid detergent composition for clothing can be blended, and specific examples include the following.
  • the liquid detergent of the present invention can contain a surfactant other than the component (A), the component (B), the component (E), and the component (H).
  • the surfactant include an anionic surfactant other than the components (A) and (E), a nonionic surfactant other than the component (B), a cationic surfactant other than the component (H), or amphoteric. Surfactant etc. are mentioned.
  • the anionic surfactant other than the component (A) and the component (E) include linear alkylbenzene sulfonate, ⁇ -olefin sulfonate, linear or branched alkyl sulfate ester salt, and alkyl ether.
  • these salts include alkali metal salts such as sodium or potassium; alkaline earth metal salts such as magnesium; or alkanolamine salts such as monoethanolamine or diethanolamine.
  • the detergency is further improved. Therefore, as the nonionic surfactant other than the component (B), It is preferable to use these compounds together.
  • the compound represented by the formula (b′-3) is an alcohol ethoxylate (polyoxyethylene alkyl ether) in which an ethylene oxide having an average addition mole number v is added to an alcohol (R 10 —OH).
  • R 10 represents a hydrocarbon group having 10 to 22 carbon atoms.
  • v represents the average number of repetitions of (CH 2 CH 2 O) and is an integer of 5 to 20.
  • the hydrocarbon group for R 10 may be linear or branched, or may contain a cyclic structure.
  • the hydrocarbon group for R 10 is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
  • the hydrocarbon group of R 10 has 10 to 22 carbon atoms, preferably 10 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms. When the number of carbon atoms of R 10 is 10 or more, the detergency is improved especially with respect to sebum. On the other hand, when the carbon number of R 10 is 22 or less, the liquid stability and the solubility in water are further improved.
  • the compound represented by the formula (b′-3) may be a single chain length mixture or a mixture of two or more chain lengths.
  • R 10 is derived from the raw material alcohol (R 10 —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as palm oil, palm oil and beef tallow, and synthetic alcohols derived from petroleum.
  • v represents an average number of repetitions of (CH 2 CH 2 O), and is an integer of 5 to 20, preferably an integer of 8 to 18, preferably 10 to 16. More preferably, it is an integer.
  • v When v is in the above range, it exhibits excellent cleaning power against sebum dirt. Furthermore, when v is 5 or more, it becomes easy to prevent deterioration of the odor of the liquid cleaning agent. On the other hand, if v exceeds 20, the HLB (Hydrophile-Lipophile Balance) becomes too high, and the cleaning power against sebum dirt may be reduced.
  • HLB Hydrophile Balance
  • the addition mole number distribution of ethylene oxide is not particularly limited, and can be controlled by the production method of the compound represented by the formula (b′-3).
  • a common alkali catalyst such as sodium hydroxide or potassium hydroxide
  • the distribution tends to be relatively wide.
  • specific oxides such as magnesium oxide added with metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , or Mn 2+ described in Japanese Patent Publication No. 6-15038
  • ethylene oxide is added to a hydrophobic raw material using an alkoxylation catalyst, a relatively narrow addition mole number distribution tends to be obtained.
  • Specific examples of the compound represented by the formula (b′-3) include 12 or 15 moles relative to an alcohol such as the trade name Neodol (C12 / C13) manufactured by Shell or Safol 23 (C12 / C13) manufactured by Sasol.
  • An alcohol such as the trade name Neodol (C12 / C13) manufactured by Shell or Safol 23 (C12 / C13) manufactured by Sasol.
  • a product obtained by adding a considerable amount of ethylene oxide a product obtained by adding 9, 12, or 15 moles of ethylene oxide to a natural alcohol such as CO-1214 or CO-1270 manufactured by P &G; or having 12 to 14 carbon atoms
  • Examples include those obtained by adding 9, 12, or 15 moles of ethylene oxide to secondary alcohol (Nippon Shokubai Co., Ltd., Softanol 90, 120 or 150).
  • “C12 / C13” means a mixture of an alcohol having 12 carbon atoms and an alcohol having 13 carbon atoms.
  • nonionic surfactants other than the compounds represented by the formula (b-1) and the formula (b′-3) include alkylene oxide adducts of higher alcohols, alkylene oxide adducts of alkylphenols, higher fatty acids.
  • Alkylene oxide adducts higher amine alkylene oxide adducts, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyls
  • Examples include amine oxide, alkenylamine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, or alkyl glycoside.
  • Examples of the cationic surfactant other than the component (H) include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts.
  • amphoteric surfactants include amphoteric interfaces such as alkylbetaines, alkylamidebetaines, imidazolines, alkylaminosulfones, alkylaminocarboxylic acids, alkylamidecarboxylic acids, amide amino acids, or phosphates. An activator is mentioned.
  • the component (G) slipperiness is imparted to the washed object after washing, and the comfort of the washed object becomes better.
  • excellent comfort can be easily obtained even under harsh washing conditions such as when a large amount of clothing is packed at once.
  • the feeling of comfort at the time of wearing especially the clothing which consists of wool fibers improves more.
  • the amino-modified silicone compound is not particularly limited as long as it is a silicone having at least an amino group as a functional group.
  • examples of commercially available examples include BY16-871 and BY16-853U manufactured by Toray Dow Corning Co., Ltd. , FZ-3705, SF8417, BY16-849, FZ-3785, BY16-890, BY16-208, BY16-893, FZ-3789, BY16-878, or BY16-891 (all are trade names) It is done.
  • the carboxy-modified silicone compound is not particularly limited as long as it is a silicone having at least a carboxy group as a functional group.
  • the polyether-modified silicone compound is not particularly limited as long as it has at least a polyether group (such as a polyoxyethylene group or a polyoxypropylene group) as a functional group, and in particular, the following general formula (g-3)
  • a polyether group such as a polyoxyethylene group or a polyoxypropylene group
  • g-3 The polyether-modified silicone represented is preferred.
  • R 18 represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms.
  • R 19 is an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a hydrogen atom.
  • Y is a polyoxyalkylene group. a is an integer of 10 to 10,000, and b is an integer of 1 to 1000.
  • the alkylene group for R 18 may be linear or branched. If the number of carbon atoms of the alkylene group is within the above range, it is easy to synthesize industrially.
  • the alkyl group or alkenyl group for R 19 may be linear or branched. When the carbon number of the alkyl group or alkenyl group is within the above range, the fluidity of the component (G) itself is good and the handling thereof is easy.
  • Y is a polyoxyalkylene group, and the oxyalkylene group is preferably an oxyethylene group, an oxypropylene group, or an oxybutylene group, and two or more oxyalkylene groups may be mixed.
  • the number of repeating oxyalkylene groups is preferably an integer of 1 to 50, and more preferably an integer of 5 to 20.
  • a is an integer of 10 to 10,000, and preferably an integer of 20 to 1,000.
  • b is an integer of 1 to 1000, and preferably an integer of 2 to 100. If a and b are each in the said range, the feeling of comfort at the time of wearing especially the clothing which consists of wool fibers will improve more.
  • the order of each repeating unit to which a or b is attached may be different. That is, the repeating unit to which a is attached and the repeating unit to which b is attached may be added randomly, or each repeating unit may be added in a block form.
  • polyether-modified silicone compounds include SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, and SILWET L-7001, SILWET L-7002 manufactured by Toray Dow Corning Co., Ltd.
  • SILWET L-7602 SILWET L-7604, SILWET FZ-2104, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABNZILF1- 009-09, ABN SILWET FZ-F1-009-54, or ABN SILWET FZ-2222 (all are trade names); Etsu Chemical Industry Co., Ltd. of KF352A, KF6008, KF615A, KF6016, or KF6017 (trade names); or GE Toshiba Silicones Co., Ltd. TSF4450, TSF4452 (trade names), and the like.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
  • a polyether-modified silicone compound is particularly preferable because both the comfort of the object to be washed and the liquid stability are better.
  • the blending amount of the component (G) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass with respect to the total mass of the liquid detergent.
  • the compounding quantity of component is 0.1 mass% or more with respect to the total mass of the said liquid detergent, the feeling of comfort at the time of wearing especially the clothing which consists of wool fibers improves more.
  • even if it is added in an amount of more than 5% by mass it is difficult to obtain an effect of improving the comfort feeling commensurate with it, which is disadvantageous economically.
  • the blending ratio of the component (F) to the component (G) is such that the mass ratio represented by the component (F) / the component (G) is preferably 1 to 100, more preferably 1 to 25, It is more preferably 1 to 20, and particularly preferably 1 to 10.
  • the mass ratio represented by (F) component / (G) component is less than 1 (the ratio of (F) component is too low), it is difficult to obtain an excellent feeling of comfort for clothing made of wool fibers. .
  • the “(F) component / (G) component” represents the ratio (mass ratio) of the content of the (F) component to the content of the (G) component in the liquid detergent.
  • a thinning agent and a solubilizer, a metal ion scavenger, an antioxidant, or an antiseptic can be blended in the liquid detergent of the present invention.
  • the thickener and solubilizer include triethylene glycol, tetraethylene glycol, or glycols such as polyethylene glycol having an average molecular weight of about 200 to 5000; paratoluenesulfonic acid or a salt thereof, cumenesulfonic acid or a salt thereof, xylene Examples thereof include sulfonic acid or a salt thereof, benzoic acid or a salt thereof (also having an effect as a preservative), urea, and the like.
  • the blending amount of the viscosity reducing agent and the solubilizer in the liquid detergent is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent.
  • the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, and lactic acid.
  • the blending amount of the metal ion scavenger in the liquid detergent is preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent.
  • the antioxidant include butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogensulfite and the like.
  • the blending amount of the antioxidant is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent.
  • a preservative Rohm and House's Caisson CG (trade name) or the like can be used.
  • the preservative content is preferably 0.001 to 1% by mass relative to the total mass of the liquid detergent.
  • liquid detergent of the present invention includes a flexibility imparting agent described later or a texture improving agent described later; alkanolamine (for example, monoethanolamine, diethanolamine, triethanolamine, etc.) for the purpose of improving detergency and liquid stability.
  • alkanolamine for example, monoethanolamine, diethanolamine, triethanolamine, etc.
  • Alkali builders such as ethanolamine, N-methyl-diethanolamine, or N, N-dimethylmonoethanolamine; pH adjusters, hydrotropes, fluorescent agents, enzymes (eg, proteases, amylases, lipases, cellulases, mannanases, etc.) ), Dye transfer inhibitor, anti-staining agent other than component (D) (for example, water-soluble polymer having alkylene terephthalate and / or alkylene isophthalate unit, polyvinyl pyrrolidone, carboxymethyl cellulose, etc.), pearl agent, or soil release Agent It can contain.
  • component (D) for example, water-soluble polymer having alkylene terephthalate and / or alkylene isophthalate unit, polyvinyl pyrrolidone, carboxymethyl cellulose, etc.
  • pearl agent or soil release Agent It can contain.
  • Flexibility agents include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenine.
  • Long chain aliphatic amide alkyl tertiary amines such as acid dimethylaminopropylamide or oleic acid dimethylaminopropylamide or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like.
  • the blending amount of the flexibility-imparting agent in the liquid detergent is preferably 1 to 5% by mass with respect to the total mass of the liquid detergent.
  • texture improver examples include FZ-3707, FZ-3504, BY16-205, FZ-3760, FZ-3705, BY16-209, FZ-3710, SF8417, BY16-849, BY16 manufactured by Toray Dow Corning Co., Ltd.
  • pH adjusters examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid; organic acids such as polyvalent carboxylic acids or hydroxycarboxylic acids; or sodium hydroxide, potassium hydroxide, alkanolamine, or ammonia. Can be mentioned. Of these, sulfuric acid, sodium hydroxide, potassium hydroxide, or alkanolamine is preferable, and sulfuric acid, sodium hydroxide, or alkanolamine is more preferable from the viewpoint of the temporal stability of the liquid detergent.
  • a pH adjuster may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
  • an enzyme conventionally blended in a detergent for clothing can be used, and examples thereof include protease, amylase, lipase, cellulase, and mannanase.
  • Specific examples of the protease include protease preparations such as Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type 2.5, Erase Ultra 2.5L, Esperase Ultra 2.5L, Esperase Ultra 16L, Esperase Ultra L .5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, or Coronase 48L (all are trade names); or Purefect L, Perfect OX, or Properase L (all are trade names) available from Genencor.
  • amylase examples include, as an amylase preparation, Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, or Steinzyme Plus 12L available from Novozymes, Inc. Name), pullulanase Amano (trade name) available from Amano Pharmaceutical, or DB-250 (trade name) available from Seikagaku Corporation.
  • pullulanase Amano trade name
  • DB-250 trade name
  • lipase examples include Lipex 100L and Lipolase 100L (all of which are trade names) available from Novozymes as lipase preparations.
  • cellulase examples include Endolase 5000L, Celluzyme 0.4L, or Carzyme 4500L (all are trade names) available from Novozymes as cellulase preparations.
  • mannanase examples include Mannaway 4L (trade name) available from Novozymes as a mannanase preparation.
  • An enzyme may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
  • the enzyme content is preferably 0.1 to 3% by mass relative to the total mass of the liquid detergent.
  • a flavoring agent, a coloring agent, an emulsifying agent, or an extract such as a natural product may be blended for the purpose of improving the added value of the product.
  • Typical examples of the flavoring agent include fragrance compositions described in JP-A Nos. 2002-146399 and 2009-108248.
  • the blending amount of the flavoring agent is preferably 0.1 to 2% by mass with respect to the total mass of the liquid detergent.
  • the blending amount of the flavoring agent is preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent.
  • Examples of the colorant include Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, or Turquoise P-GR (all of which are trade names).
  • Examples include pigments and pigments.
  • the blending amount of the colorant in the liquid detergent is preferably 0.00005 to 0.005 mass% with respect to the total mass of the liquid detergent.
  • Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used.
  • polystyrene emulsion (trade name Cybinol RPX-196 PE-3, solid content 40 mass%, manufactured by Seiden Chemical Co., Ltd.) and the like.
  • the blending amount of the emulsion in the liquid detergent is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.
  • extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou,
  • the pH of the liquid detergent of the present invention is preferably 4 to 9 at 25 ° C., more preferably 4 to 8.
  • Adjustment of the pH of the liquid detergent is controlled by adding a certain amount of sulfuric acid, sodium hydroxide, alkanolamine or the like, for example, and then an inorganic acid (preferably hydrochloric acid or sulfuric acid) or water is used for fine adjustment of pH. It is preferable to carry out by further adding potassium oxide or the like.
  • the pH of the liquid detergent (controlled at 25 ° C.) is a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).
  • the liquid detergent of the present invention can be produced by a conventional method, for example, by mixing the above-described components.
  • the liquid detergent of this invention can be used by the method similar to the normal usage method of the general liquid detergent for clothes. That is, a method in which the liquid detergent is poured into the water together with the object to be washed at the time of washing, a method in which the liquid detergent is directly applied to the mud soil area or sebum soil area of the object to be cleaned, or the liquid detergent is preliminarily added to water. Examples include a method of dissolving and immersing clothes. Also preferred is a method in which the liquid detergent is applied to the article to be washed and then allowed to stand as appropriate, followed by ordinary washing using ordinary washing liquid. In that case, the usage-amount of the liquid cleaning agent of this invention can be made smaller than the usage-amount of the conventional liquid cleaning agent.
  • a liquid detergent containing alcohol and at least one organic solvent (C) selected from the group consisting of the compounds represented by formula (c-1) is
  • the second embodiment of the present invention includes C 10 H 21 —CH (SO 3 Na) —COOCH 3 , C 12 H 25 —CH (SO 3 Na) —COOCH 3 , C 14 H 29 —CH (SO 3 Na).
  • -COOCH 3, and C 16 H 33 -CH (SO 3 Na) -COOCH least one anionic surfactant 3 is selected from the group consisting of (a), C 11 H 23 -CO- (OCH 2 CH 2) m -OCH 3, and C 13 H 27 -CO- (OCH 2 CH 2) m of at least one nonionic surfactant is selected from the group consisting of -OCH 3 (B), and diethylene glycol monobutyl ether, propylene
  • a liquid detergent containing at least one organic solvent (C) selected from the group consisting of glycol and ethanol is preferred.
  • the number after the C represents the number of carbon atoms (the same applies hereinafter).
  • the above m is 15 on average.
  • the third embodiment of the present invention includes C 10 H 21 —CH (SO 3 Na) —COOCH 3 , C 12 H 25 —CH (SO 3 Na) —COOCH 3 , C 14 H 29 —CH (SO 3 Na).
  • a polymer represented by the general formula (d-1) or a polymer (D) each containing a polymer represented by the general formula (d-2), and a general formula: R 9 -COOH (R 9 is The liquid detergent containing the (E) component which is the compound or its salt represented by the same meaning as the above is preferable.
  • M is 15 on average.
  • the fourth embodiment of the present invention includes C 10 H 21 —CH (SO 3 Na) —COOCH 3 , C 12 H 25 —CH (SO 3 Na) —COOCH 3 , C 14 H 29 —CH (SO 3 Na).
  • a liquid detergent containing at least one tertiary amine (F) selected from the group consisting of stearic acid dimethylaminopropylamide and palmitic acid dimethylaminopropylamide is preferred, an amino-modified silicone compound, a carboxy-modified silicone compound
  • M is 15 on average.
  • the fifth aspect of the present invention includes C 10 H 21 —CH (SO 3 Na) —COOCH 3 , C 12 H 25 —CH (SO 3 Na) —COOCH 3 , C 14 H 29 —CH (SO 3 Na).
  • M is 15 on average.
  • the anionic surfactant (A) is C 12 H 25 —CH (SO 3 Na) —COOCH 3 (; C 14 H 29 —CH (SO 3 Na) —COOCH 3 ; C 10 H 21 —CH (SO 3 Na) -COOCH 3 and C 12 H 25 -CH (SO 3 Na) mixture of -COOCH 3; C 12 H 25 -CH (SO 3 Na) -COOCH 3 and C 14 H 29 -CH (SO 3 Na ) —COOCH 3 (; C 14 H 29 —CH (SO 3 Na) —COOCH 3 and C 16 H 33 —CH (SO 3 Na) —COOCH 3 ; or C 10 H 21 —CH ( the SO 3 Na) -COOCH 3, and C 12 H 25 -CH (SO 3 Na) -COOCH 3, and C 14 H 29 -CH (SO 3 Na) -COOCH 3, C 16 H A mixture with 33- CH (SO 3 Na) -COOCH 3 is more preferred.
  • the nonionic surfactant (B) of the second aspect of the present invention is C 11 H 23 —CO— (OCH 2 CH 2 ) m —OCH 3 ; or C 11 H 23 —CO— (OCH 2 CH 2 ). mixture of m -OCH 3 and C 13 H 27 -CO- (OCH 2 CH 2) m -OCH 3 are more preferred.
  • the nonionic surfactant (B) of the third to fifth aspects of the present invention is C 11 H 23 —CO— (OCH 2 CH 2 ) m —OCH 3 ; C 11 H 23 —CO— (OCH 2 CH 2 ) m -OCH 3 and C 13 H 27 -CO- (OCH 2 CH 2) a mixture of m -OCH 3; or a natural alcohol [12 carbon atoms alcohol (C12OH) and an alcohol having a carbon number of 14 (C14OH)
  • a nonionic surfactant obtained by randomly adding 16 mol of ethylene oxide and 2 mol of propylene oxide to a mixture, C12OH / C14OH (mass ratio) 7/3], is more preferable.
  • M is 15 on average.
  • the component (E) is more preferably coconut fatty acid or palmitic acid.
  • the tertiary amine (F) is a fatty acid (C16 / C18) dimethylaminopropylamide, that is, a mixture of stearic acid dimethylaminopropylamide and palmitic acid dimethylaminopropylamide; or C 17 H 35 CONH (CH 2 ) 3 N (CH 3 ) 2 is more preferable.
  • the cationic surfactant (H) is more preferably alkyl chloride (C16-C18) trimethylammonium, didecylmethylammonium chloride, or benzalkonium chloride.
  • the liquid detergent of the present invention described above has good liquid flowability and liquid stability, and has a high detergency against various stains.
  • the liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in recontamination prevention performance.
  • the liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in flexibility imparting effect. Further, the liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in deodorization performance and recontamination prevention performance. .
  • the liquid cleaning agent of the present invention removes dirt by applying it directly to the object to be washed, as well as liquid flowability and liquid stability, as well as the ability to remove odor caused by sweat and sebum residue after washing. It is excellent in the application cleaning power required.
  • the reason why such an effect is obtained is estimated as follows. In general, when the concentration of a surfactant as a cleaning component increases, the liquid cleaning agent increases the detergency, but the composition itself increases in viscosity, gels, and the like, resulting in poor liquid flowability. On the other hand, in a composition having a high surfactant concentration, conventionally, a water-miscible organic solvent is used in combination to reduce the viscosity.
  • the combined use of water-miscible organic solvents can easily reduce the cleaning power.
  • the cleaning power required to remove dirt by applying a liquid cleaning agent directly on the object to be cleaned (particularly The coating cleaning power is not sufficient.
  • removal of sweat and sebum stains adhering to chemical fibers such as polyester and polyurethane is not sufficient, an odor due to the remaining sweat or sebum stains may occur after washing.
  • the group consisting of the anionic surfactant (A) represented by the general formula (a-1) and the compounds of the general formula (b-1) and the general formula (b-2) By combining with at least one nonionic surfactant (B) selected more, even if a water-miscible organic solvent (C) is used in combination, the detergency is not reduced. This is presumed to be due to the interaction between the ester bond portion present in the component (A) and the ester bond portion present in the component (B). Such interaction is considered to increase the cleaning power, thus increasing the cleaning power against various types of dirt, and is considered to be excellent in odor removal and coating cleaning power.
  • (A) component and (B) component are a specific mixture ratio.
  • (A) component, (B) component, and (C) component are used in combination at a specific blending ratio, and further exhibit good liquid fluidity and liquid stability and high cleaning effect. Is considered to be demonstrated.
  • a specific polymer (D) and a fatty acid or a salt thereof (E) are blended in a mixed system of the components (A) to (C). Therefore, it also has excellent anti-recontamination performance.
  • the reason is presumed as follows.
  • the calcium ions contained in the tap water and the fatty acid anion derived from the component (E) are combined with each other to produce water-insoluble fatty acid calcium.
  • the component (A) (fatty acid alkyl ester sulfonate) has a very excellent soap dispersibility (scum dispersibility) compared to an anionic surfactant such as alkylbenzene sulfonate.
  • the combination of the component (A) and the component (E) increases the dispersibility of the water-insoluble fatty acid calcium during the cleaning treatment. Thereby, foaming is suppressed at the time of washing, cleaning components are quickly drained at the time of rinsing, and good rinsing properties are exhibited.
  • This good rinsing property increases the adsorption efficiency of the component (D) on clothes made of hydrophobic chemical fibers such as polyester even under washing conditions at a low bath ratio. For this reason, it is speculated that the liquid detergent of the present invention exhibits excellent anti-recontamination performance.
  • the liquid detergent according to the fourth aspect of the present invention has the effect of imparting flexibility by adding the tertiary amine (F) to the mixed system of the components (A) to (C). Excellent.
  • the reason is presumed as follows.
  • the component (A) fatty acid alkyl ester sulfonate
  • an anionic surfactant such as an alkylbenzene sulfonate.
  • This composite has moderate hydrophobicity and exhibits higher adsorptivity than the component (F) alone, especially on the surface of clothing made of hydrophobic chemical fibers such as polyester or polyurethane. For this reason, it is presumed that the liquid cleaning agent of the present invention exhibits an excellent flexibility imparting effect.
  • the specific silicone compound (G) is blended to improve the comfort of the laundry after washing.
  • a complex of (F) component and (G) component or a complex of (A) component, (F) component, and (G) component is formed in water during washing, and the complex is not covered.
  • the component (G) is efficiently adsorbed to the wash and high slipperiness is imparted to the wash.
  • the friction between the fibers is reduced, and the object to be washed is given flexibility without impairing the elasticity of the fibers, so that a good feeling of comfort is obtained. Guessed.
  • Such an effect is remarkably exhibited especially for clothing made of wool fibers.
  • the liquid cleaning agent of the present invention removes the odor of clothes (for example, those using hydrophobic chemical fibers such as polyester and polyurethane) that are worn during exercise, and feels finished (flexibility or comfort). Excellent grant.
  • the liquid detergent according to the fifth aspect of the present invention has a deodorizing performance and re-treatment by mixing the components (A) to (C) with the cationic surfactant (H). Excellent anti-contamination performance.
  • the components (A) to (C) and (H) are blended at a predetermined blending ratio, so that the anionic component (A) and the cationic component (H) are mixed. Both can be dissolved stably. For this reason, the compounding effect of each component shown below is exhibited.
  • the component (A) (fatty acid alkyl ester sulfonate) is more likely to form a complex with the component (H) in water at the time of washing than an anionic surfactant such as an alkylbenzene sulfonate.
  • This composite has moderate hydrophobicity and exhibits higher adsorptivity than the component (H) alone, particularly on the clothing surface made of hydrophobic chemical fibers such as polyester and polyurethane.
  • the antibacterial property is enhanced by the adsorption of the complex to the clothing surface. For this reason, it is estimated that the liquid cleaning agent of this invention is excellent in the deodorization of the odor (room-dried odor etc.) generated from the clothes etc. after washing.
  • the component (A) has a very excellent soap dispersibility (scum dispersibility) as compared with anionic surfactants such as alkylbenzene sulfonates.
  • soap dispersibility scum dispersibility
  • anionic surfactants such as alkylbenzene sulfonates.
  • liquid detergent according to the fifth aspect of the present invention even if the amount of the cationic surfactant (H) is small, the effect of deodorizing odors that are likely to occur due to room drying is exhibited.
  • compositions of the liquid cleaning agents in each example are shown in Tables 1 to 13.
  • the raw materials used in this example are as follows.
  • a-2 C 12 H 25 —CH (SO 3 Na) —COOCH 3 .
  • a-3 C 10 H 21 —CH (SO 3 Na) —COOCH 3 , C 12 H 25 —CH (SO 3 Na) —COOCH 3 , C 14 H 29 —CH (SO 3 Na) —COOCH 3
  • a-4 A mixture of C 12 H 25 —CH (SO 3 Na) —COOCH 3 and C 14 H 29 —CH (SO 3 Na) —COOCH 3 in a mass ratio of 2/8.
  • a-5 C 14 H 29 —CH (SO 3 Na) —COOCH 3 .
  • a-6 Mixture of C 14 H 29 —CH (SO 3 Na) —COOCH 3 and C 16 H 33 —CH (SO 3 Na) —COOCH 3 in a mass ratio of 8/2.
  • reaction solvent carbon tetrachloride
  • methanol manufactured by Kanto Chemical Co., Inc.
  • the reaction liquid was adjusted to pH 7 using 20 mass% sodium hydroxide aqueous solution.
  • the reaction solvent methanol was distilled off under reduced pressure. At that time, since it foamed, isopropanol was added, and water was also distilled off azeotropically.
  • the residue was heated to 50 to 60 ° C.
  • Comparative component (A ′) of component (A) a′-1 linear alkylbenzenesulfonic acid (LAS) having a linear alkyl group having 10 to 14 carbon atoms, trade name “Lypon LH-200”, manufactured by Lion Corporation, average molecular weight 322.
  • LAS linear alkylbenzenesulfonic acid
  • a nonionic surfactant obtained by random addition of 2 mol of ethylene oxide and 2 mol of propylene oxide.
  • the number after the C represents the number of carbon atoms.
  • Calcined alumina hydroxide / magnesium (unmodified) catalyst (2.2 g) obtained by firing with 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester Were charged into a 4 liter autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 1052 g of ethylene oxide was introduced and reacted while stirring.
  • reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added respectively, and then the catalyst was filtered off to obtain b-1-1.
  • b-1-1 having a narrow rate of 33% by mass was obtained.
  • aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes. Thereafter, unreacted ethylene oxide and propylene oxide were distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid is added and neutralized so that the pH of the 1% by mass aqueous solution of the reaction product becomes about 7 by adding b-2- 1 was obtained.
  • b′-3-1 polyoxyethylene alkyl ether obtained by adding ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms with an average addition mole number of 9 moles, trade name “Softanol 90” manufactured by Nippon Shokubai Co., Ltd.
  • b′-3-2 Polyoxyethylene alkyl ether obtained by adding ethylene oxide corresponding to an average addition mole number of 15 moles to natural alcohol CO-1270 manufactured by P & G.
  • B ′ Component Synthesis Method b′-1-1 Synthesis Except for using oleic acid methyl ester 350 g instead of lauric acid methyl ester 280 g and myristic acid methyl ester 70 g, and changing the amount of ethylene oxide introduced to 781 g. B′-1-1 was obtained in the same manner as in the synthesis method of b-1-1. By controlling the amount of alkali added to the catalyst, b′-1-1 having a narrow rate of 65% by mass was obtained.
  • c-1 Diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name “butyl diglycol”.
  • c-2 Propylene glycol, manufactured by BASF.
  • c-3 Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd. Trade name “Specific alcohol 95 degree synthesis”.
  • Polymer (D)] d-1 Product name “TexCare SRN-170” manufactured by Clariant. Weight average molecular weight 2000 to 3000, pH 4 (measured at 20 ° C., 5 mass% aqueous solution), viscosity 300 mPa ⁇ s (measured at 50 ° C.).
  • TexCare SRN-170 is trade name TexCare SRN-100 [manufactured by Clariant, weight average molecular weight 2000 to 3000, pH 4 (measured at 20 ° C., 5 mass% aqueous solution), viscosity 340 mPa ⁇ s (measured at 50 ° C.), the above formula 70% by mass aqueous solution of an assembly containing the polymer represented by (d-1).
  • d-2 Product name “TexCare SRN-300” manufactured by Clariant.
  • 10 g of polymer was added to 1000 g of water at 40 ° C. in a 1 liter beaker under the conditions of the above-mentioned “water-soluble polymer” and a stirrer (thickness 8 mm, long 50 mm), which completely dissolves when stirred (200 rpm) for 12 hours.
  • e-1 Palm fatty acid, trade name “coconut fatty acid” manufactured by NOF Corporation.
  • e-2 Palmitic acid, trade name “NAA-160”, manufactured by NOF Corporation.
  • [Tertiary amine (F)] f-1 Fatty acid (C16 / C18) dimethylaminopropylamide, manufactured by Toho Chemical Co., Ltd., trade name “Catinal MPAS-R”; mass ratio of stearic acid dimethylaminopropylamide to palmitic acid dimethylaminopropylamide 7 / A mixture of 3.
  • f-2 C 17 H 35 CONH (CH 2) 3 N (CH 3) 2, dimethylaminopropyl amide stearic acid; synthetic.
  • the temperature was maintained at 185 to 190 ° C., and aged for 7 hours to distill off by-product water out of the system. Further, while maintaining the temperature at 170 to 190 ° C., the pressure was reduced (4.0 kPa) and the mixture was allowed to stand for 1 hour, whereby unreacted dimethylaminopropylamine was distilled off to obtain f-2.
  • Comparison component (F ') of component (F) f′-1 Laurylamine, manufactured by Lion Akzo Co., Ltd., trade name “Armin 12D”.
  • g-1 Amino-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name “SZ8417”.
  • g-2 Polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name “SH3775M”.
  • h-1 Alkyl chloride (carbon number: C16 to C18) trimethylammonium, manufactured by Lion Akzo Co., Ltd., trade name “ARCARD T-800”.
  • h-2 Didecylmethylammonium chloride, manufactured by Lion Akzo Co., Ltd., trade name “Arcade 210”.
  • h-3 Benzalkonium chloride, manufactured by Lion Akzo Co., Ltd., trade name “ARCARD CB-50”.
  • Sodium benzoate manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
  • Citric acid trade name “Liquid Citric Acid” manufactured by Otsuka Kogyo Co., Ltd.
  • Trisodium citrate trade name “soda citrate” manufactured by Miles (USA).
  • Paratoluenesulfonic acid Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
  • coconut fatty acid NOF Corporation, trade name “Zushi fatty acid”.
  • Polyethylene glycol Product name PEG # 1000, manufactured by Lion Corporation.
  • Dibutylhydroxytoluene Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”. Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd. Perfume: Perfume a described in JP-A-2009-108248. Dye: Product name “Green No. 3”, manufactured by Sakai Kasei Corporation. pH adjuster: sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.), sulfuric acid (manufactured by Toho Zinc Co., Ltd.) or monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.). purified water.
  • liquid detergents of respective examples were prepared by the following production methods.
  • the blending amount shown in the table indicates the blending amount (pure equivalent amount) of the blending component.
  • a blank means that the blending component is not blended.
  • “(A) + (B) [mass%]” indicates the total content of the component (A) and the component (B) in the liquid detergent.
  • “(A) / (B)” means the mass ratio of the content of the component (A) to the content of the component (B) in the liquid detergent.
  • “[(A) + (B)] / (C)” is the mass ratio of the total content of the component (A) and the component (B) to the content of the component (C) in the liquid detergent. means.
  • the content of the component (B) means the total content of the component (B1) and the component (B2).
  • “(D) / (E)” means the mass ratio of the content of the component (D) to the content of the component (E) in the liquid detergent.
  • “(A) / (F)” means the mass ratio of the content of the component (A) to the content of the component (F) in the liquid detergent.
  • “(F) / (G)” means the mass ratio of the content of the component (F) to the content of the component (G) in the liquid detergent.
  • “(A) / (H)” means the mass ratio of the content of the component (A) to the content of the component (H) in the liquid detergent.
  • the composition of the common component (X) or common component (Y) contained in the liquid cleaning agent of each example is shown below.
  • the “appropriate amount” indicating the blending amount of the pH adjuster refers to an amount blended for adjusting the pH (25 ° C.) of the liquid detergent to 7.0.
  • “Balance” indicating the blending amount of purified water means the balance added so that the total blending amount (% by mass) of all the blending components contained in the liquid detergent is 100% by mass.
  • Common component (X) in Examples 17 to 39 and Comparative Examples 8 to 17 sodium benzoate 0.5% by mass, citric acid 0.1% by mass, paratoluenesulfonic acid 2.0% by mass, dibutylhydroxytoluene 0 0.05% by mass, 1.0% by mass of monoethanolamine, 0.4% by mass of perfume, 0.0003% by mass of pigment, appropriate amount of pH adjuster, and purified water balance.
  • Common component (X) in Examples 40 to 67 and Comparative Examples 18 to 30 sodium benzoate 0.5% by mass, citric acid 0.1% by mass, paratoluenesulfonic acid 2.0% by mass, coconut fatty acid 0. 5% by mass, 0.05% by mass of dibutylhydroxytoluene, 1.0% by mass of monoethanolamine, 0.0001% by mass of dye, appropriate amount of pH adjuster, and purified water balance.
  • the liquid detergents of each example were prepared by the following procedure.
  • (A) component or (A ') component, (B) component or (B') component, and (C) component were put into a 500 mL beaker, and it fully stirred with the magnetic stirrer (MITAMURA KOGYO INC.).
  • the common component (X) excluding the pH adjuster and purified water purified water was added so that the total amount became 98 parts by mass, and the mixture was further stirred.
  • pH adjuster sodium hydroxide or sulfuric acid
  • the liquid cleaning agents of each example were prepared by the following procedure.
  • a 500 mL beaker put (A) component or (A ′) component, (B1) component, (B2) component or (B ′) component, (E) component, and (C) component, and add a magnetic stirrer ( The mixture was sufficiently stirred with MITAMURA KOGYO INC.).
  • purified water was added so that the total amount became 98 parts by mass, and further stirred.
  • pH adjuster sodium hydroxide or sulfuric acid
  • Examples 40 to 67, Comparative Examples 18 to 30 According to the blending components of the compositions shown in Tables 7 to 10 and the blending amount (mass%), the liquid detergents of each example were prepared by the following procedure. In a 500 mL beaker, put (A) component or (A ′) component; (B1) component, (B2) component or (B ′) component; and (G) component in Examples 55 to 59 and Comparative Example 30 The mixture was sufficiently stirred with a magnetic stirrer (MITAMURA KOGYO INC.).
  • a magnetic stirrer MITAMURA KOGYO INC.
  • the purified water is added so that the total amount becomes 98 parts by mass. Stir well. After adding an appropriate amount of pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. becomes 7.0, purified water is added so that the total amount becomes 100 parts by mass to obtain a liquid detergent. It was.
  • pH adjuster sodium hydroxide or sulfuric acid
  • liquid detergents for each example were prepared by the following procedure.
  • a 500 mL beaker put (A) component or (A ′) component; (B1) component, (B2) component or (B ′) component; and (C) component, and use a magnetic stirrer (MITAMURA KOGYO INC.). Stir well.
  • purified water was added so that the total amount became 98 parts by mass, and further stirred.
  • pH adjuster diethanolamine or sulfuric acid
  • the pH of the liquid detergent was adjusted by adding the pH meter electrode to a solution adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation) for 2 minutes. It was measured by reading the later value.
  • liquid detergents of Examples 17 to 39 and Comparative Examples 8 to 17 were evaluated by the following evaluation methods. Evaluation of “sex” was performed. The results are also shown in Tables 4-6.
  • liquid detergents of Examples 40 to 67 and Comparative Examples 18 to 30 were evaluated by the following evaluation methods. Evaluation of “feel” and “usability” was performed. The results are also shown in Tables 7-10.
  • liquid fluidity For the liquid detergents of Examples 68 to 92 and Comparative Examples 31 to 41, “liquid fluidity”, “liquid stability”, “detergency”, “deodorizing performance”, “recontamination” were evaluated by the following evaluation methods. The prevention performance and the usability were evaluated. The results are also shown in Tables 11-13.
  • Evaluation criteria (1) 5 points: odorless, 4 points: finally a strong smell that can be sensed, 3 points: a smell that is strong enough to sense what kind of odor, 2 points: a smell that is easy to sense, 1 point: a strong smell, 0 points: Strong smell Evaluation criteria (2)
  • Examples 40 to 67 and Comparative Examples 18 to 30 were confirmed by the following method.
  • a test cloth was prepared by applying a mixed solution of oleic acid / ethanol, drying overnight and evaporating ethanol.
  • washing time rinsing, dehydration, and water volume (low water level set, water volume about 12 L)
  • no adjustment was made and the soft course setting of the washing machine was used.
  • the test cloth subjected to the above washing treatment was left in a constant temperature and humidity room at 25 ° C. and a relative humidity of 65% RH for one day and dried.
  • washing time rinsing, dehydration, and water volume (low water level set, water volume about 12 L)
  • no adjustment was made and the soft course setting of the washing machine was used.
  • the control cloth subjected to the washing treatment was left in a constant temperature and humidity room at 25 ° C. and a relative humidity of 65% RH and dried.
  • a liquid cleaning agent for cleaning the control cloth a 20% by mass aqueous solution of alcohol ethoxylate (trade name: EMALEX 715, Japan Emulsion) was used.
  • Evaluation of odor removability The test cloth washed in b) above was allowed to stand for 1 day, and the odor remaining on the test cloth was compared with the control cloth and scored according to the following evaluation criteria (5).
  • Evaluation criteria (5) 1 point: It smells intensely compared to the control cloth (dirt (oleic acid) is hardly removed). 2 points: It smells considerably compared to the control cloth (stain (oleic acid) is slightly removed). 3 points: Slightly weak smell compared to the control cloth (dirt (oleic acid) is slightly removed). 4 points: The smell is considerably lower than that of the control cloth. 5 points: Almost no odor remains compared to the control cloth.
  • Evaluation criteria (6) A: 4 points or more, B: 3.5 points or more, less than 4 points, C: 3 points or more, less than 3.5 points, D: less than 3 points.
  • the contaminated cloth, a clean knitted cloth, and 900 mL of tap water (25 ° C., hardness 3 ° DH) were put into (UNITED STATES TESTING) and stirred for 10 minutes (bath ratio 20, 120 rpm). Thereafter, it was transferred to a two-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation) and dehydrated for 1 minute. Next, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.
  • CW-C30A1 type manufactured by Mitsubishi Electric Corporation
  • washing rate (%) (Z value of contaminated cloth after washing ⁇ Z value of contaminated cloth before washing) / (Z value of raw cloth ⁇ Z value of contaminated cloth before washing) ⁇ 100
  • the coating cleaning power against the meat sauce stain it was determined that the coating cleaning power was good if it was C, B or A in the following evaluation criteria using the cleaning rate (%) calculated by the above formula.
  • the cleaning rate (%), the average point of 6 contaminated cloths was used. Evaluation criteria A: The cleaning rate is 20% or more. B: The cleaning rate is 15% or more and less than 20%. C: The cleaning rate is 10% or more and less than 15%. D: The cleaning rate is less than 10%.
  • a piece (a total of 45 g of a red soil dirt cloth, an oil dirt cloth, a test cloth, and a cotton cloth piece) was added and washed for 10 minutes (120 rpm, 15 ° C.). After completion of washing, the washing solution was removed, the test cloth was taken out, and the test cloth was dehydrated for 1 minute in a dewatering tank of a two-tank washing machine (CW-C30A1 manufactured by Mitsubishi Electric). Further, the test cloth was rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of tap water, and dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine. Thereafter, this operation was repeated twice (a total of three rinses).
  • the reflectances of two test cloths subjected to the above operation and the untreated one (white cloth) of the white polyester jersey test cloth were measured. Then, the difference (average value) in reflectance between the two test cloths subjected to the above operation and the white cloth was calculated as the “recontamination degree ( ⁇ Z)”.
  • the reflectance was measured using a color difference meter SE2000 (NIPPON DENSHOKU), and the ⁇ Z value was less than 9 (C, B, or A) as the acceptable range.
  • B The ⁇ Z value is 3 or more and less than 6.
  • C The ⁇ Z value is 6 or more and less than 9.
  • D The ⁇ Z value is 9 or more.
  • Examples 68 to 92 and Comparative Examples 31 to 41 The anti-contamination performance of Examples 68 to 92 and Comparative Examples 31 to 41 was confirmed by the following method. 900 mL of tap water (25 ° C., hardness 3 ° DH) and 0.3 mL of a liquid detergent were placed in a Terg-O-Tometer (UNITED STATES TESTING CO. INC. Model 243S) and stirred at 60 rpm for 3 minutes.
  • 900 mL of tap water (25 ° C., hardness 3 ° DH) and 0.3 mL of a liquid detergent were placed in a Terg-O-Tometer (UNITED STATES TESTING CO. INC. Model 243S) and stirred at 60 rpm for 3 minutes.
  • test cloth was rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of tap water, and dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine. Thereafter, this operation was repeated twice (a total of three rinses).
  • the reflectances of the two test cloths subjected to the above operation and the untreated (before washing) test cloth (white cloth) of the white polyester tropical were measured. Then, the difference (average value) in reflectance between the two test cloths subjected to the above operation and the white cloth was calculated as the “recontamination degree ( ⁇ Z)”.
  • the reflectance was measured using a color difference meter SE2000 (NIPPON DENSHOKU), and the ⁇ Z value was less than 9 (C, B, or A) as the acceptable range.
  • Evaluation criteria (7) 1 point: Harder than the control cloth. 2 points: Equivalent to the control cloth. 3 points: Slightly softer than the control cloth. 4 points: considerably softer than the control cloth. 5 points: Very softer than the control fabric. And the average score of five panelists' scoring was computed, and the softness
  • the cardigan blouse washed by repeating this washing operation 5 times was left in a constant temperature and humidity room at 25 ° C. and a relative humidity of 65% RH.
  • Evaluation criteria (9) 1 point: The comfort is considerably worse than the control product. 2 points: Slightly less comfortable than the control. 3 points: Comfort is equivalent to the control product. 4 points: Slightly more comfortable than the control. 5 points: Comfort is much better than the control product. And the average score of 5 panelists' scoring was computed, and the feeling of comfort was evaluated by the following evaluation criteria (10). Evaluation criteria (10) A: 4 points or more, B: 3.5 points or more, less than 4 points, C: 3 points or more, less than 3.5 points, D: less than 3 points.
  • a cotton skin shirt and 10 mL of a liquid cleaning agent were added, and a cleaning operation was performed in which cleaning, rinsing, and dehydration were sequentially performed in a standard course.
  • a cleaning operation was performed in which cleaning, rinsing, and dehydration were sequentially performed in a standard course.
  • the film was dried all day and night in a constant temperature and humidity room at 25 ° C. and a relative humidity of 85% or more.
  • Each “unpleasant odor” of the dried clothes was evaluated according to the following six evaluation criteria (11) by sensory sense. The evaluation was conducted by five expert panelists. Evaluation criteria (11) 0 point: odorless.
  • Evaluation criteria (13) 5 points: Both meterability and applicability are very good. 4 points: Both meterability and applicability are slightly good. 3 points: Neither can be said. Two points: Both meterability and applicability are not good. 1 point: Both meterability and applicability are not very good. Evaluation criteria (14) A: The average score is 4 or more. B: The average score is 3.5 points or more and less than 4 points. C: The average score is 3 or more and less than 3.5. D: The average score is less than 3.
  • the liquid detergents of Examples 1 to 16 to which the present invention is applied have good liquid flowability and liquid stability, and a high detergency (odor removal property, In addition, it can be seen that it has a coating cleaning power necessary for directly applying to an object to be cleaned and removing dirt.
  • the liquid detergents of Examples 17 to 39 to which the present invention is applied have good liquid flowability and liquid stability, and have high detergency (odor removal property) against various stains.
  • it can be seen that it has a coating cleaning power necessary for removing stains by directly applying to an object to be cleaned, and is excellent in re-contamination prevention performance.
  • the liquid detergents of Examples 40 to 67 to which the present invention is applied have good liquid flowability and liquid stability, and high detergency against various stains (odor removal properties). And a coating and detergency necessary to remove stains by directly applying to an object to be washed, and also excellent in flexibility imparting effect and good comfort.
  • the liquid detergents of Examples 68 to 92 to which the present invention is applied have good liquid flowability and liquid stability, and have high detergency (odor removal property) against various stains.
  • it can be seen that it has a coating detergency necessary for removing dirt by applying it directly to the object to be cleaned, and is excellent in deodorizing performance and anti-recontamination performance.
  • the liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and removes stains by directly applying to odor removal and washing objects. Therefore, it has excellent application cleaning power, recontamination prevention performance, flexibility imparting effect, deodorization performance and recontamination prevention performance, so that it can be used as a detergent for clothing.

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  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un détergent liquide, qui contient (A) un ester alkylsulfonate d'acide gras spécifique, (B) un ester d'alkylalcoxylate d'acide gras spécifique et (C) au moins un type de solvant organique qui est choisi parmi des alcools ayant de 2 à 4 atomes de carbone et des composés représentés par la formule générale (c-1), et dans lequel le total du composant (A) et du composant (B) est de 40 % en masse ou plus, le rapport du composant (A)/le composant (B) (rapport en masse) est de 5/95 à 60/40, et le rapport en masse représenté par [le composant (A) + le composant (B)]/le composant (C) est de 23 ou moins. Dans la formule (c-1), R6 représente un groupe alkyle ayant de 1 à 6 atomes de carbone ou un groupe phényle, R7 représente un groupe alkylène ayant de 2 à 4 atomes de carbone, et n représente un nombre de répétitions moyen de OR7, ledit nombre de répétitions moyen étant un nombre de 1 à 5. La présente invention est capable de produire un détergent liquide qui présente une bonne fluidité liquide et une bonne stabilité liquide, tout en ayant un pouvoir nettoyant élevé en ce qui concerne différents types de salissures. En particulier, ce détergent liquide a d'excellentes propriétés désodorisantes et un excellent pouvoir nettoyant après application, ce qui est nécessaire pour éliminer la salissure par application directe sur un matériau à nettoyer.
PCT/JP2012/060133 2011-04-18 2012-04-13 Détergent liquide WO2012144438A1 (fr)

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JP2015127369A (ja) * 2013-12-27 2015-07-09 ライオン株式会社 繊維製品用の洗浄剤
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JP2018188542A (ja) * 2017-05-01 2018-11-29 ライオン株式会社 液体洗浄剤組成物
JP2019163433A (ja) * 2018-03-20 2019-09-26 ライオン株式会社 洗浄剤組成物
JP2020002350A (ja) * 2018-06-22 2020-01-09 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 布地の悪臭を低減するためのポリエステルテレフタレートの使用
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JP2015127369A (ja) * 2013-12-27 2015-07-09 ライオン株式会社 繊維製品用の洗浄剤
WO2016204277A1 (fr) * 2015-06-18 2016-12-22 ライオン株式会社 Solution contenant un sel d'ester d'acide alpha-sulfo gras
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JPWO2017208990A1 (ja) * 2016-05-31 2019-03-28 ライオン株式会社 液体洗浄剤組成物
WO2017208990A1 (fr) * 2016-05-31 2017-12-07 ライオン株式会社 Composition de détergent liquide
KR102375505B1 (ko) 2016-05-31 2022-03-17 라이온 가부시키가이샤 액체 세정제 조성물
JP2018188542A (ja) * 2017-05-01 2018-11-29 ライオン株式会社 液体洗浄剤組成物
JP2019163433A (ja) * 2018-03-20 2019-09-26 ライオン株式会社 洗浄剤組成物
JP7133954B2 (ja) 2018-03-20 2022-09-09 ライオン株式会社 衣料用洗浄剤組成物
JP2020002350A (ja) * 2018-06-22 2020-01-09 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 布地の悪臭を低減するためのポリエステルテレフタレートの使用
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KR20140007407A (ko) 2014-01-17
JP5793563B2 (ja) 2015-10-14
JP2015193859A (ja) 2015-11-05
KR101913880B1 (ko) 2018-10-31
JP6086957B2 (ja) 2017-03-01

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