WO2022215608A1 - Composition d'agent nettoyant acide - Google Patents

Composition d'agent nettoyant acide Download PDF

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Publication number
WO2022215608A1
WO2022215608A1 PCT/JP2022/015772 JP2022015772W WO2022215608A1 WO 2022215608 A1 WO2022215608 A1 WO 2022215608A1 JP 2022015772 W JP2022015772 W JP 2022015772W WO 2022215608 A1 WO2022215608 A1 WO 2022215608A1
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component
detergent composition
pka
acid
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PCT/JP2022/015772
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Japanese (ja)
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亮介 大村
篤 益田
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花王株式会社
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Publication of WO2022215608A1 publication Critical patent/WO2022215608A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • 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
    • 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
    • C11D3/36—Organic compounds containing phosphorus

Definitions

  • the present invention relates to an acidic detergent composition and a method for removing complex stains containing fatty acid calcium soap and sebum.
  • Japanese Patent Publication No. 2001-522397 and Japanese Patent Publication No. 11-514696 disclose that acidic cleaners containing organic acids are most suitable for removing calcareous scale-containing stains typically found in kitchens or bathrooms. is stated.
  • JP-A-7-233394 and JP-A-10-204480 disclose that a neutral detergent containing a cationic surfactant and a sequestering agent that is an organic acid is effective in cleaning scum stains on hard surfaces. It is disclosed to have performance.
  • Japanese Patent Application Laid-Open No. 10-204480 discloses a kitchen detergent suitable for removing inorganic stains containing a cationic surfactant and a sequestering agent.
  • the present invention provides an acidic detergent composition that has excellent detergency for stubborn complex stains containing fatty acid calcium soap and sebum adhering to hard surfaces such as bathrooms and toilets, and a complex containing fatty acid calcium soap and sebum. To provide a stain removal method.
  • the present invention comprises (a) a cationic surfactant [hereinafter referred to as component (a)], (b) an organic carboxylic acid having a first acid dissociation constant pKa 1 of 1 or more and less than 7, and a first acid dissociation constant pKa 1 contains one or more acid agents selected from organic phosphonic acids having a value of 1 or more and less than 7 [hereinafter referred to as component (b)] and water, and the content of component (a) and the content of component (b) mass ratio (b)/(a) of 0.1 or more and 7 or less, and pH at 20°C of more than 2.0 and 6.0 or less.
  • component (a) a cationic surfactant
  • component (b) an organic carboxylic acid having a first acid dissociation constant pKa 1 of 1 or more and less than 7
  • a first acid dissociation constant pKa 1 contains one or more acid agents selected from organic phosphonic acids having a value of 1 or more and less than 7 [
  • the present invention provides a method for removing complex stains containing fatty acid calcium soap and sebum, comprising bringing the acidic detergent composition into contact with a hard surface on which complex stains containing fatty acid calcium soap and sebum are adhered, and rinsing the surface with water. Regarding.
  • an acidic detergent composition having excellent detergency for stubborn complex stains containing fatty acid calcium soap and sebum adhering to hard surfaces such as bathrooms and toilets, and complex stains containing fatty acid calcium soap and sebum. is provided.
  • the present inventors have selected from organic carboxylic acids having a first acid dissociation constant pKa 1 of 1 or more and less than 7, and organic phosphonic acids having a first acid dissociation constant pKa 1 of 1 or more and less than 7, which are components (b).
  • the component (b) of the present invention can release a sufficient amount of protons in the pH range of the acidic detergent composition of the present invention, and can convert fatty acid calcium soaps into fatty acids.
  • the pH of the detergent composition is high, the amount of protons is not sufficient, and when the pH is too low, the dirt itself is altered, resulting in a decrease in detergency.
  • component (b) and the component (a) of the present invention in a specific ratio, it is possible to obtain the high detergency of the fatty acid calcium soap and the permeability to complex stains containing the fatty acid calcium soap of the component (b). is considered to enable
  • Component (a) is a cationic surfactant.
  • Cationic surfactants include quaternary ammonium salt-type cationic surfactants.
  • the quaternary ammonium salt type cationic surfactant from the viewpoint of detergency (hereinafter simply referred to as detergency) for complex stains containing fatty acid calcium soap and sebum, one of the groups bonded to the nitrogen atom or two of which are hydrocarbon groups having 8 to 16 carbon atoms, and the rest are alkyl groups having 1 to 3 carbon atoms, hydroxyalkyl groups having 1 to 3 carbon atoms, and arylalkyl groups (such as benzyl groups).
  • a quaternary ammonium salt-type cationic surfactant which is a group selected from is preferred.
  • a quaternary ammonium salt-type cationic surfactant represented by the following general formula (a1)
  • salt-type cationic surfactants are preferred.
  • R 1a represents a hydrocarbon group having 8 to 16 carbon atoms.
  • R 2a and R 3a each independently represent an alkyl group having 1 to 3 carbon atoms.
  • R 4a represents an alkylene group having 1 to 3 carbon atoms.
  • Z- represents an anionic group.
  • R 4a is a hydrocarbon group having 8 to 16 carbon atoms
  • R 5a is a hydrocarbon group having 8 to 16 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and 1 or more carbon atoms a group selected from 3 or less hydroxyalkyl groups
  • R 6a and R 7a are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms;
  • Z ⁇ are anions.
  • R 1a is a hydrocarbon having 8 or more carbon atoms, preferably 10 or more carbon atoms, and 16 or less, preferably 14 or less, more preferably 12 or less, and still more preferably 10 carbon atoms from the viewpoint of detergency. groups, preferably alkyl or alkenyl groups, more preferably alkyl groups.
  • R 2a and R 3a are each independently an alkyl group having 1 or more and 3 or less carbon atoms, preferably an alkyl group having 1 or more and 2 or less carbon atoms, and more preferably a methyl group.
  • R 4a is an alkylene group having 1 or more and 3 or less carbon atoms, preferably an alkylene group having 1 or more and 2 or less carbon atoms, more preferably a methylene group.
  • Z 1 ⁇ in general formula (a1) is preferably a halogen ion such as a chloride ion.
  • Z ⁇ is more preferably chloride ion (Cl ⁇ ).
  • R 4a is a hydrocarbon group having 8 or more, preferably 10 or more, and 16 or less, preferably 14 or less, more preferably 12 or less, preferably alkyl, from the viewpoint of detergency. or an alkenyl group, more preferably an alkyl group.
  • R 5a when R 5a is a hydrocarbon group having 8 to 16 carbon atoms, R 5a has 8 or more, preferably 10 or more, and 16 or less carbon atoms from the viewpoint of detergency. It is preferably a hydrocarbon group of 14 or less, more preferably 12 or less, preferably an alkyl group or an alkenyl group, more preferably an alkyl group.
  • R 5a when R 5a is an alkyl group having 1 to 3 carbon atoms, R 5a is preferably an alkyl group having 1 to 2 carbon atoms, more preferably a methyl group.
  • R 6a and R 7a are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms, preferably It is an alkyl group of 1 or more and 3 or less, more preferably an alkyl group of 1 or more and 2 or less carbon atoms, and still more preferably a methyl group.
  • Z ⁇ in general formula (a2) is preferably a halogen ion such as a chloride ion, more preferably a chloride ion (Cl ⁇ ).
  • Component (b) is one or more acid agents selected from organic carboxylic acids having a first acid dissociation constant pKa 1 of 1 or more and less than 7, and organic phosphonic acids having a first acid dissociation constant pKa 1 of 1 or more and less than 7. be.
  • the acid dissociation constant pKa of the component (b) of the present invention indicates the pKa at a concentration of 0.1 mol/L of the compound of the component (b) at 25° C. when water is used as a solvent.
  • the acid dissociation constant pKa at 25 ° C. is described in "The Chemical Society of Japan, Chemistry Handbook, Basic Edition, Revised 5th Edition" (February 20, 2004, published by Maruzen Co., Ltd., pp. II-334 to II-343). pKa can be used.
  • the first acid dissociation constant pKa 1 of component (b) is 1 or more, preferably 1.5 or more, more preferably 1.9 or more, still more preferably 2.9 or more, and less than 7, from the viewpoint of detergency. , preferably 6 or less, more preferably 5 or less, still more preferably 4.5 or less, and even more preferably 4 or less.
  • the component (b) may have a plurality of acid dissociation constants pKa, preferably 4 or less, preferably 3 or less from the viewpoint of detergency, and 1 or more, preferably 2 or more from the viewpoint of odor.
  • Organic carboxylic acids or organic phosphonic acids with pKa are preferred.
  • the lowest pKa that is, the first acid dissociation constant pKa 1 is preferably 1 or more, preferably 1.5 or more, more preferably 1.9 or more, still more preferably 2.9 or more, and less than 7, preferably 6 or less, more preferably 5 or less, still more preferably 4.5 or less, still more preferably 4 or less, and , the highest pKa is 12 or less, preferably 9 or less, more preferably 7 or less from the viewpoint of detergency.
  • organic carboxylic acids are preferred, monocarboxylic acids or polycarboxylic acids having an acid dissociation constant of 3 or less are preferred, and all acid dissociation constants are 1 or more and less than 7, preferably 1.5 or more and 6 or less, more preferably. is preferably an organic carboxylic acid of 2.9 or more and 6 or less.
  • Component (b) is a monocarboxylic acid having a molecular weight of 46 or more and 200 or less, preferably 180 or less, from the viewpoint of adsorption and permeability to fatty acid calcium soap-containing stains under acidic conditions. More preferably 150 or less, the molecular weight in the case of dicarboxylic acid is 90 or more and 200 or less, preferably 180 or less, more preferably 150 or less, and the molecular weight in the case of tricarboxylic acid is 150 or more, Further, it is 200 or less, preferably 180 or less, and further has a molecular weight of 70 or more, preferably 100 or more, more preferably 200 or more and 300 or less in the case of an aminocarboxylic acid, and is an organic phosphonic acid. The molecular weight of the case is 170 or more, preferably 200 or more, and 300 or less, preferably 250 or less. In addition, let these molecular weights be the value which converted the (b) component into the acid form.
  • Component (b) is specifically one or more selected from the following.
  • monocarboxylic acids include acetic acid (pKa 1 4.76), lactic acid (pKa 1 3.64), propionic acid (pKa 1 4.62), butyric acid (pKa 1 4.57), hexanoic acid (pKa 1 4.00). 85) and benzoic acid (pKa 1 4.00).
  • Dicarboxylic acids include oxalic acid (pKa 1 1.04, pKa 2 3.82), maleic acid (pKa 1 1.84, pKa 2 5.83), malic acid (pKa 1 3.23, pKa 2 4.00).
  • Tricarboxylic acids include citric acid (pKa 1 2.90, pKa 2 4.35, pKa 3 5.69).
  • aminocarboxylic acids examples include ethylenediaminetetraacetic acid (pKa 1 2.00, pKa 2 2.67, pKa 3 6.36, pKa 4 10.27), dicarboxymethylglutamic acid (pKa 2.6, pKa 2 3.5, pKa 3 5.0, pKa 4 9.4).
  • Organic phosphonic acids include hydroxyethane-1,1-diphosphonic acid (pKa 1 1.99, pKa 2 2.67, pKa 3 6.16, pKa 4 10.26).
  • the bracketed pKa 1 of the compound indicates the first acid dissociation constant, pKa 2 the second acid dissociation constant, pKa 3 the third acid dissociation constant, and pKa 4 the fourth acid dissociation constant.
  • the (b) component of the present invention is preferably one or more selected from monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids from the viewpoint of detergency, and particularly one selected from dicarboxylic acids and tricarboxylic acids from the viewpoint of odor. The above is preferable.
  • the (b) component of the present invention from the viewpoint of detergency, from the viewpoint of detergency, from the viewpoint of detergency,
  • the acidic detergent composition of the present invention preferably contains component (a) in an amount of 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, from the viewpoint of detergency. , still more preferably 1.3% by mass or more, still more preferably 1.5% by mass or more, still more preferably 1.7% by mass or more, still more preferably 1.9% by mass or more, and preferably 10 % by mass or less, more preferably 6.0% by mass or less, even more preferably 5.5% by mass or less, and even more preferably 4.5% by mass or less.
  • the acidic detergent composition of the present invention contains the component (b) in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, from the viewpoint of detergency. , more preferably 1.3% by mass or more, even more preferably 2.5% by mass or more, and preferably 10% by mass or less, more preferably 6.0% by mass or less, and even more preferably 5.7% by mass Below, more preferably 5.5% by mass or less, still more preferably 5.3% by mass or less, and even more preferably 5.1% by mass or less.
  • the mass ratio (b)/(a) between the content of component (a) and the content of component (b) is preferably 0.1 or more, from the viewpoint of detergency. is 0.2 or more, more preferably 0.25 or more, still more preferably 0.3 or more, still more preferably 0.35 or more, still more preferably 0.4 or more, still more preferably 0.45 or more, and , 7 or less, preferably 6.5 or less, more preferably 6 or less, even more preferably 5.5 or less, even more preferably 5 or less, even more preferably 4.5 or less, even more preferably 4 or less, even more It is preferably 3.5 or less, more preferably 3 or less, and even more preferably 2.8 or less.
  • the acidic detergent composition of the present invention has a pH at 20°C of more than 2.0, preferably 2.5 or more, more preferably 2.9 or more, still more preferably 4 or more, from the viewpoint of detergency at 20°C. , 6.0 or less, preferably 5.5 or less, more preferably 5 or less. From the standpoint of detergency, the acidic detergent composition of the present invention has a pH at 20°C that is the value obtained by multiplying the acid dissociation constant pKa of the compound contained as component (b) by 1.1 (where the product is 6 If it exceeds 0.0, it should be 6.0 or less).
  • the highest acid dissociation constant pKa having an acid dissociation constant pKa of less than 6.0 shall be adopted.
  • the acid dissociation constant pKa is less than 6.0 and The highest acid dissociation constant pKa shall be taken.
  • the acidic detergent composition of the present invention contains citric acid (pKa 1 2.90, pKa 2 4.35, pKa 3 5.69) as the component (b)
  • the acidic detergent composition of the present invention The pH of the product at 20° C.
  • the acidic detergent composition of the present invention contains ethylenediaminetetraacetic acid (pKa 1 1.99, pKa 2 2.67, pKa 3 6.16, pKa 4 10.26) as the component (b).
  • the pH of the acidic detergent composition of the present invention at 20°C should be 2.9 or less, which is obtained by multiplying the secondary acid dissociation constant pKa 2 of ethylenediaminetetraacetic acid (2.67) by 1.1. is preferred.
  • the component (b) of the present invention is preferably an acid stronger than oleic acid from the viewpoint of promoting decomposition by acting as a proton donor to the calcium salt of the fatty acid. That is, the acid dissociation constant pKa of component (b) is preferably 5 or less, which is the pKa of oleic acid. preferably.). On the other hand, if the acid dissociation constant pKa of the component (b) is extremely small, the ions are always in a dissociated state and do not function as proton donors. It is preferably 2.9 or more, more preferably 2.9 or more.
  • the acidic detergent composition of the present invention preferably further contains glycol ether as component (c).
  • a compound represented by the following general formula (c1) is preferable.
  • R 1c O—(R 2c O) n —H (c1) (In the formula, R 1c is a hydrocarbon group having 1 to 8 carbon atoms, R 2c is an alkylene group having 2 or 3 carbon atoms, and n is an integer of 1 to 4.)
  • R 1c is a hydrocarbon group having 1 or more carbon atoms, preferably 2 or more carbon atoms, and 8 or less, preferably 7 or less, more preferably 6 or less carbon atoms, preferably an alkyl group, an alkenyl group, or an aryl group; An alkyl group is more preferred.
  • n is preferably 3 or less, more preferably 2 or less.
  • glycol One or more selected from glycol, benzyldiglycol, phenyldiglycol, and isobutyldiglycol is preferable, and one or more selected from butylpropylene glycol, butyldiglycol and benzyldiglycol is more preferable, and butyldiglycol and benzyldiglycol. Glycols are more preferred.
  • the acidic detergent composition of the present invention contains component (c) preferably at least 0.5% by mass, more preferably at least 1% by mass, even more preferably at least 2% by mass, and even more preferably is 3% by mass or more, more preferably 4% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 7% by mass or less, and more More preferably, the content is 6% by mass or less.
  • the mass ratio (b)/[(a)+(c)] of the content of component (b) to the total content of components (a) and (c) is , From the viewpoint of detergency, preferably 0.02 or more, more preferably 0.1 or more, still more preferably 0.2 or more, even more preferably 0.3 or more, still more preferably 0.4 or more, and still more It is preferably 0.5 or more, and preferably 1 or less, more preferably 0.9 or less, even more preferably 0.8 or less, and even more preferably 0.7 or less.
  • the acidic detergent composition of the present invention may contain a surfactant other than the component (a) as the component (d) within a range that does not impair the effects of the present invention.
  • surfactants include (d1) anionic surfactants (hereinafter also referred to as (d1) component), (d2) amphoteric surfactants (hereinafter also referred to as (d2) component), and (d3) nonionic surfactants.
  • component (d3) One or more selected from activators (hereinafter also referred to as component (d3)) can be mentioned.
  • Component (d1) is one or more selected from alkyl or alkenyl sulfate esters or salts thereof, polyoxyalkylene alkyl or alkenyl ether sulfate esters or salts thereof, fatty acids or salts thereof, and alkyl or alkenyl benzene sulfonic acids or salts thereof. is mentioned.
  • Salts of anionic surfactants are preferably alkali metal salts such as sodium salts and potassium salts.
  • R 1d represents a hydrocarbon group having 7 to 18 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and R 2d and R 3d are the same or different and have 1 or more carbon atoms Represents an alkyl group of 3 or less.
  • R 1d is used in combination with the component (a) to improve detergency for stubborn complex stains containing fatty acid calcium soap and sebum.
  • a hydrocarbon group preferably having 7 or more carbon atoms and 17 or less, preferably 15 or less, more preferably 13 or less, still more preferably 11 or less, and still more preferably 9 or less carbon atoms, preferably an alkyl group or an alkenyl group , and more preferably an alkyl group.
  • R 2d and R 3d are preferably C 1 methyl groups.
  • a polyoxyalkylene alkyl ether having an alkyl group having 8 to 18 carbon atoms an average of 1 to 8 moles or less of an alkylene oxide having 2 or 3 carbon atoms is added), and 8 or more carbon atoms.
  • Polyoxyalkylene alkenyl ethers having alkenyl groups of 18 or less (those to which an average of 1 to 8 mol of alkylene oxide having 2 or 3 carbon atoms is added), polyoxyalkylene sorbitan having fatty acid groups of 8 to 18 carbon atoms Fatty acid ester (having an average of 1 to 8 mol of alkylene oxide having 2 or 3 carbon atoms added thereto), an alkyl glycoside having an alkyl group having 8 to 18 carbon atoms, and an alkyl group having 8 to 18 carbon atoms One or more selected from alkyl polyglycosides, sucrose fatty acid esters having a fatty acid group having 8 to 18 carbon atoms, and alkyl polyglyceryl ethers or alkyl glyceryl ethers having an alkyl group having 8 to 18 carbon atoms, and washing Alkyl glycosides having an alkyl group having 8 to 14 carbon atoms, alkyl polyglycosides having an alky
  • component (d2) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and The content is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and even more preferably 2% by mass or less.
  • the content of component (a) in all surfactants (total of component (a) and component (d)) is preferably 50% by mass or more from the viewpoint of detergency. , More preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass % or less, and may be 100% by mass.
  • the acidic detergent composition of the present invention has a viscosity at 25° C. of preferably 1 mPa ⁇ s or more, more preferably 4 mPa ⁇ s or more, and preferably It is 200 mPa ⁇ s or less, more preferably 100 mPa ⁇ s or less, and still more preferably 50 mPa ⁇ s or less.
  • This viscosity is measured using a Brookfield viscometer (model number: TVB-10 manufactured by Toki Sangyo Co., Ltd., using a No. 2 rotor, 60 r/min).
  • the viscosity of the acidic detergent composition of the present invention is adjusted by adding a thickening agent.
  • the acidic detergent composition of the present invention can be suitably used for hard surfaces.
  • Hard surfaces include bathrooms, toilets, tubs, basins, tiles, restrooms, vanities, mirrors, kitchen sinks, countertops, plumbing, and the like.
  • the acidic detergent composition of the present invention is suitable for cleaning hard surfaces, and is particularly suitable for bathrooms and toilets to which dirt containing fatty acid calcium soap tends to adhere and accumulate.
  • "for bathrooms” refers not only to bathrooms, but also to articles having hard surfaces in bathrooms, such as bathtubs and basins.
  • the present invention is a method for removing complex soil containing fatty acid calcium soap and sebum by contacting the acidic detergent composition of the present invention with a hard surface on which complex soil containing fatty acid calcium soap and sebum is adhered and rinsing with water.
  • a removal method (hereinafter also referred to as the method of the present invention) is provided.
  • the method of the present invention can appropriately apply the items described for the acidic detergent composition of the present invention.
  • a concentrated composition containing components (a), (b) and optional components is prepared, and the concentrated composition is diluted with water to prepare the acidic detergent composition of the present invention.
  • a concentrated composition containing the components (a) and (b) of the present invention and optional components is diluted with water to prepare the acidic detergent composition of the present invention, and the composition is
  • a method for removing complex stains containing fatty acid calcium soap and sebum may be provided in which a hard surface to which complex stains containing fatty acid calcium soap and sebum are adhered is brought into contact.
  • the method of the present invention is performed by bringing the acidic detergent composition of the present invention into contact with a hard surface to which complex dirt containing fatty acid calcium soap and sebum is adhered, and then applying an external force such as a mechanical force.
  • an external force such as a mechanical force.
  • an external force such as a mechanical force means, for example, not performing an intentional operation for cleaning other than contact with the composition.
  • an external force such as a mechanical force means, for example, not performing an intentional operation for cleaning other than contact with the composition.
  • the composition brought into contact naturally flows down the hard surface, or that vibrations not intended for cleaning are transmitted to the hard surface when left without applying an external force. After standing, it is usually rinsed with water.
  • an external force physical force
  • the acidic detergent composition of the present invention may be contacted by spraying or applying to a hard surface stained with a complex containing fatty acid calcium soap and sebum.
  • the method of bringing the acidic detergent composition of the present invention into contact with a hard surface is preferably spraying or coating, and examples thereof include a method of spraying in the form of droplets or a method of coating in the form of foam.
  • spray means can be used. That is, it is preferable to use a detergent product obtained by filling a container equipped with a sprayer with the acidic detergent composition of the present invention.
  • the present invention provides a cleaning article packed in a spray container, which is obtained by filling a container equipped with a sprayer with the acidic cleaning composition of the present invention.
  • the diameter of the injection nozzle of the spray container containing the composition is is preferably 0.1 mm or more, more preferably 0.3 mm or more, because it is easy to spray, the sprayed droplets are not rough, the sprayed droplets are not sprayed in a straight line, and the sprayable area is not extremely narrowed.
  • the range is preferably 2 mm or less, more preferably 1 mm or less.
  • the detergent article in a spray container of the present invention is preferably 0.1 mL or more, more preferably 0.3 mL or more in one operation, and , preferably 5 mL or less, more preferably 2 mL or less of the composition is sprayed.
  • the detergent article in a spray container of the present invention is preferably 0.5 mL or more, more preferably 1 mL or more, and preferably 30 mL or less in one operation, More preferably 15 mL or less, more preferably 5 mL or less of the composition is sprayed.
  • the method of the present invention can be applied to the hard surfaces of hard articles, as well as hard surfaces such as bathrooms, toilets, bathtubs, basins, tiles, lavatories, washbasins, mirrors, sinks around kitchens, countertops, around plumbing, especially fatty acid calcium. It is preferable as a method for cleaning the hard surfaces of bathrooms and toilets to which complex dirt containing soap and sebum tends to adhere and accumulate.
  • component (a) a cationic surfactant [hereinafter referred to as component (a)], (b) an organic carboxylic acid having a first acid dissociation constant pKa 1 of 1 or more and less than 7, and a first acid dissociation constant pKa 1 of 1 or more and 7
  • component (b) an organic carboxylic acid having a first acid dissociation constant pKa 1 of 1 or more and less than 7, and a first acid dissociation constant pKa 1 of 1 or more and 7
  • One or more acid agents selected from organic phosphonic acids [hereinafter referred to as component (b)] and water, and the mass ratio of the content of component (a) to the content of component (b) ( b)/(a) is 0.1 or more and 7 or less, and the pH at 20°C is more than 2.0 and 6.0 or less.
  • ⁇ 2> Among the groups bonded to the nitrogen atom in component (a), one or two are hydrocarbon groups having 8 or more and 16 or less carbon atoms, and the rest are alkyl groups having 1 or more and 3 or less carbon atoms, and 1 or more and 3 carbon atoms.
  • the acidic detergent composition according to ⁇ 1> which is a quaternary ammonium salt-type cationic surfactant which is a group selected from the group consisting of the following hydroxyalkyl groups and arylalkyl groups (benzyl group, etc.).
  • the component (a) is a quaternary ammonium salt-type cationic surfactant represented by the following general formula (a1), and a quaternary ammonium salt-type cationic surfactant represented by the following general formula (a2).
  • the acidic detergent composition according to ⁇ 1> or ⁇ 2> which is one or more selected from
  • R 1a represents a hydrocarbon group having 8 to 16 carbon atoms.
  • R 2a and R 3a each independently represent an alkyl group having 1 to 3 carbon atoms.
  • R 4a represents an alkylene group having 1 to 3 carbon atoms.
  • Z- represents an anionic group.
  • R 4a is a hydrocarbon group having 8 to 16 carbon atoms
  • R 5a is a hydrocarbon group having 8 to 16 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and 1 or more carbon atoms a group selected from 3 or less hydroxyalkyl groups
  • R 6a and R 7a are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms;
  • Z ⁇ are anions.
  • component (b) is an organic carboxylic acid having an acid dissociation constant pKa of less than 7.
  • Component (b) is a monocarboxylic acid with a molecular weight of 46 to 150, a dicarboxylic acid with a molecular weight of 90 to 180, a tricarboxylic acid with a molecular weight of 150 to 200, an aminocarboxylic acid with a molecular weight of 200 to 300, and a molecular weight of 170 to 250.
  • the acidic detergent composition according to any one of ⁇ 1> to ⁇ 5>, which is one or more selected from organic phosphonic acids.
  • Component (a) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, still more preferably 1.3% by mass or more, still more preferably 1.5% by mass or more, more preferably 1.7% by mass or more, still more preferably 1.9% by mass or more, and preferably 10% by mass or less, more preferably 6.0% by mass or less, and even more preferably is 5.5% by mass or less, more preferably 4.5% by mass or less, the acidic detergent composition according to any one of ⁇ 1> to ⁇ 9>.
  • Component (b) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, still more preferably 1.3% by mass or more, still more preferably 2.5% by mass or more, preferably 10% by mass or less, more preferably 6.0% by mass or less, even more preferably 5.7% by mass or less, even more preferably 5.5% by mass or less, and even more preferably is 5.3% by mass or less, more preferably 5.1% by mass or less, the acidic detergent composition according to any one of ⁇ 1> to ⁇ 10>.
  • the mass ratio (b)/(a) of the content of component (a) to the content of component (b) is preferably 0.2 or more, more preferably 0.25 or more, and still more preferably 0.3 or more , more preferably 0.35 or more, still more preferably 0.4 or more, still more preferably 0.45 or more, and preferably 6.5 or less, more preferably 6 or less, still more preferably 5.5 or less , still more preferably 5 or less, still more preferably 4.5 or less, still more preferably 4 or less, still more preferably 3.5 or less, still more preferably 3 or less, still more preferably 2.8 or less , the acidic detergent composition according to any one of ⁇ 1> to ⁇ 11>.
  • component (c) is a compound represented by the general formula (c1), wherein R 1c is an alkyl group, alkenyl group, or aryl group having 2 to 7 carbon atoms, and n is 2 or less. of acidic detergent compositions.
  • Component (c) is 2-ethylhexyl glycol, hexyl glycol, hexyl diglycol, butyl propylene diglycol, butyl propylene glycol, propyl propylene diglycol, butyl glycol, propyl propylene glycol, butyl diglycol, 2-tert-butoxyethanol,
  • the acidic detergent composition according to ⁇ 13> or ⁇ 14> which is at least one selected from isobutyldiglycol, methylpropyleneglycol, methylglycol, methyldipropyleneglycol, benzylglycol, and benzyldiglycol.
  • the mass ratio (b)/[(a)+(c)] of the content of component (b) to the total content of components (a) and (c) is preferably 0.02 or more, more preferably is 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, still more preferably 0.4 or more, still more preferably 0.5 or more, and preferably 1 or less, more preferably is 0.9 or less, more preferably 0.8 or less, still more preferably 0.7 or less, according to any one of ⁇ 13> to ⁇ 18>.
  • component is (d1) anionic surfactant (hereinafter also referred to as (d1) component), (d2) amphoteric surfactant (hereinafter also referred to as (d2) component), and (d3) nonionic interface
  • component (d3) anionic surfactant selected from active agents
  • component (d) is component (d2), preferably one or more surfactants selected from betaine surfactants and amine oxide surfactants. thing.
  • Component (d) is a betaine surfactant, preferably N-alkanoylaminopropyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N , N-dimethyl-N-sulfopropylammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl
  • Component (d) is component (d3), preferably a polyoxyalkylene alkyl ether having an alkyl group having 8 to 18 carbon atoms (an average of 1 mol to 8 mol of alkylene oxide having 2 or 3 carbon atoms is added) polyoxyalkylene alkenyl ether having an alkenyl group having 8 to 18 carbon atoms (an average of 1 mol to 8 mol or less of alkylene oxide having 2 or 3 carbon atoms is added), 8 to 18 carbon atoms Polyoxyalkylene sorbitan fatty acid ester having a fatty acid group (1 to 8 mol on average of alkylene oxide having 2 or 3 carbon atoms added), alkyl glycoside having an alkyl group having 8 to 18 carbon atoms, 8 carbon atoms selected from alkyl polyglycosides having an alkyl group of 18 or less, sucrose fatty acid esters having a fatty acid group of 8 to 18 carbon atoms, and alkyl polyglyceryl
  • the viscosity at 25°C is preferably 1 mPa s or more, more preferably 4 mPa s or more, and preferably 200 mPa s or less, more preferably 100 mPa s or less, and still more preferably 50 mPa s or less, ⁇ 1 > to the acidic detergent composition according to any one of ⁇ 28>.
  • the acidic detergent composition according to any one of ⁇ 1> to ⁇ 30> is brought into contact with a hard surface on which complex dirt containing fatty acid calcium soap and sebum is adhered, and rinsed with water.
  • the acidic detergent composition according to any one of ⁇ 1> to ⁇ 30> is filled in a container equipped with a sprayer and sprayed onto a hard surface in the form of droplets or in the form of foam. > method for removing complex stains containing fatty acid calcium soap and sebum.
  • Acidic detergent compositions shown in Tables 1 to 3 were prepared using the following ingredients, and the following items were evaluated. The results are shown in Tables 1-3.
  • the acidic detergent compositions in Tables 1 to 3 were prepared by adding components (a) to (d) in the amounts shown in the tables and dissolving them at room temperature (20°C). After blending, the pH was adjusted to the values shown in Tables 1-3 using sodium hydroxide and/or hydrochloric acid. In addition, pH was measured by the glass electrode method. In addition, the mass % of the compounding ingredients in Tables 1 to 3 are all numerical values based on the active ingredients.
  • Component C10BAC a compound represented by the general formula (a1), wherein R 1a is an alkyl group having 10 carbon atoms, R 2a and R 3a are methyl groups, R 4a is a methylene group, and Z - is a chloride ion; RK, C8BAC manufactured by Kao Corporation: In general formula (a1), R 1a is an alkyl group having 8 carbon atoms, R 2a and R 3a are methyl groups, R 4a is a methylene group, and Z - is a chloride ion.
  • (b') component (comparative component of (b) component) ⁇ Phosphoric acid: pKa 1 1.83, pKa 2 6.43, pKa 3 11.46, manufactured by Kishida Chemical Co., Ltd.
  • component BzDG benzyl diglycol, manufactured by Nippon Nyukazai Co., Ltd.
  • BFG butyl propylene glycol, manufactured by Nippon Nyukazai Co., Ltd.
  • BDG butyl diglycol, manufactured by Nippon Nyukazai Co., Ltd.
  • Component C12 sulfobetaine Hydroxylaurylsulfobetaine, Amphithol 20HD, manufactured by Kao Corporation C8 amine oxide: Octyldimethylamine oxide, Amphitol 08N, manufactured by Kao Corporation C12/14 amine oxide: Lauryldimethylamine A mixture of oxide and myristyl dimethylamine oxide, Amphitol 20N, manufactured by Kao Corporation C12APB: Lauramidopropyl betaine, manufactured by Kao Corporation AG: Alkyl glycoside having an alkyl group having C10-16 carbon atoms, Kao Corporation ) made
  • Detergency was evaluated for model bathroom stains composed of a combination of fatty acid calcium soap and sebum.
  • the method for creating model stains is shown below.
  • a solution A was obtained by mixing 90% by mass of solid soap (manufactured by Kao Corporation, Kao White) and 10% by mass of model sebum soil at 50 to 60° C. and keeping the mixture warm.
  • the composition of the model sebum stain is 40% by mass of linoleic acid, 20% by mass of oleic acid, 20% by mass of palmitic acid, 10% by mass of cholesterol, and 10% by mass of liquid paraffin.
  • a 6% by weight aqueous solution of calcium chloride was kept at 20 to 30° C. to obtain solution B.
  • Table 4 shows formulation examples of the acidic detergent composition of the present invention.
  • the acidic detergent composition having the following formulation has excellent detergency against stubborn complex stains containing fatty acid calcium soap and sebum adhering to hard surfaces such as bathrooms and toilets.

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Abstract

L'invention concerne une composition d'agent nettoyant acide présentant un excellent pouvoir détergent vis-à-vis de taches complexes tenaces contenant du savon de calcium d'acide gras et du sébum adhérant à une surface dure telle que celle d'une salle de bains ou de toilettes, et un procédé d'élimination de taches complexes contenant du savon de calcium d'acide gras et du sébum.　La présente invention concerne une composition d'agent nettoyant acide contenant (a) un tensioactif ionique positif (ci-après désigné composant (a)), (b) un ou plusieurs agents acides choisis parmi des acides carboxyliques organiques présentant une première constante de dissociation acide pKa 1 d'au moins 1 mais inférieure à 7 et des acides phosphoniques organiques présentant une première constante de dissociation acide pKa 1 d'au moins 1 mais inférieure à 7 (ci-après désigné composant (b)), et de l'eau. Le rapport massique (b)/(a) entre la teneur en composant (a) et la teneur en composant (b) va de 0,1 à 7. La valeur de pH de la composition d'agent nettoyant acide à 20 °C est supérieure à 2,0 mais n'est pas supérieure à 6,0.
PCT/JP2022/015772 2021-04-08 2022-03-30 Composition d'agent nettoyant acide WO2022215608A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511798A (ja) * 1996-05-21 1999-10-12 ザ、プロクター、エンド、ギャンブル、カンパニー 酸性クリーニング組成物
JP2012111846A (ja) * 2010-11-25 2012-06-14 Dainippon Jochugiku Co Ltd 酸性抗菌洗浄剤組成物
JP2015113454A (ja) * 2013-12-16 2015-06-22 花王株式会社 硬質表面用洗浄剤組成物
JP2017110323A (ja) * 2015-12-18 2017-06-22 花王株式会社 除菌性清掃物品
JP2019151734A (ja) * 2018-03-02 2019-09-12 花王株式会社 硬質表面用殺黴洗浄剤組成物
JP2020510729A (ja) * 2017-03-01 2020-04-09 エコラボ ユーエスエー インコーポレイティド 高分子量ポリマーによって低減した吸入ハザードの消毒剤および殺菌剤

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511798A (ja) * 1996-05-21 1999-10-12 ザ、プロクター、エンド、ギャンブル、カンパニー 酸性クリーニング組成物
JP2012111846A (ja) * 2010-11-25 2012-06-14 Dainippon Jochugiku Co Ltd 酸性抗菌洗浄剤組成物
JP2015113454A (ja) * 2013-12-16 2015-06-22 花王株式会社 硬質表面用洗浄剤組成物
JP2017110323A (ja) * 2015-12-18 2017-06-22 花王株式会社 除菌性清掃物品
JP2020510729A (ja) * 2017-03-01 2020-04-09 エコラボ ユーエスエー インコーポレイティド 高分子量ポリマーによって低減した吸入ハザードの消毒剤および殺菌剤
JP2019151734A (ja) * 2018-03-02 2019-09-12 花王株式会社 硬質表面用殺黴洗浄剤組成物

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