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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
• • 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
  • C11D1/94—Mixtures with anionic, cationic or non-ionic 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/201—Monohydric alcohols linear
• • 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
  • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
• • 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
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/90—Betaines

Definitions

• the present invention relates to a liquid cleaning agent for wiping.
• This application claims priority based on Japanese Patent Application Nos. 2013-150952 and 2013-150953 filed in Japan on July 19, 2013, the contents of which are incorporated herein by reference.
• toilet paper is often used for cleaning toilet seats and the vicinity of toilets, and handy toilet paper is often used.
• a liquid detergent is used and the dirt is wiped off with the toilet paper (wiping and cleaning)
• the toilet paper is easily broken.
• the cleaning object after wiping and cleaning has a liquid cleaning agent remaining, and is easily sticky or nullified.
• Patent Document 1 a toilet cleaning composition containing a specific amphoteric surfactant, ethanol 15 to 25% by mass, and ethylenediaminetetraacetic acid has been proposed (for example, Patent Document 1).
• Patent Document 1 According to the invention described in Patent Document 1, excellent cleaning power against stuck urine stains, toilet paper is difficult to tear even when toilet paper is used, there is no stickiness or nulling of the cleaning object, and no wiping marks are left This is an excellent convenience.
• flavor is mix
• liquid cleaning agents used for toilets and the like have been required to have fragrance persistence (residual fragrance) in a space after cleaning.
• a fragrance component having excellent residual fragrance has a strong hydrophobic property. For this reason, if an attempt is made to simply add a fragrance component with excellent residual fragrance to the invention described in Patent Document 1 having a high ethanol content, the fragrance component is difficult to dissolve in the liquid detergent, and a sufficient amount of the fragrance component cannot be added. There is a problem. In addition, if the blending amount of the highly hydrophobic fragrance component is simply increased, the liquid stability at low temperatures (0 ° C. or lower) tends to be lowered.
• this invention aims at the liquid cleaning agent for wiping which is excellent in the convenience in wiping cleaning, liquid stability, and foaming property, and is excellent in residual fragrance property.
• the liquid detergent for wiping is at least one selected from the component (A): secondary alkane sulfonate and a compound represented by the following general formula (a2)
• Component ethanol containing 15% by mass or more with respect to the total mass of the liquid detergent
• component a fragrance containing a fragrance component having a ClogP value of 3.0 or more, and the component (A) /
• the mass ratio represented by the component (B) is 0.3 to 30.
• R 1 and R 2 are each independently an alkyl group having 6 to 18 carbon atoms or an alkenyl group having 6 to 18 carbon atoms.
• M a is hydrogen, alkali metal, alkaline earth s indicates metal, ammonium, or alkanolamine any of ionized ions, t represents the valence of M a.
• R 11 is, .R 12 represents an alkyl or alkenyl group having 8 to 20 carbon atoms having 8 to 20 carbon atoms is, .R 13 and an alkylene group having 1 to 5 carbon atoms
• R 14 independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms
• R 15 represents an alkylene group having 1 to 5 carbon atoms.
• R 21 represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms.
• R 22 and R 23 represent Each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkenyl group having 2 to 4 carbon atoms, and R 24 represents a linear or branched alkenyl group having 1 to 6 carbon atoms, or Represents a branched alkylene group or a linear or branched hydroxyalkylene group having 1 to 6 carbon atoms.
• the mass ratio represented by [the component (A) + the component (B)] / the component (D) is 0.5 to 30 [ 1]
• the liquid detergent for wiping according to one embodiment of the present invention contains (E) component: a nonionic surfactant represented by the following general formula (e1), and [the component (A) + the above (The liquid cleaning agent for wiping according to [1] or [2], wherein the mass ratio represented by (B) component] / (E) component is 2 to 30.
• component a nonionic surfactant represented by the following general formula (e1), and [the component (A) + the above
• the liquid cleaning agent for wiping of the present invention the convenience in wiping and cleaning, the liquid stability and the foaming property are excellent, and the remaining fragrance is excellent.
• liquid cleaning agent for wiping contains the following components (A) to (D).
• the pH of the liquid detergent is preferably 5-9, more preferably 6-8. If pH is in the said range, it will suppress that the (D) component mentioned later changes in quality with a strong acid or a strong alkali, and a residual fragrance property is improved more.
• the pH value described above is a value measured at 25 ° C. Even a pH outside the range specified in the present specification is included in the scope of the present invention if the pH is within the range specified in the present specification when corrected to a pH at 25 ° C.
• the pH of the liquid detergent can be measured appropriately using a test paper, a test solution, an electrical pH measuring device (such as a pH meter) or other measuring means. In the present embodiment, as an example, a value measured by a pH meter (HM-30G, manufactured by Toa DKK Corporation) or the like can be used.
• the viscosity of the liquid detergent is not particularly limited, but is preferably 2 to 50 mPa ⁇ s, for example. If the viscosity is equal to or higher than the lower limit value, it easily stays in the cleaning target when applied to the cleaning target. If the viscosity is equal to or lower than the upper limit value, it is easy to pour out and wipe off the liquid cleaning agent.
• the viscosity of the liquid composition is a value measured at 25 ° C. with a B-type viscometer (in this embodiment, a B-type viscometer manufactured by TOKIMEC) (measurement conditions: rotor No. 2, rotation speed 60 rpm, Viscosity after 60 revolutions).
• Component (A) is a secondary alkane sulfonate (hereinafter also referred to as component (a1)) and a compound represented by formula (a2) described later (hereinafter also referred to as component (a2)).
• the component (a1) is a secondary alkane sulfonate.
• the component (a1) is a surfactant also called paraffin sulfonate, and is usually provided in the form of a mixture of compounds having 10 to 21 carbon atoms.
• the content of the component (a1) having 13 to 18 carbon atoms is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, particularly 100% by mass with respect to the total mass of the mixture. It may be mass%.
• the component (A) may contain a primary alkane sulfonate, disulfonate, polysulfonate, or the like.
• the content of these components is the total mass of the mixture of the component (a1).
• the content is preferably in the range of 0 to 20% by weight.
• Suitable examples of the component (a1) include compounds represented by the following general formula (a1).
• Examples of M as the counter ion include ions obtained by ionizing (ionizing) the following substances. Examples of these substances include alkali metals, alkaline earth metals, ammonia, alkanolamines, and the like. Examples of the alkali metal include sodium, potassium, and lithium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Among them, M is preferably an alkali metal, and sodium or potassium is more preferable for the alkali metal. In the formula (a1), s represents the valence of M. For example, if M is calcium, s is 2.
• HOSTAPUR SAS30 (trade name, manufactured by Clariant Japan Co., Ltd., containing 90% by mass or more of secondary sodium alkanesulfonate having 13 to 17 carbon atoms)
• HOSTAPUR SAS60 (trade name) , Manufactured by Clariant Japan Co., Ltd., containing 90 mass% or more of secondary alkane sulfonate having 13 to 17 carbon atoms)
• MERSOL80 trade name, manufactured by Bayer, Inc., average carbon number 15 (secondary having 13 to 17 carbon atoms) Contains 80% by mass or more of sodium alkanesulfonate.
• PS65, PS60, PS60W of the MARLON series (trade name, manufactured by SASOL. 90 mass of secondary alkanesulfonate of carbon number 10-18 (carbon number 13-17) %)))
• MARLON series (trade name, manufactured by SASOL. 90 mass of secondary alkanesulfonate of carbon number 10-18 (carbon number 13-17) %))
• the component (a2) is a compound represented by the following general formula (a2), and is a dialkylsulfosuccinic acid ester or a salt thereof.
• R 1 and R 2 are each independently an alkyl group having 6 to 18 carbon atoms or an alkenyl group having 6 to 18 carbon atoms.
• R 1 and R 2 preferably have 8 to 14 carbon atoms. If it is more than the said lower limit, the detergency with respect to oil dirt will be raised more, and since the solubility of (D) component in a liquid detergent becomes favorable, the liquid stability in low temperature will become favorable. If it is below the above upper limit, the solubility of this component in the liquid detergent becomes good, and precipitation or the like during storage at low temperatures is unlikely to occur.
• R 1 and R 2 may be linear or branched, with a branched chain being preferred.
• R 1 and R 2 are preferably alkyl groups.
• M a is a counter ion.
• examples include ions obtained by ionizing (ionizing) the following substances. Examples of these substances include hydrogen, alkali metals, alkaline earth metals, ammonia, and alkanolamines. Examples of the alkali metal include sodium, potassium, and lithium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Among them, the M a, alkali metals are preferred, and more preferably sodium or potassium.
• t represents the valence of M a . For example, t is 2 if M a is calcium.
• component (a2) examples include di-2-ethylhexyl sulfosuccinic acid ester salt, di-tridecyl sulfosuccinic acid ester salt, and dilauryl sulfosuccinic acid ester salt. These (a2) components may be used individually by 1 type, and may be used in combination of 2 or more type.
• a component may be used individually by 1 type and may be used in combination of 2 or more type.
• the content of the component (A) in the liquid detergent is preferably 0.1 to 1.9% by mass and more preferably 0.1 to 1.5% by mass with respect to the total mass of the liquid detergent. If it is more than the said lower limit, the component (D) mentioned later can be solubilized more reliably and residual fragrance property can be improved more, and if it is below the said upper limit, the wiping trace residue can be prevented more favorably.
• the component (B) includes a compound represented by the following general formula (b1) (hereinafter sometimes referred to as the (b1) component) and a compound represented by the following general formula (b2) (hereinafter referred to as the (b2) component). At least one amphoteric surfactant selected from.
• the component (b1) is a compound represented by the following general formula (b1).
• R 11 is an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms.
• R 11 preferably has 9 to 15 carbon atoms. If it is more than the said lower limit, since the solubility of (D) component in a liquid cleaning agent will become favorable, the liquid stability in low temperature will become favorable. If it is below the above upper limit, the solubility of the present component in the liquid detergent becomes good, and precipitation during storage is unlikely to occur.
• R 11 may be a straight chain or a branched chain, and among them, a straight chain is preferable.
• R 11 is preferably an alkyl group.
• R 12 is an alkylene group having 1 to 5 carbon atoms.
• R 12 preferably has 2 to 3 carbon atoms. If it is in the said range, the solubility of (D) component in a liquid cleaning agent will increase more, and the liquid stability in low temperature will become favorable.
• R 12 may be a straight chain or a branched chain, and among them, a straight chain is preferable.
• R 13 and R 14 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.
• R 13 and R 14 are preferably alkyl groups.
• the alkyl group preferably has 1 to 2 carbon atoms. If it is in the said range, the solubility of (D) component in a liquid cleaning agent will become favorable, and the liquid stability in low temperature will become favorable.
• R 13 or R 14 is an alkyl group, the alkyl group may be a straight chain or a branched chain, and among them, a straight chain is preferable.
• R 15 is an alkylene group having 1 to 5 carbon atoms.
• R 15 preferably has 1 to 3 carbon atoms. If it is in the said range, the solubility of (D) component in a liquid cleaning agent will become favorable, and the liquid stability in low temperature will become favorable.
• R 15 may be a straight chain or a branched chain, and among them, a straight chain is preferable.
• component (b1) examples include octylamidopropyl-N, N-dimethylacetic acid betaine (amidopropyloctane octoate), laurylamidopropyl-N, N-dimethylacetic acid betaine (amidopropyl betaine laurate), stearyl-N N-dimethylacetic acid betaine (amidopropyl betaine stearate), stearyl-N, N-dimethyl-2-hydroxypropyl betaine or coconut oil fatty acid amidopropyl betaine.
• a (b1) component lauric acid amide propyl betaine is preferable.
• These (b1) components may be used individually by 1 type, and 2 or more types may be used in combination.
• the component is commercially available.
• Examples of the lauric acid amidopropyl betaine include “Enalicol L-30B” manufactured by Lion Corporation, and examples of the coconut oil fatty acid amidopropyl betaine include “CAB-30” manufactured by Otsuka Kogyo Kogyo Co., Ltd. or Degussa Corporation. Examples include “TEGO BETAIN CK-OK”.
• Examples of the palm kernel oil fatty acid amidopropyl betaine include “Amholex PB-1” manufactured by Miyoshi Oil & Fat Co., Ltd.
• the component (b2) is a compound represented by the following general formula (b2).
• R 21 represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms.
• R 21 preferably has 10 to 16 carbon atoms. If it is more than the said lower limit, the solubility of (D) component in a liquid cleaning agent will become favorable, and the liquid stability in low temperature will become favorable. If it is below the above upper limit value, the solubility of the present component in the liquid detergent becomes good, so that precipitation during storage is unlikely to occur.
• R 21 may be linear or branched, and is preferably linear.
• R 21 is preferably an alkyl group.
• R 22 and R 23 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkenyl group having 2 to 4 carbon atoms.
• R 22 and R 23 preferably have 1 to 2 carbon atoms. If it is in the said range, the solubility of (D) component in a liquid cleaning agent will become favorable, and the liquid stability in low temperature will become favorable.
• R 22 and R 23 may be linear or branched, and among them, linear is preferable.
• R 22 and R 23 are preferably an alkyl group.
• R 24 is a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched hydroxyalkylene group having 1 to 6 carbon atoms.
• R 24 preferably has 1 to 3 carbon atoms. If it is in the said range, the solubility of (D) component in a liquid cleaning agent will become favorable, and the liquid stability in low temperature will become favorable.
• R 24 may be a straight chain or a branched chain, and among them, a straight chain is preferable.
• R 24 is preferably an alkylene group.
• component (b2) examples include coconut oil alkyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, palmityldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine.
• a (b2) component lauryl dimethylamino acetic acid betaine is preferable.
• These (b2) components may be used individually by 1 type, and may be used in combination of 2 or more type.
• the component (b2) is commercially available.
• lauryldimethylaminoacetic acid betaine examples include “Levon LD-36” manufactured by Sanyo Chemical Industries, Ltd., and “Ovazoline LB-SF” manufactured by Toho Chemical Industries, Ltd.
• stearyldimethylaminoacetic acid betaine examples include “Amphitol 86B” manufactured by Kao Corporation.
• the (B) component mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.
• the component (B) it is preferable to use the component (b1) and the component (b2) in combination.
• the mass ratio represented by the component (b1) / the component (b2) (hereinafter sometimes referred to as the b1 / b2 ratio) is preferably 0.5 to 10. 1 to 7 are more preferable. If b1 / b2 ratio is more than the said lower limit, foaming property can be improved more, and if it is below the said upper limit, residual fragrance property and liquid stability in low temperature can be improved more.
• the content of the component (B) in the liquid detergent is preferably 0.1 to 1.9% by mass and more preferably 0.5 to 1.9% by mass with respect to the total mass of the liquid detergent. If it is more than the said lower limit, the component (D) mentioned later can be solubilized more reliably and residual fragrance property can be improved more, and if it is below the said upper limit, the wiping trace residue can be prevented more favorably.
• the total amount of the component (A) and the component (B) is preferably 0.5 to 5% by mass, and more preferably 1 to 3% by mass with respect to the total mass of the liquid cleaning agent. If it is more than the said lower limit, the component (D) mentioned later can be solubilized more reliably and residual fragrance property can be improved more, and if it is below the said upper limit, the wiping trace residue can be prevented more favorably.
• the mass ratio represented by (A) component / (B) component (hereinafter sometimes referred to as A / B ratio) is 0.3 to 3, preferably 0.5 to 2. If the A / B ratio is within the above range, the balance between the component (A) and the component (B) is good, the component (D) is easy to solubilize, good residual fragrance, and liquid stability at low temperatures. Can be obtained. In addition, if the A / B ratio is equal to or less than the above upper limit value, the foamability can be improved.
• the component (C) is ethanol. Since the liquid detergent contains the component (C), the toilet paper is not easily torn even when the toilet paper is wiped off and cleaned.
• the content of the component (C) in the liquid detergent is 15% by mass or more, preferably 15 to 25% by mass, and more preferably 18 to 22% by mass with respect to the total mass of the liquid detergent. If it is less than the above lower limit value, toilet paper tends to be torn, and if it exceeds the above upper limit value, the amount of the (D) component dissolved decreases, and the residual fragrance may be lowered.
• a component is a fragrance
• a liquid cleaning agent can improve a residual fragrance property by containing (D) component.
• a component is a composition which consists of a fragrance
• the perfume ingredients are described in, for example, “Perfume and Flavor Chemicals”, Vol. I and II, Stephen Arctander, Allured Pub. Co. (1994), “Synthetic perfume chemistry and product knowledge”, Motoichi Into, Chemical Industry Daily (1996), “Perfume and Flavor Materials of Natural Origin”, Stephen Arctander, Allred Pub. Co.
• the component (d1) is a fragrance component having a ClogP value of 3.0 or more.
• the ClogP value is a value representing the 1-octanol / water partition coefficient P representing the ratio of equilibrium concentrations in 1-octanol and in water in the form of logarithmic logP with respect to the base 10 for the chemical substance.
• the ClogP value is obtained by decomposing the chemical structure of a compound into its constituent elements by the f method (hydrophobic fragment constant method) and integrating the hydrophobic fragment constants ⁇ f of each fragment (for example, Clog 3 Reference). (See Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March, 1994).
• the fragrance component is more hydrophobic as the ClogP value is larger, the fragrance containing more fragrance components having a higher ClogP value is more hydrophobic than the fragrance containing more fragrance components having a lower ClogP value.
• the component (d1) has good scent persistence.
• a fragrance component having a ClogP value of less than 3.0 hereinafter sometimes referred to as a component (d2)
• a component (d2) has a good fragrance, but the fragrance persistence is insufficient.
• the ClogP value of the component (d1) but the ClogP value is 8.0 or less as a guide.
• D1 As a component, the fragrance
• the content of the component (d1) in the component (D) is not particularly limited, and may be more than 0% by mass and 100% by mass or less with respect to the total mass of the component (D). % Is preferable, and 30 to 50% by mass is more preferable. If it is more than the said lower limit, residual fragrance property can be improved more, and if it is below the said upper limit, (D) component will provide moderate hydrophilicity, and fragrance will become favorable.
• the content of the component (d1) in the liquid detergent is not particularly limited, and is preferably 0.06 to 0.2% by mass, for example, 0.09 to 0.15 with respect to the total mass of the liquid detergent.
• the mass% is more preferable. If the amount is less than the above lower limit, the residual fragrance may be lowered, and if it exceeds the above upper limit, the components (A) to (B) for solubilizing the component (d1) become too much, and sticky or nullified. Or wiping marks may remain.
• the component (d2) is a fragrance component having a ClogP value of less than 3.0.
• the sustained release property of the component (D) is increased and the fragrance is improved.
• the lower limit of the ClogP value of the component (d2) is not particularly provided, the ClogP value is 1.0 or more as a guide.
• the content of the component (D) in the liquid detergent is preferably 0.1 to 1% by mass, and more preferably 0.2 to 0.5% by mass with respect to the total mass of the liquid detergent. If it is more than the said lower limit, residual fragrance property can be improved more, and if it is below the said upper limit, liquid stability at low temperature can be improved more.
• the mass ratio represented by [(A) component + (B) component] / (D) component (hereinafter sometimes referred to as (A + B) / D ratio) is preferably 0.5-30. 3 to 25 is more preferable, and 3 to 10 is more preferable.
• the (A + B) / D ratio is equal to or higher than the lower limit, the contents of the component (A) and the component (B) are not decreased too much, and the residual fragrance is further increased, and the liquid stability at a low temperature is easily increased.
• the (A + B) / D ratio is not more than the above upper limit value, the content of the component (D) is not decreased too much, and the residual fragrance property is easily improved.
• the wiping liquid detergent according to another aspect of the embodiment of the present invention contains the following component (E) in addition to (A) to (D) of the embodiment.
• the component (E) is a nonionic surfactant represented by the following general formula (e1) and is a so-called alcohol ethoxylate. Since the liquid detergent contains the component (E), the component (D) is solubilized in the solvent, the residual fragrance is increased, and the liquid stability at low temperature can be increased.
• R 31 is a branched alkyl group.
• R 31 has 8 to 18 carbon atoms, preferably 12 to 15 carbon atoms. If it is more than the said lower limit, (D) component can fully be solubilized with respect to a solvent, residual fragrance property can be improved, and liquid stability at low temperature can be improved. If it is below the said upper limit, the water solubility of (E) component will not become low too much, and the liquid stability in low temperature can be improved.
• the average number of side chains of R 31 (hereinafter sometimes referred to as the average branch number) is 0.2 to 2, and preferably 0.4 to 1.5. If it is in the said range, (D) component can be solubilized with respect to a solvent, residual fragrance property can be improved, and liquid stability at low temperature can be improved.
• the number (number of branches) of the side chain of R 31 is defined as the number obtained by subtracting 1 from the number of methyl groups in one molecule (E) component.
• the average branch number is a statistical average value of the number of side chains in the component (E).
• the average number of methyl groups in the component (E) is easily measured by 1 H-NMR spectroscopy.
• the average number of branches in this paper is calculated by the following equation (1). That is, the average number of branches is determined by dividing the signal region corresponding to the methyl proton (CH 3 group) in the 1 H-NMR spectrum by 3, and this value and the signal of the methylene proton of the CH 2 —OH group divided by 2. This is a value obtained by comparing the area.
• Average number of branches ⁇ (integral value of signal region corresponding to methyl proton of CH 3 group / 3) ⁇ (integral value of signal region corresponding to methylene proton of CH 2 —OH group / 2) ⁇ / (CH 2 ⁇ Integral value of signal region corresponding to methylene proton of OH group / 2) (1)
• the measurement target (component (E)) is dissolved in heavy water or deuterated chloroform, and the sample concentration is set to 30% by mass. This is measured by 1 H-NMR (JNM-LA300 FT NMR SYSTEM manufactured by JEOL).
• OE represents an oxyethylene group
• n is a number representing the average number of repeating oxyethylene groups (that is, the average number of moles of ethylene oxide added).
• n is preferably 2 to 7, and more preferably 2 to 4. If it is more than the said lower limit, the water solubility of (E) component will not become low too much, residual fragrance property can be improved, and liquid stability at low temperature can be made favorable. If it is below the upper limit, the component (D) can be solubilized in the solvent, the residual fragrance can be improved, and the liquid stability at low temperatures can be improved.
• (E) component for example, Rutensol AO3 manufactured by BASF (trade name. Mixture of 13 and 15 carbon atoms of R 31 , average branch number 0.8, average repeat of oxyethylene group number 3.), a mixture of 13 and 15 carbon atoms of Lutensol AO2 (trade name .R 31 manufactured by BASF Corporation, average branching of 0.8, the average number of repeating oxyethylene groups 2.), BASF Corp.
• Rutensol AO3 manufactured by BASF (trade name. Mixture of 13 and 15 carbon atoms of R 31 , average branch number 0.8, average repeat of oxyethylene group number 3.)
• Lutensol AO2 trade name .R 31 manufactured by BASF Corporation, average branching of 0.8, the average number of repeating oxyethylene groups 2.
• Rutensol O7 (trade name, a mixture of 13 and 15 carbon atoms of R 31 , an average branch number of 0.8, an average number of repeating oxyethylene groups of 7), or Rutensol XP30 manufactured by BASF (product) And the number of carbon atoms of R 31 is 10, the average number of branches is 1, and the average number of repeating oxyethylene groups is 3.). Further, the component (E) may be one obtained by adding ethylene oxide to a commercially available alcohol.
• an ethylene oxide adduct of 2-ethylhexanol (R 31 is 2-ethylhexyl, average number of branches 1, average number of repeating oxyethylene groups is 3), mixed alcohol of 12 and 13 carbon atoms (Saffor 23 (trade name) ), An ethylene oxide adduct (a mixture of R 31 having 12 and 13 carbon atoms, an average branching number of 1.2 and an average number of repeating oxyethylene groups of 3), or 16 and 17 carbon atoms.
• An ethylene oxide adduct of a mixed alcohol (Neodol 67 (trade name, manufactured by Shell)) (a mixture of R 31 with 16 and 17 carbon atoms, an average number of branches of 1.8, and an average number of repeating oxyethylene groups of 3) Etc.).
• the content of component (E) in the liquid detergent is preferably 0.1 to 0.8% by mass, more preferably 0.1 to 0.5% by mass. If it is more than the said lower limit, residual fragrance property can be improved more, and if it is below the said upper limit, liquid stability at low temperature can be improved more.
• Component (E) is produced, for example, by adding ethylene oxide to alcohol (R 31 OH) using a known catalyst.
• the mass ratio represented by [(A) component + (B) component] / (E) component (hereinafter sometimes referred to as (A + B) / E ratio) is 2 to 30, and 3 ⁇ 22 are more preferred. If it is in the said range, the balance of (A) component, (B) component, and (E) component will become favorable, and the liquid stability at low temperature can be improved. In addition, if it is more than the said lower limit, foamability can be improved.
• the mass ratio represented by component (D) / component (E) (hereinafter sometimes referred to as D / E ratio) is preferably 0.5 to 4.5, more preferably 2 to 4. . If it is more than the said lower limit, residual fragrance property can be improved more, and if it is below the said upper limit, the liquid stability in low temperature can be improved.
• the liquid cleaning agent of this embodiment contains a solvent.
• the solvent is added for the purpose of dissolving the above components (A) to (E) or uniformly dispersing them in the liquid detergent.
• water such as tap water, ion exchange water, or distilled water can be used, and ion exchange water is particularly preferable.
• the content of the solvent in the liquid detergent is not particularly limited. For example, when the solvent is water, the content is preferably 50 to 90% by mass, more preferably 60 to 80% by mass with respect to the total mass of the liquid detergent.
• the liquid detergent may contain optional components other than the components (A) to (E) as long as the effects of the present invention are not impaired.
• optional components include surfactants (optional surfactants) other than the components (A) to (B) and (E), thickeners, preservatives, colorants, or pH adjusters.
• the liquid detergent is produced by a conventionally known method.
• Examples of the method for producing the liquid detergent include a method of adding (A) to (D) and optionally (E) component and optionally an optional component to water and stirring the mixture. .
• the liquid cleaning agent is stored in a spray-type discharge container or a squeeze-type discharge container, and an appropriate amount of liquid cleaning agent is applied from these containers to the object to be cleaned such as a toilet seat or floor surface. And a method of wiping off the applied liquid detergent together with dirt.
• the liquid cleaning agent paper or cloth such as toilet paper can be used.
• the liquid cleaning agent of the embodiment can sufficiently clean the object to be cleaned.
• a method of applying a liquid cleaning agent to paper or cloth such as toilet paper (or including liquid cleaning agent in these paper or cloth) and wiping the object to be cleaned with this toilet paper or the like can be mentioned.
• a liquid cleaning agent for example, 0.1 to 2 ml of liquid detergent is applied per unit area of paper or cloth (for example, 8 folds of 11.5 cm ⁇ 30 cm toilet paper) and By wiping one to three times, the object to be cleaned can be sufficiently cleaned with the liquid cleaning agent of this embodiment.
• the liquid detergent of the present invention since it contains the components (A) to (C), it has excellent convenience that the toilet paper is not easily torn during wiping and cleaning. In addition, since it contains the components (A) to (D) and the A / B ratio and the (A + B) / D ratio are in a specific range, it is difficult for wiping marks to remain, and excellent residual fragrance properties can be exhibited.
• the components (A) to (E) are contained, and the A / B ratio is within a specific range, and the (A + B) / E ratio Is in a specific range, it is excellent in convenience in wiping and cleaning, liquid stability and foaming properties, and excellent in remaining fragrance.
• the liquid cleaning agent of this embodiment is particularly suitable as a wiping cleaning agent for toilets.
• A-1 Secondary alkane sulfonate sodium (SAS, average molecular weight 328), “HOSTAPUR SAS60” (trade name) manufactured by Clariant Japan KK (A1)
• SAS Secondary alkane sulfonate sodium
• HOSTAPUR SAS60 trade name
• A-2 sodium dialkylsulfosuccinate “Ripal 870P” (trade name) manufactured by Lion Corporation.
• R 1 and R 2 are 2-ethylhexyl
• M a is sodium
• t is 1. This corresponds to the component (a2).
• ⁇ (A ′) component Comparative product of component (A)>
• A′-1 sodium linear alkylbenzene sulfonate (LAS, carbon number of linear alkyl group of 10 to 15).
• A′-2 sodium polyoxyethylene alkyl ether sulfate ester (AES).
• AES sodium polyoxyethylene alkyl ether sulfate ester
• A′-3 sodium ⁇ -olefin sulfonate (AOS, mixture of carbon numbers 14 and 16)
• Liporan LB-440 (trade name) manufactured by Lion Corporation.
• A′-4 sodium myristate.
• NonSal MN-1 (trade name) manufactured by NOF Corporation.
• A′-5 ether carboxylate.
• Energy Call EC-30 (trade name) manufactured by Lion Corporation.
• A′-6 N-acyl amino acid salt.
• Enagicol L-30AM (trade name) manufactured by Lion Corporation.
• A′-7 alkyl diphenyl ether sulfonate.
• Dow Chemical “Dowfax AXC6L” (trade name) manufactured by Dow Chemical.
• ⁇ (B ′) component Comparative product of component (B)> B′-1: dodecyldimethylamine oxide (AX). “Aromox DM12 DW (C)” (trade name) manufactured by Lion Akzo Corporation. B′-2: laurylamidopropyldimethylamine oxide (APAX).
• Softazolin LAO (trade name) manufactured by Kawaken Fine Chemical Co., Ltd.
• B′-3 N-coconut oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine.
• Softazolin NS (trade name) manufactured by Kawaken Fine Chemical Co., Ltd.
• B′-4 hydroxyalkylhydroxyethylethylenediamine Na.
• SOFTAZOLINE LMEB (trade name) manufactured by Kawaken Fine Chemical Co., Ltd.
• ⁇ (C) component> C-1 ethanol. Kyowa Hakko Kogyo Co., Ltd. “fermented alcohol 95 degrees” (trade name).
• D-1 Fragrance D-1 described in Table 2.
• D-2 Fragrance D-2 described in Table 2.
• D′ Fragrance D′-1 described in Table 2.
• E-1 Alcohol ethoxylate (mixture of R 31 having 13 and 15 carbon atoms. Average number of branches: 0.8, average number of repeating oxyethylene groups (denoted as OE mol number in the table; the same applies hereinafter). ) Is 3.). “Rutensol AO3” (trade name) manufactured by BASF Japan Ltd.
• E-2 Alcohol ethoxylate (mixture of R 31 having 13 and 15 carbon atoms. Average branching number 0.8, average repeating number of oxyethylene groups is 2.)
• Ruletensol AO2 (trade name) manufactured by BASF Japan Ltd.
• E-3 Alcohol ethoxylate (R 31 is a mixture of 13 and 15 carbon atoms.
• the average number of branches is 0.8 and the average number of repeating oxyethylene groups is 7.
• “Rutensol AO7” (trade name) manufactured by BASF Japan Ltd.
• E-4 alcohol ethoxylate (2-ethylhexyl, average branching number 1.0, average repeating number of oxyethylene groups is 3). A product obtained by adding 3 moles of ethylene oxide to 2-ethylhexyl alcohol. Synthetic product.
• E-5 Alcohol ethoxylate (R 31 has 10 carbon atoms, average number of branches is 1.0, and average number of repeating oxyethylene groups is 3).
• “Rutensol XP30” (trade name) manufactured by BASF Japan Ltd.
• E-6 Alcohol ethoxylate (R 31 is a mixture of 12 and 13 carbon atoms. The average number of branches is 1.2 and the average number of repeating oxyethylene groups is 3.) 3 mol of ethylene oxide added to "Safol 23" manufactured by Sasol.
• E-7 Alcohol ethoxylate (mixture of R 31 having 16 and 17 carbon atoms. Average number of branches 1.8 and average number of repeating oxyethylene groups 3). A product obtained by adding 3 moles of ethylene oxide to “Neodol 67” manufactured by Shell. Synthetic product.
• ⁇ (E ') component Comparative product of (E) component>
• E′-1 alcohol ethoxylate (R 31 is a mixture of 13 and 15 carbon atoms.
• Average branching number is 0.8 and average repeating number of oxyethylene groups is 8.
• “Rutensol AO8” (trade name) manufactured by BASF Japan Ltd.
• E′-2 polyoxyethylene (5) octyldodecyl ether (R 31 has 20 carbon atoms, average number of branches is 1.0, and average number of repeating oxyethylene groups is 5.)
• “EMALEX OD-5” (trade name) manufactured by Nippon Emulsion Co., Ltd.
• E′-3 polyoxyethylene (3) lauryl ether (R 31 has 12 carbon atoms. No branching and the average number of repeating oxyethylene groups is 3).
• “EMALEX 703” (trade name) manufactured by Nippon Emulsion Co., Ltd.
• E′-4 alcohol ethoxylate (the carbon number of R 31 is 13. The average number of branches is 2.4, and the average number of repeating oxyethylene groups is 3.)
• “Rutensol TO3” (trade name) manufactured by BASF Japan Ltd.
• Example A (Examples A1 to A27, Comparative Examples A1 to A26) According to the composition shown in Tables 3 to 6, 500 g of the liquid cleaning agent of each example was prepared by the following procedure (components not described in the table were not added). The component (C) and the common component were added to water and mixed, then the components (A) to (B) and the component (E) were added and mixed, and then the component (D) was added and mixed. If necessary, a pH adjusting agent (citric acid or potassium hydroxide) was newly added to adjust the pH to 7.0, thereby obtaining the liquid cleaning agent of each example.
• a pH adjusting agent citric acid or potassium hydroxide
• the blending amount “appropriate amount” of the pH adjuster is an amount required to bring the liquid detergent to pH 7.0.
• the “Balancing” amount of water is an amount necessary to make the total amount of the liquid detergent 100% by mass.
• the pH was read 30 seconds after the electrode was immersed in the liquid detergent using a glass electrode pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.) after adjusting the liquid detergent to 25 ° C. Value.
• the pH measurement method is based on JIS K3362-1998.
• Examples A1 to A27 to which the present invention is applied have a paper tear prevention effect of “A” or “B”, and a wiping trace residual prevention effect of 3 to 5 points. It was excellent in nature.
• the residual fragrance was 3 to 5 points
• the liquid stability at low temperature was “A” or “B”
• the foaming property was “A” or “B”.
• Comparative Examples A1, A2, A4, and A5 that did not contain any of the component (A), the component (B), the component (D), and the component (E) were inferior in fragrance.
• Comparative Example A3 containing no component (C) the effect of preventing paper breakage was “D”.
• Comparative Examples A6 to A12 using the component (A ′) in place of the component (A) and Comparative Examples A13 to A16 using the component (B ′) in place of the component (B) have two residual fragrances.
• the liquid stability at low temperature was “D” or “C”.
• Comparative Example A17 using the component (C ′) in place of the component (C) the paper breakage preventing effect was “D”, the wipe remaining residue preventing effect was 1 point, and the residual fragrance was 2 points.
• Comparative Example A18 using the component (D ′) instead of the component (D) the residual fragrance was 2 points.
• Comparative Examples A19 to A22 using the component (E ′) instead of the component (E) the liquid stability at low temperature was “D” or “C”.
• Test Example B (Examples B1 to B22, Comparative Examples B1 to B20) According to the compositions shown in Tables 7 to 10, 500 g of the liquid cleaning agent in each example was prepared in the following procedure in the same manner as in Test Example A (components not described in the table were not added). Evaluations for the paper tear prevention effect, the remaining wiping residue prevention effect, the remaining fragrance property and the appearance were performed according to the same evaluation criteria as in Test Example A.
• Example B1 to B22 As shown in Tables 7 to 10, in Examples B1 to B22 to which the present invention is applied, the paper tear prevention effect is “A” or “B”, and the remaining wipe prevention effect is 3 to 5 points. It was excellent in nature. In addition, Examples B1 to B22 had a residual fragrance of 3 to 5 points. On the other hand, Comparative Examples B1, 2, and 4 that did not contain any of the (A) component, the (B) component, and the (D) component were inferior in fragrance. Comparative Example B3 containing no component (C) had a paper tear prevention effect of “D”.
• Comparative Examples B5 to B11 using the component (A ′) instead of the component (A), and Comparative Examples B12 to B13 using the component (B ′) instead of the component (B) have 2 points of residual fragrance. It was the following. In Comparative Examples B14 to B15 using the component (C ′) instead of the component (C), the paper tear preventing effect is “D” or “C”, and the remaining wipe preventing effect is 1 point or 2 points. It was. In Comparative Example B16 using the component (D ′) instead of the component (D), the residual fragrance was 2 points.
• Comparative Example B17 having an A / B ratio of 0.1 had a residual fragrance of 1 point
• Comparative Example B18 having an A / B ratio of 38 had a wiping trace remaining preventing effect of 2 points.
• Comparative Example B19 in which the (A + B) / D ratio was 0.4 and Comparative Examples B19 to B20 in which the (A + B) / D ratio was 33.3 all had a residual fragrance of 2 points or less. From these results, it was found that by applying the present invention, both excellent convenience and excellent residual fragrance can be achieved.
• the liquid cleaning agent for wiping of the present invention the convenience in wiping and cleaning, the liquid stability and the foaming property are excellent, and the remaining fragrance is excellent.

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• 2014
  • 2014-07-16 CN CN201480037360.7A patent/CN105452434B/zh active Active
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