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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/65—Mixtures of anionic with 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
  • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
  • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
  • D06L1/20—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents combined with mechanical means
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
  • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
• • 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
  • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/143—Sulfonic acid esters
• • 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
  • C11D1/42—Amino alcohols or amino 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/12—Soft surfaces, e.g. textile
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/45—Shrinking resistance, anti-felting properties

Definitions

• the present invention relates to a liquid cleaning composition and a method for cleaning textile products.
• anionic surfactants especially alkylbenzene sulfonates, olefin sulfonates, and even internal olefin sulfonates obtained from internal olefins having a double bond inside the olefin chain rather than at the end, with a carbon number of 2
• Nonionic surfactants containing ⁇ 3 oxyalkylene groups are widely used as household and industrial cleaning ingredients.
• JP 2021-134324A discloses that (A) internal olefin sulfonate [hereinafter referred to as component (A)] from 1% by mass to 50% by mass, (B) alkanolamine [hereinafter referred to as component (B)] ] of 0.01% by mass or more and 10% by mass or less, (C) an organic solvent having a hydroxyl group [hereinafter referred to as component (C)] of 0.1% by mass or more and 40% by mass or less, and water; ) A fiber product in which the proportion of an internal olefin sulfonate having 18 carbon atoms [hereinafter referred to as component (A1)] in the component is 80% by mass or more, and the pH at 20°C is 6.0 or more and 11.0 or less.
• a liquid detergent article for textile products is disclosed in which a liquid detergent composition is contained in a bag-like container.
• a cleaning composition using an internal olefin sulfonate having a hydrocarbon group with a specific number of carbon atoms as a surfactant has not only cleaning performance for textile products but also improved cleaning performance (softness for textile products).
• the cleaning performance and washing finish are known to be excellent. The inventors have found that achieving both of these performances does not satisfy consumers.
• the present invention provides a liquid detergent composition that has good liquid color stability at high temperatures and low-temperature storage stability, and has excellent sebum stain cleaning properties and wrinkle prevention properties for textile products even when using highly hard water. To provide a method for cleaning textile products, which is excellent in sebum stain cleaning properties and wrinkle prevention properties even when high hardness water is used.
• the present invention provides (a) an anionic surfactant (hereinafter referred to as component (a)) containing an internal olefin sulfonate having 16 to 24 carbon atoms (hereinafter referred to as component (a1)), and (b1) an amine-based alkaline agent. (hereinafter referred to as (b1) component), (b2) carbonate-based alkaline agent (hereinafter referred to as (b2) component), and water, and the content of component (a1) in component (a) is 70 mass % or more and 100% by mass or less, and has a pH of 8.5 or more and 11.0 or less at 20°C.
• the present invention also provides (a) an anionic surfactant (hereinafter referred to as component (a)) containing an internal olefin sulfonate having 16 to 24 carbon atoms (hereinafter referred to as component (a1)), (b1) an amine-based alkali (hereinafter referred to as component (b1)), (b2) carbonate-based alkaline agent (hereinafter referred to as component (b2)), and water, and the content of component (a1) in component (a) is 70 mass. % or more and 100% by mass or less and a pH of 7.5 or more and 10.5 or less.
• component (a) an anionic surfactant (hereinafter referred to as component (a)) containing an internal olefin sulfonate having 16 to 24 carbon atoms (hereinafter referred to as component (a1)), (b1) an amine-based alkali (hereinafter referred to as component (b1)), (b2) carbonate-based alkaline agent (her
• the liquid detergent has good liquid color stability at high temperatures and low-temperature storage stability, and has excellent sebum stain cleaning properties and wrinkle prevention properties for textile products even when using high hardness water.
• a method for cleaning textile products that has excellent sebum stain cleaning properties and anti-wrinkle properties for textile products even when using a detergent composition and highly hard water.
• liquid detergent composition of the present invention has good liquid color stability at high temperatures and low-temperature storage stability, and excellent sebum dirt cleaning properties and anti-wrinkle properties on textile products are not necessarily clear, but are as follows: It is estimated that Component (a1) forms micelles and vesicles in the cleaning solution, the micelles act on sebum stains attached to textile products, and the vesicles modify the surface of textile products, improving sebum stain cleaning performance and finish. It is possible to achieve both.
• component (a1) when high hardness water is used in the cleaning solution, component (a1) combines with a large amount of calcium contained in the water, resulting in the formation of many vesicles and fewer micelles, resulting in poor sebum stain cleaning performance. It won't be enough. Therefore, the present inventors have discovered a liquid cleaning composition of the present invention in which component (a1) and specific alkaline agents as components (b1) and (b2) are used together in a specific mass ratio. When water with high hardness is used in the cleaning solution, most of the component (a1) forms vesicles, which deteriorates the ability to cleanse sebum stains.
• component (a1) is used in combination with another surfactant that is effective in cleaning sebum stains, the cleaning properties of sebum stains will improve, but this will greatly hinder the formation of vesicles of component (a1), which will reduce the cleansability of sebum stains and wrinkles. It is not possible to achieve both preventive properties.
• the (a1) component, the (b1) component, and the (b2) component are used, and the specific alkaline agents of the (b1) component and (b2) component are used in the vesicles of the (a1) component.
• the liquid cleaning composition of the present invention has liquid color stability at high temperatures and low-temperature storage stability by using the alkaline agent as the component (b1) and the alkaline agent as the component (b2) in a specific mass ratio. It is presumed that both characteristics were improved.
• Component (a) of the present invention is an anionic surfactant containing an internal olefin sulfonate having 16 to 24 carbon atoms (component (a1)).
• the number of carbon atoms in the internal olefin sulfonate having 16 to 24 carbon atoms represents the number of carbon atoms in the internal olefin to which the sulfonate is covalently bonded.
• the carbon number of the internal olefin sulfonate having 16 to 24 carbon atoms is 17 or more, preferably 18 or more from the viewpoint of wrinkle prevention properties of the fiber, and 24 or less, preferably 22 from the viewpoint of sebum dirt cleaning property. Below, it is more preferably 20 or less.
• the internal olefin sulfonate of the present invention is a sulfone obtained by sulfonating, neutralizing, and hydrolyzing an internal olefin having 16 to 24 carbon atoms (olefin having a double bond inside the olefin chain) as a raw material. It is an acid salt.
• Such internal olefins include those containing a trace amount of so-called alpha olefins (hereinafter also referred to as ⁇ -olefins) in which the double bond is present at the 1st position of the carbon chain.
• ⁇ -sultones are produced quantitatively, and some of the ⁇ -sultones are converted into ⁇ -sultones and olefin sulfonic acids, which are further converted into hydroxyl in the neutralization/hydrolysis process.
• Converted to alkanesulfonates and olefinsulfonates eg, J. Am. Oil Chem. Soc. 69, 39 (1992)).
• the hydroxy group of the resulting hydroxyalkanesulfonate is located inside the alkane chain, and the double bond of the olefin sulfonate is located inside the olefin chain.
• the obtained products are mainly mixtures of these, and some of them include hydroxyalkanesulfonates having a hydroxyl group at the end of the carbon chain, or olefins having a double bond at the end of the carbon chain. May contain trace amounts of sulfonates.
• each of these products and mixtures thereof are collectively referred to as internal olefin sulfonate (component (a1)).
• hydroxyalkanesulfonate is referred to as a hydroxy form of internal olefin sulfonate (hereinafter also referred to as HAS), and olefin sulfonate is referred to as olefin form of internal olefin sulfonate (hereinafter also referred to as IOS).
• HAS hydroxy form of internal olefin sulfonate
• IOS internal olefin sulfonate
• the mass ratio of HAS to IOS of the compound in component (a1) can be measured using a high performance liquid chromatography mass spectrometer (hereinafter abbreviated as HPLC-MS). Specifically, the mass ratio can be determined from the HPLC-MS peak area of component (a1).
• HPLC-MS high performance liquid chromatography mass spectrometer
• Salts of internal olefin sulfonates include alkali metal salts, alkaline earth metal (1/2 atom) salts, ammonium salts, and organic ammonium salts.
• alkali metal salts include sodium salts and potassium salts.
• organic ammonium salts include alkanol ammonium salts having 2 or more and 6 or less carbon atoms.
• the salt of the internal olefin sulfonate is preferably an alkali metal salt, more preferably one or more selected from sodium salts and potassium salts.
• the sulfonic acid group of the internal olefin sulfonate as component (a1) exists inside the carbon chain, that is, the olefin chain or the alkane chain, and is partially present in the internal olefin sulfonate.
• a trace amount of sulfonic acid groups may also be present at the end of the carbon chain.
• the content of the internal olefin sulfonate having a sulfonic acid group present at the 5th position or higher, preferably at the 5th or higher position and lower than the 9th position is preferably 5% by mass from the viewpoint of anti-wrinkle properties of the fibers.
• each compound having a different sulfonic acid group position in component (a1) can be measured by HPLC-MS according to the method described in Examples.
• the content of each compound having a sulfonic acid group at a different position is determined as a mass ratio based on the HPLC-MS peak area of the compound having a sulfonic acid group at each position in all HAS forms of component (a1). shall be.
• the content of the olefin sulfonate in which the sulfonic acid group is present in the 1-position in the component (a1) is such that the content of the olefin sulfonate in which the sulfonic acid group is present in the 1st position is such that even if the temperature of the water used for washing is at a low temperature of 0°C or more and 15°C or less, the fiber will have good wrinkle resistance.
• the content is preferably 0.01% by mass or more.
• the position of the sulfonic acid group in these compounds is in the olefin or alkane chain.
• the above-mentioned internal olefin sulfonate can be a mixture of a hydroxy form and an olefin form.
• the mass ratio between the content of the olefin form of the internal olefin sulfonate and the content of the hydroxy form of the internal olefin sulfonate in the component (a1) (olefin form/hydroxy form) is 0/100 or more, and further 5/10. It can be 95 or more, further 10/90 or more, 50/50 or less, further 40/60 or less, further 30/70 or less, further 25/75 or less, and further 20/80 or less.
• the mass ratio between the content of the hydroxy form of the internal olefin sulfonate and the content of the olefin form of the internal olefin sulfonate in the component (a1) can be measured by HPLC-MS by the method described in the example. .
• Component (a1) can be produced by sulfonating, neutralizing, and hydrolyzing a raw material internal olefin having 16 to 24 carbon atoms.
• the sulfonation reaction can be carried out by reacting 1.0 to 1.2 moles of sulfur trioxide gas with respect to 1 mole of internal olefin.
• the reaction temperature can be 20 to 40°C.
• Neutralization is carried out by reacting with an aqueous alkali solution of sodium hydroxide, ammonia, 2-aminoethanol, etc. in an amount of 1.0 to 1.5 times the theoretical value of the sulfonic acid group by mole.
• the hydrolysis reaction may be carried out at 90 to 200°C for 30 minutes to 3 hours in the presence of water. These reactions can be performed sequentially.
• sulfonation, neutralization, and hydrolysis may be performed using a raw material internal olefin having a carbon number distribution of 16 to 24. Sulfonation, neutralization, and hydrolysis may be performed using raw material internal olefins having different numbers of carbon atoms, or, if necessary, pre-produced internal olefin sulfonates of different numbers may be mixed. It's okay.
• the internal olefin refers to an olefin having a double bond inside the olefin chain, as described above.
• the number of carbon atoms in the internal olefin, which is the raw material for component (a1), is 16 or more and 24 or less.
• the internal olefins used as the raw material for component (a1) may be used alone or in combination of two or more.
• anionic surfactants other than component (a1) as component (a) include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates other than component (a1), and alkanesulfones.
• examples include one or more selected from acid salts, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acid salts, ⁇ -sulfo fatty acid salts, N-acylamino acids, phosphoric acid mono- or diesters, and sulfosuccinic acid esters.
• alkyl ether sulfates include polyoxyethylene alkyl ether sulfates.
• the alkyl group or alkenyl group of the anionic surfactant has, for example, 8 to 22 carbon atoms.
• the average number of moles of oxyethylene groups added to the anionic surfactant is, for example, 0 or more and 10 or less.
• Counter ions for the anionic groups of these anionic surfactants include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as calcium ions and magnesium ions; ammonium ions; alkanol groups having 2 or 3 carbon atoms. Examples include alkanolamines having 1 to 3 (eg, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). These anionic surfactants can be used alone or in combination of two or more.
• Component (b1) is an amine-based alkaline agent.
• Examples of the amine-based alkaline agent as the component (b1) include one or more selected from alkanolamines and amino acids.
• the alkanolamine is preferably a monoamine compound of primary or higher class and lower than tertiary class, and includes an amine compound having 1 to 3 hydroxyalkyl groups having 2 to 4 carbon atoms bonded to a nitrogen atom.
• an alkanolamine has a group other than a hydroxyalkyl group, such a group includes an organic group, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
• alkanolamines include monoethalamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, tris(hydroxymethyl)aminomethane, N-methylethanolamine, N-methylpropanolamine, and N-ethylethanolamine.
• amino acid examples include one or more selected from neutral amino acids and basic amino acids.
• neutral amino acids include glycine, sarcosine, L-serine, ⁇ -alanine, aminobutyric acid, and the like.
• basic amino acids include arginine and lysine.
• Component (b1) is preferably one or more selected from monoethanolamine, diethanolamine, triethanolamine, glycine, arginine, and tris(hydroxymethyl)aminomethane from the viewpoint of sebum stain cleaning properties and low-temperature stability. , more preferably one or more selected from monoethanolamine, diethanolamine, triethanolamine, and glycine, still more preferably one or more selected from monoethanolamine and glycine, even more preferably monoethanolamine It is.
• Component (b1) may be blended into the composition as a counter ion for component (a), for example, the internal olefin sulfonate of component (a1). Furthermore, component (b1) may exist in the composition as ammonium ions depending on the pH of the composition. In the present invention, such a compound in the form of an ammonium ion is also used as the component (b1).
• Component (b2) of the present invention is a carbonate-based alkaline agent.
• the carbonate-based alkaline agent of component (b2) includes one or more selected from sodium carbonate, potassium carbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, and from the viewpoint of manufacturing cost, One or more types selected from sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate are preferable, and from the viewpoint of liquid color stability and solubility at high temperatures, one type selected from potassium carbonate and potassium hydrogen carbonate. The above is more preferable.
• the liquid detergent composition of the present invention preferably contains component (a) in an amount of 5% by mass or more, more preferably 8% by mass or more, still more preferably 12% by mass, from the viewpoint of anti-wrinkle properties of fibers and sebum stain cleaning properties. % or more, and from the viewpoint of liquid color stability at high temperatures, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more The content is preferably 18% by mass or less.
• the specification regarding the mass of component (a) (including component (a1)) shall be based on a value converted to sodium salt.
• the content of component (a1) in component (a) is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, from the viewpoint of wrinkle prevention properties of the fibers.
• the content may be greater than or equal to 100% by mass, and may be 100% by mass.
• the liquid detergent composition of the present invention preferably contains component (a1) in an amount of 5% by mass or more, more preferably 8% by mass or more, still more preferably 12% by mass, from the viewpoint of fiber wrinkle prevention properties and product stability. % or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 18% by mass or less.
• component (b1) is preferably 0.5% by mass or more, more preferably 0.65% by mass or more, still more preferably 0.8% by mass or more, and from the viewpoint of liquid color stability at high temperatures, preferably 2.8% by mass or less, more preferably 2.5% by mass or less, even more preferably 1.9% by mass or less, and more More preferably, the content is 1.5% by mass or less.
• component (b2) is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of sebum stain cleaning performance and liquid color stability at high temperatures. , more preferably 1.1% by mass or more, and from the viewpoint of low temperature stability, preferably 4.2% by mass or less, more preferably 3.4% by mass or less, still more preferably 2.5% by mass or less, and more preferably More preferably, the content is 2% by mass or less.
• the mass ratio (b2)/[(b1)+(b2)] of the content of component (b2) and the total content of components (b1) and (b2) is: From the viewpoint of sebum dirt cleaning performance and liquid color stability at high temperatures, it is preferably 0.1 or more, more preferably 0.17 or more, even more preferably 0.37 or more, even more preferably 0.4 or more, and From the viewpoint of sebum stain cleaning performance and low temperature stability, it is preferably 0.83 or less, more preferably 0.75 or less, still more preferably 0.65 or less.
• the mass ratio [(b1)+(b2)]/(a) of the total content of components (b1) and (b2) and the content of component (a) is: From the viewpoint of sebum stain cleaning properties, preferably 0.13 or more, more preferably 0.15 or more, even more preferably 0.18 or more, and sebum stain cleaning properties, liquid color stability at high temperatures, and fiber wrinkle prevention. From the viewpoints of properties and low temperature stability, it is preferably 0.65 or less, more preferably 0.5 or less, even more preferably 0.35 or less.
• the mass ratio [(b1)+(b2)]/(a1) of the total content of components (b1) and (b2) and the content of component (a1) is: From the viewpoint of sebum stain cleaning properties, preferably 0.13 or more, more preferably 0.15 or more, even more preferably 0.18 or more, and sebum stain cleaning properties, liquid color stability at high temperatures, and fiber wrinkle prevention. From the viewpoints of properties and low temperature stability, it is preferably 0.65 or less, more preferably 0.5 or less, even more preferably 0.35 or less.
• the liquid detergent composition of the present invention can contain a polyalkylene glycol having a weight average molecular weight of 100 or more and 100,000 or less as the component (c) from the viewpoint of low-temperature stability and viscosity adjustment.
• Component (c) includes one or more selected from polyethylene glycol and polypropylene glycol.
• the weight average molecular weight of component (c) is 100 or more, preferably 500 or more, and 10,000 or less, preferably 2,000 or less, more preferably 1,500 or less.
• the weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard substance.
• component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass, from the viewpoint of not interfering with low-temperature stability, viscosity adjustment, and anti-wrinkle properties of fibers. % or more, more preferably 0.15% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, even more preferably 0.5% by mass or less. .
• the liquid cleaning composition of the present invention can contain a fragrance composition as the component (d).
• the liquid detergent composition of the present invention preferably contains a fragrance composition whose formulation is comprised of various fragrance compounds used in detergent products for textile products. Examples of the fragrance compound constituting the fragrance composition include the fragrance compounds described in JP-A No. 2017-214676.
• the fragrance composition may be blended into the liquid cleaning composition in the form of being included in microcapsule particles, or may be blended in the form of an external fragrance (non-microcapsule).
• Microcapsules are encapsulated fragrance compositions that are functional ingredients. For example, a fragrance composition is encapsulated in the outer shell (wall material) of a microcapsule using a resin by a known method.
• the liquid cleaning composition of the present invention contains water.
• water deionized water (sometimes also referred to as ion-exchanged water) or water to which sodium hypochlorite is added in an amount of 1 mg/kg to 5 mg/kg to ion-exchanged water can be used. You can also use tap water.
• the liquid cleaning composition of the present invention preferably contains water in an amount of 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass. % or less, more preferably 85% by mass or less.
• the liquid cleaning composition of the present invention can contain components added to common compositions used for treating textile products, such as organic solvents, pH adjusters, preservatives, pigments, chelating agents, Hydrotropes and the like (excluding those corresponding to components (a), (b1), (b2), (c), and (d)) can be contained.
• components added to common compositions used for treating textile products such as organic solvents, pH adjusters, preservatives, pigments, chelating agents, Hydrotropes and the like (excluding those corresponding to components (a), (b1), (b2), (c), and (d)) can be contained.
• the pH at 20°C of the liquid cleaning composition of the present invention is 8.5 or more, preferably 8.7 or more, more preferably 9.0 or more, from the viewpoint of sebum stain cleaning performance and liquid color stability at high temperatures. , and is 11.0 or less, preferably 10.5 or less, more preferably 10.0 or less.
• the pH is measured according to the pH measurement method described below. To adjust the pH to this level, use ordinary acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, and lactic acid, and alkaline agents such as sodium hydroxide, potassium hydroxide, component (b1), and component (b2). be able to.
• ⁇ pH measurement method> Connect the composite electrode for pH measurement (glass rubbed sleeve type, manufactured by HORIBA) to a pH meter (PH/Ion Meter F-23, manufactured by HORIBA), and turn on the power.
• a saturated potassium chloride aqueous solution (3.33 mol/L) is used as the pH electrode internal solution.
• the pH measurement electrode is immersed in a standard solution adjusted to a constant temperature for 3 minutes, and the calibration operation is performed in the order of pH 6.86 ⁇ pH 9.18 ⁇ pH 4.01.
• the sample to be measured is adjusted to 20° C., the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.
• the viscosity of the liquid cleaning composition of the present invention at 20° C. is preferably 10 mPa ⁇ s or more, more preferably 30 mPa ⁇ s or more, even more preferably 50 mPa ⁇ s or more, and preferably It is 400 mPa ⁇ s or less, more preferably 300 mPa ⁇ s or less, still more preferably 200 mPa ⁇ s or less.
• these viscosities were measured using a B-type viscometer (VISCOMETER MODEL DVM-B, manufactured by Tokyo Keiki Co., Ltd.) using rotor No. 3 or 4, the rotation speed was 60 r/min, and the measurement time was 60 seconds.
• the rotor is selected to be suitable for the viscosity of the sample, but if the measurable viscosity regions overlap and different values are obtained, No. 3 shall be adopted.
• the liquid cleaning composition of the present invention can be suitably used for cleaning textile products.
• the fibers to be cleaned with the liquid detergent composition of the present invention may be either hydrophobic fibers or hydrophilic fibers.
• hydrophobic fibers include protein fibers (milk protein casein fiber, Promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), and polyvinyl alcohol fibers.
• Fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride/ Polyvinyl alcohol copolymer fibers (polycleral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), polyfluoroethylene fibers (polytetrafluoroethylene, etc.), glass fiber, carbon fiber, alumina fiber, silicone carbide fiber, rock Examples include fibers (rock fibers), mineral slag fibers (slag fibers), metal fibers (gold threads, silver threads, steel fibers), and the like.
• hydrophilic fibers examples include seed hair fibers (cotton, ramie, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (manila hemp, sisal, etc.), coconut fibers, Rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicu ⁇ a, angora, etc.), silk fibers (domestic silkworm silk, wild silkworm silk), feathers, cellulose fibers (rayon, polynosic, cupro, acetate, etc.) etc. are exemplified.
• the fibers are preferably fibers containing cotton fibers from the viewpoint that the finish quality of the fibers after washing with the liquid detergent composition of the present invention is more easily felt.
• the content of cotton fiber in the fiber is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, even more preferably 20% by mass or more, from the viewpoint of the finish of the fiber. It is even more preferably 40% by mass or more, even more preferably 60% by mass or more, even more preferably 80% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.
• textile products include fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics using the above-mentioned hydrophobic fibers and hydrophilic fibers, as well as undershirts, T-shirts, Y-shirts, blouses, slacks, and hats obtained using the same. , refers to products such as handkerchiefs, towels, knitwear, socks, underwear, and tights.
• the liquid detergent composition of the present invention is suitable for cleaning textile products in water containing hard components.
• suitable for cleaning textile products in water containing hardness components means that even when textile products are washed in water containing hardness components using the liquid detergent composition of the present invention, textile products are not washed in water containing hardness components. This means that it reduces wrinkles, gives a clean finish, and can wash away sebum stains that adhere to textile products.
• the hardness of the water is preferably 8° dH or more, more preferably 8.5° dH on the German hardness scale, from the viewpoint of sebum dirt cleaning performance and fiber wrinkle prevention property. Above, it is more preferably 9°dH or more, and preferably 20°dH or less, more preferably 17°dH or less, and still more preferably 15°dH or less.
• the calcium and magnesium concentrations for this German hardness are determined by chelate titration using ethylenediaminetetraacetic acid disodium salt.
• a specific method for measuring the German hardness of water in this specification is shown below. ⁇ How to measure the German hardness of water> ⁇ reagent ⁇ ⁇ 0.01 mol/l EDTA/2Na solution: 0.01 mol/l aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01 M EDTA-2Na, manufactured by SIGMA-ALDRICH) ⁇ Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories Co., Ltd.) ⁇ Ammonia buffer solution for hardness measurement (a solution in which 67.5 g of ammonium chloride was dissolved in 570 ml of 28 w/v% ammonia water and the total volume was made up to 1000 ml with ion-exchanged water) [Measurement of hardness] (1) Collect
• the present invention provides (a) an anionic surfactant (hereinafter referred to as component (a)) containing an internal olefin sulfonate having 16 to 24 carbon atoms (hereinafter referred to as component (a1)), and (b1) an amine-based alkaline agent. (hereinafter referred to as component (b1)), (b2) carbonate-based alkaline agent (hereinafter referred to as component (b2)), and water, and the content of component (a1) in component (a) is 70% by mass.
• a method for cleaning textile products in which textile products are washed with a cleaning liquid that is 100% by mass or less and has a pH of 7.5 or more and 10.5 or less.
• the cleaning liquid is preferably obtained by mixing the liquid detergent composition of the present invention and water.
• the cleaning liquid may further contain component (c).
• the cleaning liquid may further contain component (d).
• Component (a), component (a1), component (b1), component (b2), component (c), and component (d) are the same as those described in the liquid cleaning composition of the present invention.
• the embodiments described for the liquid detergent composition of the present invention can be applied as appropriate.
• the hardness of the water mixed with the liquid cleaning composition of the present invention is preferably 8° dH or higher, more preferably 8 on the German hardness scale, from the viewpoint of wrinkle prevention properties of textile products and sebum stain cleaning properties. .5° dH or more, more preferably 9° dH or more, and preferably 20° dH or less, more preferably 17° dH or less, still more preferably 15° dH or less. Further, the cleaning liquid may have a hardness within the above range.
• the hardness of the cleaning liquid is a value calculated using the above-mentioned "Method for measuring German hardness of water.”
• the hardness of the cleaning liquid can be selected from the preferred range of hardness of water containing the hardness component described in the liquid cleaning composition of the present invention.
• the hardness of the cleaning liquid can also be measured in the same manner as the hardness of water.
• the hardness of the water used in the cleaning method for example, the water used for preparing the cleaning liquid, the water used for rinsing, etc., is selected from the preferred range of hardness of water containing the hardness component described in the liquid cleaning composition of the present invention. can.
• the hardness of water can also be measured in the same manner as the hardness of water described above.
• the content of component (a) in the cleaning liquid is preferably 50 ppm or more, more preferably 80 ppm or more, even more preferably 120 ppm or more, and preferably 1500 ppm or less, more preferably 1200 ppm or less, and still more preferably 900 ppm or less. .
• the content of component (a1) in the cleaning liquid is preferably 50 ppm or more, more preferably 80 ppm or more, even more preferably 120 ppm or more, and preferably 1500 ppm or less, more preferably 1200 ppm or less, and still more preferably 900 ppm or less. .
• the content of component (b1) in the cleaning liquid is preferably 3 ppm or more, more preferably 5 ppm or more, even more preferably 8 ppm or more, and preferably 84 ppm or less, more preferably 75 ppm or less, and still more preferably 57 ppm or less. .
• the content of component (b2) in the cleaning liquid is preferably 3 ppm or more, more preferably 5 ppm or more, even more preferably 11 ppm or more, and preferably 126 ppm or less, more preferably 102 ppm or less, and still more preferably 75 ppm or less. .
• the mass ratio (b2)/[(b1) of the content of component (a1) in component (a), the content of component (b2), and the total content of component (b1) and (b2) )+(b2)]] the mass ratio of the total content of components (b1) and (b2) to the content of component (a) [(b1)+(b2)]/(a), (b1) components and the mass ratio [(b1)+(b2)]/(a1) of the total content of component (b2) and the content of component (a1) are respectively in the same range as the liquid cleaning composition of the present invention. It is preferable that
• the content of component (c) in the cleaning liquid is preferably 0.5 ppm or more, more preferably 1 ppm or more, even more preferably 1.5 ppm or more, and preferably It is 300 ppm or less, more preferably 150 ppm or less, even more preferably 30 ppm or less.
• the temperature of the cleaning liquid is preferably 0°C or higher, more preferably 3°C or higher, and even more preferably 5°C or higher, from the viewpoint of improving the ability to clean dirt adhering to textile products.
• the temperature is preferably 40°C or lower, more preferably 35°C or lower, from the viewpoint of making the textile product softer and with fewer wrinkles without removing too much of the oil contained in it.
• the pH of the cleaning solution at 20°C is 7.5 or higher, preferably 7.8 or higher, more preferably 8.0 or higher from the viewpoint of sebum dirt cleaning performance, and from the viewpoint of preventing fiber damage and not impairing finish quality. , 10.5 or less, preferably 10.0 or less, more preferably 9.5 or less.
• the pH of the cleaning liquid can be measured in the same manner as the pH of the liquid cleaning composition.
• the ratio (sometimes referred to as bath ratio) tends to decrease. If a household washing machine is used and the bath ratio is small, the agitation during washing increases the friction between textile products, which may impair the finish of the textile products.
• the method for cleaning textile products of the present invention can make textile products soft and clean-looking even under cleaning conditions where the bath ratio is low.
• the bath ratio is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, from the viewpoint of making the textile product softer and cleaner, and from the viewpoint of maintaining detergency. It is 45 or less, more preferably 40 or less, even more preferably 30 or less, even more preferably 20 or less.
• the cleaning time is preferably 1 minute or more, more preferably 2 minutes or more, and still more preferably 3 minutes or more, from the viewpoint of sebum stain cleaning performance and wrinkle prevention properties of textiles.
• the heating time is preferably 1 hour or less, more preferably 30 minutes or less, even more preferably 20 minutes or less, even more preferably 15 minutes or less.
• the method of cleaning textile products of the present invention is suitable for a method in which the fibers are immersed in a liquid used for refining while being fed with a roller or the like, and a rotary cleaning method.
• the rotary cleaning method refers to a cleaning method in which a textile product that is not fixed to a rotating device rotates together with a cleaning liquid around a rotation axis.
• the rotary washing method can be carried out with a rotary washing machine. Therefore, in the present invention, it is preferable to wash the textile products using a rotary washing machine, since the textile products can be finished more neatly.
• Specific examples of the rotary washing machine include a drum washing machine, a pulsator washing machine, and an agitator washing machine. As these rotary washing machines, those commercially available for household use can be used.
• Example ⁇ Composition ingredients> In the Examples and Comparative Examples, the following components were used.
• the position distribution of the sulfonic acid group of the HAS form contained in the internal olefin sulfonate of a-1 and the mass ratio of the olefin form and the hydroxy form (HAS form) were measured using a high performance liquid chromatograph mass spectrometer. Note that the internal olefin sulfonate having a double bond at the 6th position or higher had overlapping peaks and could not be clearly fractionated.
• the equipment and analysis conditions used for measurement are as follows.
• LC device "LC-20ASXR” (manufactured by Shimadzu Corporation)
• LC-MS device "LCMS-2020” (manufactured by Shimadzu Corporation)
• Detector: ESI (-), m/z 349.15 (C18), 321.
• ⁇ a-2 Sodium lauryl sulfate, "Sodium Dodecyl Sulfate", manufactured by Tokyo Chemical Industry Co., Ltd.
• [(b1) component] ⁇ b1-1 Monoethanolamine
• ⁇ b1-2 Diethanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• ⁇ b1-3 Triethanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• ⁇ b1-4 Glycine, Fuji Film manufactured by Wako Pure Chemical Industries, Ltd.
• Liquid cleaning compositions shown in Tables 1 and 2 were prepared using the above ingredients in the following manner.
• a 5 cm long Teflon (registered trademark) stirrer piece was placed in a 200 mL glass beaker and its mass was measured.
• 20 g of ion-exchanged water and components (a1), (a), (b1), (b2), (c), and (d) were added, and the composition was mixed while stirring at 100 r/min.
• Potassium hydroxide or hydrochloric acid was added so that the pH of the mixture became the values shown in Tables 1 and 2, and ion-exchanged water was added so that the total amount was 100 g.
• a liquid cleaning composition was prepared by stirring at 100 r/min for 15 minutes. Note that all mass % of the ingredients in Tables 1 and 2 are values based on the effective content.
• model sebum artificially contaminated cloth was prepared by attaching a model sebum artificially contaminated liquid having the following composition to cloth.
• the model sebum artificial contamination liquid was attached to the cloth by printing the artificial contamination liquid on the cloth using a gravure roll coater.
• the process of attaching the model sebum artificially contaminated solution to the cloth to produce the model sebum artificially contaminated cloth was carried out at a gravure roll cell capacity of 58 cm 3 /m 2 , an application speed of 1.0 m/min, a drying temperature of 100° C., and a drying time of 1 min. Ta.
• the cloth used was cotton 2003 (manufactured by Tanigashira Shoten).
• ⁇ Composition of model sebum artificial contamination liquid 0.4% by mass of lauric acid, 3.1% by mass of myristic acid, 2.3% by mass of pentadecanoic acid, 6.2% by mass of palmitic acid, 0.4% by mass of heptadecanoic acid, stearin.
• the rinsed and contaminated cloth was dehydrated for 1 minute using a two-layer washing machine, and then left to dry at 20° C. and 43% RH for 12 hours. Cleanability was evaluated based on detergency.
• the detergency (%) was measured by the method described below, and the average value of the four sheets was determined.
• the reflectance at a wavelength of 550 nm of the original cloth before contamination and the artificially contaminated cloth before and after washing was measured using a colorimeter (Z-300A, manufactured by Nippon Denshoku Co., Ltd.).
• Improvement rate of cleaning power 100 ⁇ [(Cleaning power of each example (%) - Cleaning power of Comparative example 8 (%)) / (Cleaning power of Comparative example 8 (%) - Cleaning power of Comparative example 9 (%))]
• the above formula shows the detergency (18.0%) of Comparative Example 9 which contains component (a1) of the present invention but does not contain components (b1) and (b2), and the detergency of Comparative Example 9 with a strong alkaline agent.
• the cleaning power of the liquid cleaning compositions of each Example and Comparative Example was determined based on the difference from the cleaning power of Comparative Example 8 (24.2%) in which the pH was adjusted to 9.6 by adding a certain potassium hydroxide.
• the improvement rate (%) was calculated. It can be said that the higher the improvement rate (%) of detergency, the better the sebum stain cleaning performance.

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• 2023
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