WO2015008787A1 - Wipe-off-type liquid cleaning agent - Google Patents
Wipe-off-type liquid cleaning agent Download PDFInfo
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- WO2015008787A1 WO2015008787A1 PCT/JP2014/068904 JP2014068904W WO2015008787A1 WO 2015008787 A1 WO2015008787 A1 WO 2015008787A1 JP 2014068904 W JP2014068904 W JP 2014068904W WO 2015008787 A1 WO2015008787 A1 WO 2015008787A1
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- fragrance
- cleaning agent
- liquid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—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.
Abstract
Description
本願は、2013年7月19日に、日本に出願された特願2013-150952号及び特願2013-150953号及びに基づき優先権を主張し、その内容をここに援用する。 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.
こうした問題に対し、特定の両性界面活性剤と、エタノール15~25質量%と、エチレンジアミンテトラ酢酸とを含有するトイレ用洗浄剤組成物が提案されている(例えば、特許文献1)。特許文献1に記載の発明によれば、こびり付いた尿汚れに対する優れた洗浄力と、トイレットペーパーを用いてもトイレットペーパーが破れにくい、洗浄対象のべた付きやヌル付きがない、拭き跡を残さないという優れた利便性との両立が図られている。 Conventionally, for example, toilet paper is often used for cleaning toilet seats and the vicinity of toilets, and handy toilet paper is often used. However, if a liquid detergent is used and the dirt is wiped off with the toilet paper (wiping and cleaning), the toilet paper is easily broken. In addition, the cleaning object after wiping and cleaning has a liquid cleaning agent remaining, and is easily sticky or nullified.
To solve these problems, 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). 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.
残香性に優れる香料成分は、疎水性が強い。このため、エタノールの含有量が多い特許文献1に記載の発明に、残香性に優れる香料成分を単に配合しようとすると、香料成分が液体洗浄剤に溶解しにくく、十分量の香料成分を配合できないという問題がある。
加えて、疎水性の強い香料成分の配合量を単に増やすと、特に低温(0℃以下)での液安定性が低下しやすい。また、スプレー式の吐出容器等から吐出した際に泡立ちにくくなる(起泡性が低下する)。
疎水性の強い香料成分を可溶化するために、界面活性剤を単に増量すると、洗浄対象に界面活性剤が残存して、拭き跡が残ったり、べた付きやヌル付きの原因となる。
そこで、本発明は、拭き取り掃除での利便性、液安定性及び起泡性に優れ、かつ残香性に優れる拭き取り用の液体洗浄剤を目的とする。 By the way, in order to increase commercial value, a fragrance | flavor is mix | blended with a liquid detergent. In recent years, 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. Moreover, it becomes difficult to foam when it discharges from a spray-type discharge container etc. (foaming property falls).
If the amount of the surfactant is simply increased in order to solubilize the highly hydrophobic fragrance component, the surfactant remains on the object to be cleaned, leaving wiping marks, or causing stickiness or nulling.
Then, 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.
(上記(a2)式中、R1及びR2は、それぞれ独立に、炭素数6~18のアルキル基又は炭素数6~18のアルケニル基である。Maは、水素、アルカリ金属、アルカリ土類金属、アンモニア、又はアルカノールアミンがイオン化したイオンのいずれかを示し、tはMaの価数を表す。)
(In the formula (a2), 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.)
(上記(b1)式中、R11は、炭素数8~20のアルキル基又は炭素数8~20のアルケニル基を示す。R12は、炭素数1~5のアルキレン基を示す。R13及びR14は、それぞれ独立に、水素又は炭素数1~3のアルキル基を示す。R15は、炭素数1~5のアルキレン基を示す。)
(In the above (b1) formula, 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, and R 15 represents an alkylene group having 1 to 5 carbon atoms.)
(上記(b2)式中、R21は、炭素数8~18の直鎖若しくは分岐鎖のアルキル基又は炭素数8~18の直鎖若しくは分岐鎖のアルケニル基を示す。R22及びR23は、それぞれ独立に、炭素数1~4の直鎖若しくは分岐鎖のアルキル基又は炭素数2~4の直鎖若しくは分岐鎖のアルケニル基を示す。R24は、炭素数1~6の直鎖若しくは分岐鎖のアルキレン基又は炭素数1~6の直鎖若しくは分岐鎖のヒドロキシアルキレン基を示す。)
(In the above 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 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.)
なお、上述のpHの値は、25℃において測定した値である。本明細書に規定した範囲外のpHであっても、25℃におけるpHに補正したときに本明細書に規定した範囲のpHであれば、それは本発明の範囲に含まれるものとする。
液体洗浄剤のpHは、試験紙、試験溶液又は電気的なpH測定装置(pHメーター等)その他の測定手段を適宜用いて測定することができる。本実施形態では、一例としてpHメーター(HM-30G、東亜ディーケーケー株式会社製)等により測定される値を用いることができる。 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.
粘度が上記下限値以上であれば、洗浄対象に塗布した際に、洗浄対象に滞留しやすく、上記上限値以下であれば、液体洗浄剤を注出しやすく、拭き取りやすい。
液体組成物の粘度は、B型粘度計(本実施形態では、TOKIMEC社製のB型粘度計を用いた)により25℃で測定される値(測定条件:ロータNo.2、回転数60rpm、60回転後の粘度)である。 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).
(A)成分は、二級アルカンスルホン酸塩(以下、(a1)成分ということがある)、及び後述する一般式(a2)で表される化合物(以下、(a2)成分ということがある)から選ばれる少なくとも1種の界面活性剤である。液体洗浄剤は、(A)成分と後述の(B)成分とを併有することで、後述する(D)成分を溶媒に可溶化して、残香性を高められる。 <(A) component>
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)). At least one surfactant selected from the group consisting of: Since the liquid detergent has both the component (A) and the component (B) described later, the component (D) described later is solubilized in the solvent, and the residual fragrance can be enhanced.
(a1)成分は、二級アルカンスルホン酸塩である。(a1)成分は、パラフィンスルホン酸塩とも呼ばれる界面活性剤であって、通常、炭素数10~21の化合物の混合物の形態で提供される。この(a1)成分の混合物中、炭素数13~18の(a1)成分の含有量は、混合物の全体質量に対して80~100質量%が好ましく、90~100質量%がさらに好ましく、特に100質量%でもよい。
また、(A)成分には、一級アルカンスルホン酸塩、ジスルホン酸塩又はポリスルホン酸塩等が含まれていてもよいが、これらの成分の含有量は、前記(a1)成分の混合物の全体質量に対して、0~20重量%の範囲内であることが望ましい。 ≪ (a1) component≫
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. In the mixture of the component (a1), 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.
(a1)式中、Mは対イオンである。前記対イオンとなるMとしては、以下に挙げる物質がイオン化した(電離した)イオンが挙げられる。これらの物質としては、例えばアルカリ金属、アルカリ土類金属、アンモニア又はアルカノールアミン等が挙げられる。アルカリ金属としては、ナトリウム、カリウム又はリチウム等が挙げられる。アルカリ土類金属としては、カルシウム又はマグネシウム等が挙げられる。アルカノールアミンとしては、モノエタノールアミン、ジエタノールアミン又はトリエタノールアミン等が挙げられる。中でも、Mとしては、アルカリ金属が好ましく、アルカリ金属ではナトリウム又はカリウムがより好ましい。
(a1)式中、sは、Mの価数を表す。例えば、Mがカルシウムであれば、sは2である。 (A1) In the formula, p + q = 10 to 14. That is, the compound represented by the above formula (a1) is a secondary alkane sulfonate having 13 to 17 carbon atoms (however, the carbon number in “M” in the formula (a1) is not included). If p + q is 10 or more, since the detergency with respect to oil stains increases and the solubility of the component (D) in the liquid detergent increases, the liquid stability at low temperatures becomes good. If p + q is 14 or less, the solubility of the present component in the liquid detergent becomes good, so that precipitation or the like during storage at low temperatures is unlikely to occur.
In the formula (a1), M is a counter ion. 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.
(a2)成分は、下記一般式(a2)で表される化合物であり、ジアルキルスルホコハク酸エステル又はその塩である。 << (a2) component >>
The component (a2) is a compound represented by the following general formula (a2), and is a dialkylsulfosuccinic acid ester or a salt thereof.
R1及びR2の炭素数は、8~14が好ましい。上記下限値以上であれば、油汚れに対する洗浄力をより高め、液体洗浄剤中の(D)成分の溶解性が良好となるため低温での液安定性が良好となる。上記上限値以下であれば、液体洗浄剤中での本成分の溶解性が良好となり、低温での保存時における析出等を生じにくい。
R1及びR2は、直鎖でもよく、又は分岐鎖でもよく、中でも、分岐鎖が好ましい。
R1及びR2としては、アルキル基が好ましい。
Maは、対イオンである。以下に挙げる物質がイオン化した(電離した)イオンが挙げられる。これらの物質としては、例えば水素、アルカリ金属、アルカリ土類金属、アンモニア又はアルカノールアミンのいずれかである。アルカリ金属としては、ナトリウム、カリウム又はリチウム等が挙げられる。アルカリ土類金属としては、カルシウム又はマグネシウム等が挙げられる。アルカノールアミンとしては、モノエタノールアミン、ジエタノールアミン又はトリエタノールアミン等が挙げられる。中でも、Maとしては、アルカリ金属が好ましく、ナトリウム又はカリウムがより好ましい。
tは、Maの価数を表す。例えば、Maがカルシウムであれば、tは2である。 (A2) In the formula, 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.
液体洗浄剤中の(A)成分の含有量は、液体洗浄剤の全体質量に対して0.1~1.9質量%が好ましく、0.1~1.5質量%がより好ましい。上記下限値以上であれば、後述する(D)成分をより確実に可溶化して、残香性をより高められ、上記上限値以下であれば、拭き跡残りをより良好に防止できる。 (A) 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.
(B)成分は、下記一般式(b1)で表される化合物(以下、(b1)成分ということがある)、及び下記一般式(b2)で表される化合物(以下、(b2)成分ということがある)から選ばれる少なくとも1種の両性界面活性剤である。 <(B) component>
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.
(b1)成分は、下記一般式(b1)で表される化合物である。 << (b1) component >>
The component (b1) is a compound represented by the following general formula (b1).
R11の炭素数は、9~15が好ましい。上記下限値以上であれば、液体洗浄剤中の(D)成分の溶解性が良好となるため低温での液安定性が良好となる。上記上限値以下であれば、液体洗浄剤中の本成分の溶解性が良好となり、保存時における析出等を生じにくい。
R11は、直鎖でもよく、又は分岐鎖でもよく、中でも、直鎖が好ましい。
R11としては、アルキル基が好ましい。 In the 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.
R12の炭素数は、2~3が好ましい。上記範囲内であれば、液体洗浄剤中の(D)成分の溶解性がより高まり、低温での液安定性が良好となる。
R12は、直鎖でもよく、又は分岐鎖でもよく、中でも、直鎖が好ましい。 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.
R13又はR14がアルキル基である場合、このアルキル基の炭素数は1~2が好ましい。上記範囲内であれば、液体洗浄剤中の(D)成分の溶解性が良好となり、低温での液安定性が良好となる。
R13又はR14がアルキル基である場合、このアルキル基は、直鎖でもよく、又は分岐鎖でもよく、中でも、直鎖が好ましい。
R15は、炭素数1~5のアルキレン基である。R15の炭素数は、1~3が好ましい。上記範囲内であれば、液体洗浄剤中の(D)成分の溶解性が良好となり、低温での液安定性が良好となる。
R15は、直鎖でもよく、又は分岐鎖でもよく、中でも、直鎖が好ましい。 R 13 and R 14 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms. Among these, from the viewpoint of further increasing the solubility of the component (D) in the liquid detergent, R 13 and R 14 are preferably alkyl groups.
When R 13 or R 14 is an alkyl group, 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.
When 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.
R21の炭素数は、10~16が好ましい。上記下限値以上であれば、液体洗浄剤中の(D)成分の溶解性が良好となり、低温での液安定性が良好となる。上記上限値以下であれば、液体洗浄剤中の本成分の溶解性が良好となるため、保存時における析出等を生じにくい。
R21は、直鎖でもよく、又は分岐鎖でもよく、中でも、直鎖が好ましい。
R21としては、アルキル基が好ましい。 (B2) In the formula, 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.
R22及びR23の炭素数は、1~2が好ましい。上記範囲内であれば、液体洗浄剤中の(D)成分の溶解性が良好となり、低温での液安定性が良好となる。
R22及びR23は、直鎖でもよく、又は分岐鎖でもよく、中でも、直鎖が好ましい。
R22及びR23としては、アルキル基が好ましい。 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.
R24の炭素数は、1~3が好ましい。上記範囲内であれば、液体洗浄剤中の(D)成分の溶解性が良好となり、低温での液安定性が良好となる。
R24は、直鎖でもよく、又は分岐鎖でもよく、中でも、直鎖が好ましい。
R24としては、アルキレン基が好ましい。 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.
(b2)成分は、商業的に入手可能である。ラウリルジメチルアミノ酢酸ベタインとして、例えば、三洋化成工業株式会社製「レボンLD-36」、又は、東邦化学工業株式会社製「オバゾリンLB-SF」等が挙げられる。ステアリルジメチルアミノ酢酸ベタインとしては、花王株式会社製「アンヒトール86B」等が挙げられる。 Examples of the component (b2) include coconut oil alkyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, palmityldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine. Especially, as 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. Examples of lauryldimethylaminoacetic acid betaine include “Levon LD-36” manufactured by Sanyo Chemical Industries, Ltd., and “Ovazoline LB-SF” manufactured by Toho Chemical Industries, Ltd. Examples of stearyldimethylaminoacetic acid betaine include “Amphitol 86B” manufactured by Kao Corporation.
(B)成分としては、(b1)成分及び(b2)成分を併用するのが好ましい。(b1)成分及び(b2)成分を併用することで、低温での液安定性、起泡性又は残香性をより高められる。
(b1)成分及び(b2)成分を併用する場合、(b1)成分/(b2)成分で表される質量比(以下、b1/b2比ということがある)は、0.5~10が好ましく、1~7がより好ましい。b1/b2比が上記下限値以上であれば、起泡性をより高められ、上記上限値以下であれば、残香性や、低温での液安定性をより高められる。 (B) component mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.
As the component (B), it is preferable to use the component (b1) and the component (b2) in combination. By using the component (b1) and the component (b2) in combination, the liquid stability at low temperature, the foaming property, or the remaining fragrance can be further enhanced.
When the component (b1) and the component (b2) are used 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.
(C)成分は、エタノールである。液体洗浄剤は、(C)成分を含有することで、トイレットペーパーを用いて拭き取り掃除をした場合でも、トイレットペーパーが破れたりしにくい。 <(C) component>
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.
(D)成分は、ClogP値が3.0以上の香料成分(以下、(d1)成分ということがある)を含有する香料である。液体洗浄剤は、(D)成分を含有することで、残香性を高められる。
(D)成分は、香料成分からなる組成物である。香料成分は、例えば、「Perfume and Flavor Chemicals」,Vol.I and II,Steffen Arctander,Allured Pub.Co.(1994)、「合成香料化学と商品知識」,印藤元一著,化学工業日報社(1996)、「Perfume and Flavor Materials of NaturalOrigin」,Steffen Arctander,Allured Pub.Co.(1994)、「香りの百科」,日本香料協会編,朝倉書店(1989)、「Perfumery MaterialPerformance V.3.3」,Boelens Aroma Chemical Information Service(1996)、又は、「Flower oils and Floral Compounds In Perfumery」,Danute Lajaujis Anonis,Allured Pub.Co.(1993)等に挙げられている。 <(D) component>
(D) A component is a fragrance | flavor containing the fragrance | flavor component (henceforth (d1) component) whose ClogP value is 3.0 or more. A liquid cleaning agent can improve a residual fragrance property by containing (D) component.
(D) A component is a composition which consists of a fragrance | flavor component. 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. (1994), “Encyclopedia of Scents”, edited by the Japan Fragrance Association, Asakura Shoten (1989), “Performer Material Performance V.3.3”, Boelens Aroma Chemical Information Service (1996), or “Flower Information” "Danete Lajaujis Anonis, Allured Pub. Co. (1993).
(d1)成分は、ClogP値が3.0以上の香料成分である。
ClogP値は、化学物質について、1-オクタノール中及び水中の平衡濃度の比を表す1-オクタノール/水分配係数Pを底10に対する対数logPの形態で表した値である。前記ClogP値は、f法(疎水性フラグメント定数法)により、化合物の化学構造をその構成要素に分解し、各フラグメントの有する疎水性フラグメント定数・fを積算して求められる(例えば、Clog 3 Reference Manual DaylightSoftware 4.34,Albert Leo,David Weininger,Version 1,March、1994参照)。一般に、香料成分はClogP値が大きいほど疎水的であることから、ClogP値が大きい香料成分を多く含む香料は、ClogP値が小さい香料成分を多く含む香料よりも疎水的である。(d1)成分は、香りの持続性がよい。一方、ClogP値が3.0未満の香料成分(以下、(d2)成分ということがある)は、香りが良いが、香りの持続性が不十分である。(d1)成分のClogP値には上限は特にないが、目安としてClogP値は8.0以下である。
(d1)成分としては、例えば、表1の香料成分が挙げられる。 << (d1) component >>
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). In general, since 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. On the other hand, a fragrance component having a ClogP value of less than 3.0 (hereinafter sometimes referred to as a component (d2)) has a good fragrance, but the fragrance persistence is insufficient. There is no particular upper limit to 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 | flavor component of Table 1 is mentioned, for example.
(d2)成分は、ClogP値が3.0未満の香料成分である。(d2)成分を含有することで、(D)成分の徐放性が高まり、香り立ちがよくなる。(d2)成分のClogP値の下限は特に設けられないが、目安としてClogP値は1.0以上である。 << (d2) component >>
The component (d2) is a fragrance component having a ClogP value of less than 3.0. By containing the component (d2), the sustained release property of the component (D) is increased and the fragrance is improved. Although 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.
また、本発明の上記実施形態の別の態様に係る拭き取り用の液体洗浄剤は、上記実施形態の(A)~(D)に加えて、下記(E)成分を含有する。 (Change mode of liquid detergent for wiping off)
Further, 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.
(E)成分は、下記一般式(e1)で表される非イオン性界面活性剤であり、いわゆるアルコールエトキシレートである。液体洗浄剤は、(E)成分を含有することで、(D)成分を溶媒に対して可溶化して、残香性を高め、低温での液安定性を高められる。 <(E) component>
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.
R31の炭素数は、8~18であり、12~15が好ましい。上記下限値以上であれば、溶媒に対して(D)成分を十分に可溶化して、残香性を高め、かつ低温での液安定性を高められる。上記上限値以下であれば、(E)成分の水溶性が低くなりすぎず、低温での液安定性を高められる。
R31の側鎖の平均数(以下、平均分岐数ということがある)は、0.2~2であり、0.4~1.5が好ましい。上記範囲内であれば、溶媒に対して(D)成分を可溶化して、残香性を高め、かつ低温での液安定性を高められる。 (E1) In the formula, 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.
nは、2~7が好ましく、2~4がより好ましい。上記下限値以上であれば、(E)成分の水溶性が低くなりすぎず、残香性を高め、低温での液安定性を良好にできる。上記上限値以下であれば、溶媒に対して(D)成分を可溶化し、残香性を高め、低温での液安定性を高められる。 In the formula (e1), OE represents an oxyethylene group, and 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.
また、(E)成分は、市販のアルコールにエチレンオキシドが付加されたものでもよい。例えば、2-エチルヘキサノールのエチレンオキシド付加物(R31が2-エチルヘキシル、平均分岐数1、オキシエチレン基の平均繰り返し数が3。)、炭素数12と13との混合アルコール(サフォール23(商品名、サソール社製))のエチレンオキシド付加物(R31の炭素数が12と13との混合物、平均分岐数1.2、オキシエチレン基の平均繰り返し数が3。)、又は、炭素数16と17との混合アルコール(ネオドール67(商品名、シェル社製))のエチレンオキシド付加物(R31の炭素数が16と17との混合物、平均分岐数1.8、オキシエチレン基の平均繰り返し数が3。)等が挙げられる。 As a suitable commercial item of (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 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. For example, 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.).
本実施形態の液体洗浄剤には、溶媒が含まれる。溶媒は上記した(A)~(E)成分を溶解し、又は液体洗浄剤内に互いに均一に分散させる等の目的で加えられるものである。溶媒は、例えば水道水、イオン交換水、又は蒸留水等の水を用いることができ、中でもイオン交換水が好ましい。
液体洗浄剤中の溶媒の含有量は、特に限定されず、例えば溶媒が水であれば液体洗浄剤の全体質量に対して50~90質量%が好ましく、60~80質量%がより好ましい。 <Solvent>
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. As the solvent, 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.
液体洗浄剤は、本発明の効果を損なわない範囲で、(A)~(E)成分以外の任意成分を含有してもよい。
任意成分としては、(A)~(B)成分及び(E)成分以外の界面活性剤(任意界面活性剤)、増粘剤、防腐剤、着色剤、又はpH調整剤等が挙げられる。 <Other ingredients>
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.
Examples of optional components include surfactants (optional surfactants) other than the components (A) to (B) and (E), thickeners, preservatives, colorants, or pH adjusters.
液体洗浄剤は、従来公知の方法により製造される。液体洗浄剤の製造方法としては、例えば、水に、(A)~(D)及び、選択的に(E)成分と、必要に応じて任意成分とを加え、これを攪拌する方法が挙げられる。 (Production method)
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. .
液体洗浄剤の使用方法は、例えば、液体洗浄剤をスプレー式の吐出容器やスクイズ式の吐出容器に収容し、これらの容器から、便座や床面等の洗浄対象に適量の液体洗浄剤を塗布し、塗布した液体洗浄剤を汚れと共に拭き取る方法が挙げられる。液体洗浄剤を拭き取る際には、トイレットペーパー等の紙や布を用いることができる。このように使用する際は、例えば、洗浄対象の単位面積(30cm×30cm)当たり0.1~5mlの液体洗浄剤を塗布し、紙や布によって1~3回の拭き取りを行うことで、本実施形態の液体洗浄剤によって充分に洗浄対象の洗浄を行うことができる。
あるいは、トイレットペーパー等の紙や布に液体洗浄剤を塗布し(又は、これらの紙や布に液体洗浄剤を含ませ)、このトイレットペーパー等で洗浄対象を拭き取る方法が挙げられる。このように使用する際は、例えば、紙や布の単位面積(例えば、11.5cm×30cmのトイレットペーパー8ツ折)当たり0.1~2mlの液体洗浄剤を塗布し、洗浄対象に対して1~3回の拭き取りを行うことで、本実施形態の液体洗浄剤によって充分に洗浄対象の洗浄を行うことができる。 (how to use)
For example, 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. When wiping off the liquid cleaning agent, paper or cloth such as toilet paper can be used. When used in this way, for example, by applying 0.1 to 5 ml of liquid cleaning agent per unit area (30 cm × 30 cm) to be cleaned, and wiping once or three times with paper or cloth, The liquid cleaning agent of the embodiment can sufficiently clean the object to be cleaned.
Alternatively, 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. When used in this way, 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.
<(A)成分>
・A-1:二級アルカンスルホン酸ナトリウム(SAS、平均分子量328)、クラリアントジャパン株式会社製の「HOSTAPUR SAS60」(商品名)。(a1)式中のp+q=10~14の混合物、Mがナトリウム、sが1である(a1)成分に相当。
・A-2:ジアルキルスルホコハク酸ナトリウム。ライオン株式会社製の「リパール870P」(商品名)。(a2)式中、R1及びR2が2-エチルヘキシル、Maがナトリウム、tが1である(a2)成分に相当。
<(A’)成分:(A)成分の比較品>
・A’-1:直鎖アルキルベンゼンスルホン酸ナトリウム(LAS、直鎖アルキル基の炭素数10~15)。テイカ株式会社製の「テイカパワーL121」(商品名)。
・A’-2:ポリオキシエチレンアルキルエーテル硫酸エステルナトリウム(AES)。ライオン株式会社製の「サンノールTD-3130」(商品名)。
・A’-3:α-オレフィンスルホン酸ナトリウム(AOS、炭素数14と16との混合物)。ライオン株式会社製の「リポランLB-440」(商品名)。
・A’-4:ミリスチン酸ナトリウム。日油株式会社製の「ノンサールMN-1」(商品名)。
・A’-5:エーテルカルボン酸塩。ライオン株式会社製の「エナジコールEC-30」(商品名)。
・A’-6:N-アシルアミノ酸塩。ライオン株式会社製の「エナジコールL-30AM」(商品名)。
・A’-7:アルキルジフェニルエーテルスルホン酸塩。ダウケミカル社製「Dowfax AXC6L」(商品名)。 (Raw material)
<(A) component>
A-1: Secondary alkane sulfonate sodium (SAS, average molecular weight 328), “HOSTAPUR SAS60” (trade name) manufactured by Clariant Japan KK (A1) A mixture of p + q = 10 to 14 in the formula, corresponding to the component (a1) in which M is sodium and s is 1.
A-2: sodium dialkylsulfosuccinate “Ripal 870P” (trade name) manufactured by Lion Corporation. In the formula (a2), R 1 and R 2 are 2-ethylhexyl, M a is sodium, and 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). "Taika Power L121" (trade name) manufactured by Teika Co., Ltd.
A′-2: sodium polyoxyethylene alkyl ether sulfate ester (AES). “Sannor TD-3130” (trade name) manufactured by Lion Corporation.
A′-3: sodium α-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. “Dowfax AXC6L” (trade name) manufactured by Dow Chemical.
・B-1:ラウリン酸アミドプロピルベタイン(LPB)。ライオン株式会社製の「エナジコールL-30B」(商品名)。(b1)成分に相当。
・B-2:ラウリルジメチルアミノ酢酸ベタイン(LDB)。三洋化成工業株式会社製の「レボンLD-36」(商品名)。(b2)成分に相当。
<(B’)成分:(B)成分の比較品>
・B’-1:ドデシルジメチルアミンオキシド(AX)。ライオンアクゾ株式会社製の「アロモックス DM12 D-W(C)」(商品名)。
・B’-2:ラウリルアミドプロピルジメチルアミンオキシド(APAX)。川研ファインケミカル株式会社製の「ソフタゾリンLAO」(商品名)。
・B’-3:N-ヤシ油脂肪酸アシル-N-カルボキシエチル-N-ヒドロキシエチルエチレンジアミン。川研ファインケミカル株式会社製の「ソフタゾリンNS」(商品名)。
・B’-4:ヒドロキシアルキルヒドロキシエチルエチレンジアミンNa。川研ファインケミカル株式会社製の「ソフタゾリンLMEB」(商品名)。 <(B) component>
B-1: Amidopropyl betaine laurate (LPB). “Enajol L-30B” (trade name) manufactured by Lion Corporation. Corresponds to component (b1).
B-2: lauryldimethylaminoacetic acid betaine (LDB). “Lebon LD-36” (trade name) manufactured by Sanyo Chemical Industries, Ltd. Corresponds to component (b2).
<(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-1:エタノール。協和発酵工業株式会社製の「発酵アルコール95度」(商品名)。
<(C’)成分:(C)成分の比較品>
・C’-1:ブチルカルビトール。協和発酵工業株式会社製の「ブチルカルビトール95-P」(商品名)。 <(C) component>
C-1: ethanol. Kyowa Hakko Kogyo Co., Ltd. “fermented alcohol 95 degrees” (trade name).
<(C ′) component: Comparative product of component (C)>
C′-1: butyl carbitol. “Butyl carbitol 95-P” (trade name) manufactured by Kyowa Hakko Kogyo Co., Ltd.
・D-1:表2に記載の香料D-1。
・D-2:表2に記載の香料D-2。
<(D’)成分:(D)成分の比較品>
・D’-1:表2に記載の香料D’-1。 <(D) component>
D-1: Fragrance D-1 described in Table 2.
D-2: Fragrance D-2 described in Table 2.
<(D ′) Component: Comparative Product of (D) Component>
D′-1: Fragrance D′-1 described in Table 2.
・E-1:アルコールエトキシレート(R31の炭素数が13と15との混合物。平均分岐数0.8、オキシエチレン基の平均繰り返し数(表中、OEモル数と記載。以下、同じ。)が3。)。BASFジャパン株式会社製の「ルテンゾールAO3」(商品名)。
・E-2:アルコールエトキシレート(R31の炭素数が13と15との混合物。平均分岐数0.8、オキシエチレン基の平均繰り返し数が2。)。BASFジャパン株式会社製の「ルテンゾールAO2」(商品名)。
・E-3:アルコールエトキシレート(R31の炭素数が13と15との混合物。平均分岐数0.8、オキシエチレン基の平均繰り返し数が7。)。BASFジャパン株式会社製の「ルテンゾールAO7」(商品名)。
・E-4:アルコールエトキシレート(2-エチルヘキシル。平均分岐数1.0、オキシエチレン基の平均繰り返し数が3。)。2-エチルヘキシルアルコールに、3モルのエチレンオキシドを付加したもの。合成品。
・E-5:アルコールエトキシレート(R31の炭素数が10。平均分岐数1.0、オキシエチレン基の平均繰り返し数が3。)。BASFジャパン株式会社製の「ルテンゾールXP30」(商品名)。
・E-6:アルコールエトキシレート(R31の炭素数が12と13との混合物。平均分岐数1.2、オキシエチレン基の平均繰り返し数が3。)。サソール社製の「サフォール23」に3モルのエチレンオキシドを付加したもの。合成品。
・E-7:アルコールエトキシレート(R31の炭素数が16と17との混合物。平均分岐数1.8、オキシエチレン基の平均繰り返し数が3。)。シェル社製の「ネオドール67」に3モルのエチレンオキシドを付加したもの。合成品。
<(E’)成分:(E)成分の比較品>
・E’-1:アルコールエトキシレート(R31の炭素数が13と15との混合物。平均分岐数0.8、オキシエチレン基の平均繰り返し数が8。)。BASFジャパン株式会社製の「ルテンゾールAO8」(商品名)。
・E’-2:ポリオキシエチレン(5)オクチルドデシルエーテル(R31の炭素数が20。平均分岐数1.0、オキシエチレン基の平均繰り返し数が5。)。日本エマルジョン株式会社製の「EMALEX OD-5」(商品名)。
・E’-3:ポリオキシエチレン(3)ラウリルエーテル(R31の炭素数が12。分岐なし、オキシエチレン基の平均繰り返し数が3。)。日本エマルジョン株式会社製の「EMALEX 703」(商品名)。
・E’-4:アルコールエトキシレート(R31の炭素数が13。平均分岐数2.4、オキシエチレン基の平均繰り返し数が3。)。BASFジャパン株式会社製の「ルテンゾールTO3」(商品名)。 <(E) component>
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.) “Rutensol 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. Synthetic product.
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.
各例の液体洗浄剤には、以下の共通成分を配合した。各成分の末尾の数値は、液体洗浄剤への配合量である。
・エチレンジアミンテトラ酢酸:アクゾノーベル株式会社製の「ディゾルビンZ」(商品名)・・・・0.5質量%。
・クエン酸:扶桑化学工業株式会社製の「クエン酸」・・・・0.4質量%。
・水酸化カリウム:旭硝子株式会社製の「液体苛性カリ」・・・・0.6質量%。 <Common ingredients>
The following common components were blended in the liquid cleaning agent of each example. The numerical value at the end of each component is the blending amount into the liquid detergent.
・ Ethylenediaminetetraacetic acid: “Disorbin Z” (trade name) manufactured by Akzo Nobel Co., Ltd. 0.5 mass%.
Citric acid: “citric acid” manufactured by Fuso Chemical Industry Co., Ltd. 0.4 mass%.
-Potassium hydroxide: "Liquid caustic potash" manufactured by Asahi Glass Co., Ltd .... 0.6% by mass.
・水:イオン交換水。 <Solvent>
-Water: Ion exchange water.
(実施例A1~A27、比較例A1~A26)
表3~6に示す組成に従い、各例の液体洗浄剤500gを下記の手順で調製した(表中に記載のない成分は添加しなかった)。
(C)成分と共通成分とを水に加え混合し、次いで、(A)~(B)成分及び(E)成分を加え混合した後、(D)成分を加え混合した。必要に応じ、pH調整剤(クエン酸又は水酸化カリウム)を新たに加えてpH7.0に調整して、各例の液体洗浄剤を得た。
得られた液体洗浄剤について、紙破れ防止効果、拭き跡残り防止効果、残香性、低温での液安定性及び起泡性を評価し、その結果を表中に示す。
なお、pH調整剤の配合量「適量」は、液体洗浄剤をpH7.0にするのに要した量である。水の配合量「バランス」は、液体洗浄剤の全量を100質量%にするのに必要な量である。
pHは、液体洗浄剤を25℃に調整し、ガラス電極式pHメーター(製品名:ホリバF-22、株式会社堀場製作所製)を用い、電極を液体洗浄剤に浸漬した30秒後に読み取られた値である。pHの測定方法は、JIS K3362-1998に準拠したものである。 (Test 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.
About the obtained liquid cleaning agent, paper tear prevention effect, wiping trace remaining prevention effect, residual fragrance property, liquid stability at low temperature and foaming property are evaluated, and the results are shown in the table.
In addition, 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.
<紙破れ防止効果>
11.5cm×30cmのトイレットペーパー(日本製紙クレシア株式会社製の「クリネックス(シングル)」(商品名)を8ツ折にした。
クッションフロア全面に乾燥した尿汚れがあると想定して、30cm角のクッションフロア中央に液体洗浄剤1mLを塗布し、これを8ツ折にしたトイレットペーパーに含浸させながらクッションフロア全面をまんべんなく拭き取った。拭き取り後のトイレットペーパーの破れ具合を目視で確認し、下記評価基準に従って評価した。「A」及び「B」を合格とした。 (Evaluation methods)
<Paper tear prevention effect>
Toilet paper of 11.5 cm × 30 cm (“Kleenex (single)” (trade name) manufactured by Nippon Paper Crecia Co., Ltd.) was folded into 8 folds.
Assuming that there is dry urine stain on the entire cushion floor, 1mL of liquid detergent was applied to the center of the 30cm square cushion floor, and the entire cushion floor was wiped evenly while impregnating it into eight folded toilet paper. . The degree of tearing of the toilet paper after wiping was visually confirmed and evaluated according to the following evaluation criteria. “A” and “B” were accepted.
A:破れていない。
B:ほんの一部破れたが、ほとんど気にならない。
C:明らかに破れている。
D:ボロボロに破れている。 ≪Evaluation criteria≫
A: Not torn.
B: Although only a part was torn, I was hardly interested.
C: Clearly torn.
D: Tattered.
液体洗浄剤100μLをスライドガラスに乗せ、8ツ折にしたトイレットペーパーで軽く一拭きした。乾燥後、拭き跡の残り具合を目視で観察し、下記評価基準に従って評価した。3~5点を合格とした。 <Anti-wiping effect prevention>
100 μL of the liquid detergent was placed on a slide glass and gently wiped with toilet paper folded in eight. After drying, the remaining condition of the wiping marks was visually observed and evaluated according to the following evaluation criteria. 3 to 5 points were accepted.
5:拭き跡が全く残らない。
4:わずかに細い線状の拭き跡が残るが、気にならない。
3:線状に拭き跡が残るが、ほとんど気にならない。
2:面状に拭き跡が残る。
1:全面に拭き跡が残る。 ≪Evaluation criteria≫
5: No wiping marks remain.
4: Slightly thin linear wiping marks remain, but I do not care.
3: A trace of wiping remains, but it is hardly anxious.
2: Wipe marks remain on the surface.
1: Wipe marks remain on the entire surface.
一般的な大きさである1.82m×0.91m(0.5坪)のトイレ空間にて、トイレの便座及び床にそれぞれ液体洗浄剤1mLを塗布し、これを8ツ折にしたトイレットペーパーで塗り広げるようにして、拭き取り掃除をした。下記評価基準に従い、専門パネラ5名が、拭き取り掃除の直後の香りと、拭き取り掃除の1時間後の香りとを比較評価した。
専門パネラの評価結果の平均値を求め3~5点を合格とした。 <Rescent>
Toilet paper with 1 liter of liquid cleaning agent applied to the toilet seat and floor of the toilet in a typical 1.81m x 0.91m (0.5 tsubo) toilet space. I wiped it up and cleaned it. In accordance with the following evaluation criteria, five professional panelists compared and evaluated the scent immediately after wiping cleaning and the scent after 1 hour of wiping cleaning.
The average value of the evaluation results of the specialized panelists was obtained, and 3 to 5 points were accepted.
5:拭き取り掃除の1時間後の香りが全く弱まっていない。
4:拭き取り掃除の1時間後の香りがわずかに弱まっているが、十分に感知できる強度。
3:拭き取り掃除の1時間後の香りは弱まっているが、感知できる強度。
2:拭き取り掃除の1時間後の香りが弱く、ほとんど感知できない強度。
1:拭き取り掃除の1時間後の香りが明らかに弱く、感知できない強度。 ≪Evaluation criteria≫
5: The scent after 1 hour of wiping and cleaning is not weakened at all.
4: Slightly weakened scent after 1 hour of wiping and cleaning, but sufficiently perceivable intensity.
3: Although the fragrance after 1 hour of wiping and cleaning is weakened, it is perceivable intensity.
2: The intensity is almost undetectable after 1 hour after wiping and cleaning.
1: The intensity of the scent after 1 hour of wiping and cleaning is clearly weak and undetectable.
液体洗浄剤を無色透明ガラス瓶に入れ、-5℃の恒温槽に24時間静置した。その後、下記評価基準に従い、外観を目視で評価した。「A」「B」を合格とした。 <Liquid stability at low temperature>
The liquid detergent was placed in a colorless transparent glass bottle and allowed to stand in a thermostatic bath at -5 ° C. for 24 hours. Thereafter, the appearance was visually evaluated according to the following evaluation criteria. “A” and “B” were accepted.
A:無色透明で異物が無い。
B:わずかに白く濁っているが問題ないレベル。
C:薄っすら白く濁っているが問題ないレベル。
D:明らかな白濁、沈殿又は分離が見られる。 ≪Evaluation criteria≫
A: Colorless and transparent with no foreign matter.
B: Slightly cloudy white but no problem.
C: The level is slightly white and cloudy but no problem.
D: Obvious cloudiness, precipitation or separation is observed.
液体洗浄剤を無色透明ガラス瓶に入れ、-5℃の恒温槽に24時間静置した。この液体洗浄剤をトリガースプレー容器に入れ、液体洗浄剤を吐出した。下記評価基準に従い、吐出された泡の状態を目視で評価した。「A」「B」を合格とした。本試験は、起泡しにくい低温での起泡性を評価した。 <Foamability>
The liquid detergent was placed in a colorless transparent glass bottle and allowed to stand in a thermostatic bath at -5 ° C. for 24 hours. This liquid detergent was put into a trigger spray container, and the liquid detergent was discharged. According to the following evaluation criteria, the state of the discharged foam was visually evaluated. “A” and “B” were accepted. This test evaluated the foaming property in the low temperature which is hard to foam.
A:きめ細かい泡立ちである。直径2mm未満の気泡である。
B:ややきめ細かい泡立ちである。直径2mm以上5mm未満の気泡があるが、直径5mm以上の気泡がない。
C:粗い泡立ちである。直径5mm以上の気泡が見られる。
D:全く泡立たない。 ≪Evaluation criteria≫
A: Fine foaming. Bubbles with a diameter of less than 2 mm.
B: Slightly fine foaming. There are bubbles with a diameter of 2 mm or more and less than 5 mm, but there are no bubbles with a diameter of 5 mm or more.
C: Coarse foaming. Bubbles with a diameter of 5 mm or more can be seen.
D: No foaming at all.
一方、(A)成分、(B)成分、(D)成分、(E)成分のいずれかを含有しない比較例A1、A2、A4、A5は、残香性が劣っていた。
(C)成分を含有しない比較例A3は、紙破れ防止効果が「D」であった。
(A)成分に代えて(A’)成分を用いた比較例A6~A12、(B)成分に代えて(B’)成分を用いた比較例A13~A16は、いずれも残香性が2点以下、低温での液安定性が「D」又は「C」であった。
(C)成分に代えて(C’)成分を用いた比較例A17は、紙破れ防止効果が「D」、拭き跡残り防止効果が1点、残香性が2点であった。
(D)成分に代えて(D’)成分を用いた比較例A18は残香性が2点であった。
(E)成分に代えて(E’)成分を用いた比較例A19~A22は、低温での液安定性が「D」又は「C」であった。
A/B比が0.2である比較例A23、A/B比が4である比較例A24は、いずれも残香性が2点、低温での液安定性が「C」、起泡性が「C」であった。
(A+B)/E比が1.3である比較例A25、(A+B)/E比が33.3である比較例A26は、低温での液安定性が「D」又は「C」であった。
これらの結果から、本発明を適用することで、利便性、液安定性及び起泡性を高め、かつ残香性を高められることが判った。 As shown in Tables 3 to 6, 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. In addition, in Examples A1 to A27, the residual fragrance was 3 to 5 points, the liquid stability at low temperature was “A” or “B”, and the foaming property was “A” or “B”.
On the other hand, 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.
In 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. Hereinafter, the liquid stability at low temperature was “D” or “C”.
In 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.
In Comparative Example A18 using the component (D ′) instead of the component (D), the residual fragrance was 2 points.
In Comparative Examples A19 to A22 using the component (E ′) instead of the component (E), the liquid stability at low temperature was “D” or “C”.
Comparative Example A23 with an A / B ratio of 0.2 and Comparative Example A24 with an A / B ratio of 4 both have a residual fragrance of 2 points, a liquid stability at low temperature of “C”, and a foaming property of “C”.
In Comparative Example A25 where (A + B) / E ratio is 1.3 and Comparative Example A26 where (A + B) / E ratio is 33.3, the liquid stability at low temperature was “D” or “C”. .
From these results, it was found that by applying the present invention, convenience, liquid stability and foaming properties can be improved and the residual fragrance property can be improved.
(実施例B1~B22、比較例B1~B20)
表7~10に示す組成に従い、その他は試験例Aと同様として、各例の液体洗浄剤500gを下記の手順で調製した(表中に記載のない成分は添加しなかった)。紙破れ防止効果、拭き跡残り防止効果、残香性及び外観についての評価を、試験例Aと同様の評価基準で行った。 (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.
一方、(A)成分、(B)成分、(D)成分のいずれかを含有しない比較例B1、2、4は、残香性が劣っていた。
(C)成分を含有しない比較例B3は、紙破れ防止効果が「D」であった。
(A)成分に代えて(A’)成分を用いた比較例B5~B11、(B)成分に代えて(B’)成分を用いた比較例B12~B13は、いずれも残香性が2点以下であった。
(C)成分に代えて(C’)成分を用いた比較例B14~B15は、紙破れ防止効果が「D」又は「C」であり、拭き跡残り防止効果が1点又は2点であった。
(D)成分に代えて(D’)成分を用いた比較例B16は残香性が2点であった。
A/B比が0.1である比較例B17は、残香性が1点であり、A/B比が38である比較例B18は、拭き跡残り防止効果が2点であった。
(A+B)/D比が0.4である比較例B19及び(A+B)/D比が33.3である比較例B19~B20は、いずれも残香性が2点以下であった。
これらの結果から、本発明を適用することで、優れた利便性と優れた残香性とを両立できることが判った。 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, and Comparative Example B18 having an A / B ratio of 38 had a wiping trace remaining preventing effect of 2 points.
In 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.
Claims (5)
- (A)成分:二級アルカンスルホン酸塩、及び下記一般式(a2)で表される化合物から選ばれる少なくとも1種の界面活性剤と、
(B)成分:下記一般式(b1)で表される化合物、及び下記一般式(b2)で表される化合物から選ばれる少なくとも1種の両性界面活性剤と、
(C)成分:エタノールを液体洗浄剤の全体質量に対して15質量%以上と、
(D)成分:ClogP値が3.0以上の香料成分を含有する香料と、を含有し、
前記(A)成分/前記(B)成分で表される質量比が0.3~30である拭き取り用の液体洗浄剤。
(上記(a2)式中、R1及びR2は、それぞれ独立に、炭素数6~18のアルキル基又は炭素数6~18のアルケニル基である。Maは、水素、アルカリ金属、アルカリ土類金属、アンモニア、又はアルカノールアミンがイオン化したイオンのいずれかを示し、tはMaの価数を表す。)
(上記(b1)式中、R11は、炭素数8~20のアルキル基又は炭素数8~20のアルケニル基を示す。R12は、炭素数1~5のアルキレン基を示す。R13及びR14は、それぞれ独立に、水素又は炭素数1~3のアルキル基を示す。R15は、炭素数1~5のアルキレン基を示す。)
(上記(b2)式中、R21は、炭素数8~18の直鎖若しくは分岐鎖のアルキル基又は炭素数8~18の直鎖若しくは分岐鎖のアルケニル基を示す。R22及びR23は、それぞれ独立に、炭素数1~4の直鎖若しくは分岐鎖のアルキル基又は炭素数2~4の直鎖若しくは分岐鎖のアルケニル基を示す。R24は、炭素数1~6の直鎖若しくは分岐鎖のアルキレン基又は炭素数1~6の直鎖若しくは分岐鎖のヒドロキシアルキレン基を示す。) (A) component: secondary alkane sulfonate and at least one surfactant selected from compounds represented by the following general formula (a2);
(B) component: at least one amphoteric surfactant selected from a compound represented by the following general formula (b1) and a compound represented by the following general formula (b2);
(C) component: 15 mass% or more of ethanol with respect to the total mass of the liquid detergent,
(D) component: containing the fragrance | flavor containing the fragrance | flavor component whose ClogP value is 3.0 or more,
A liquid detergent for wiping, wherein the mass ratio represented by the component (A) / the component (B) is 0.3 to 30.
(In the formula (a2), 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.)
(In the above (b1) formula, 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, and R 15 represents an alkylene group having 1 to 5 carbon atoms.)
(In the above 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 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.) - [前記(A)成分+前記(B)成分]/前記(D)成分で表される質量比が0.5~30である請求項1に記載の拭き取り用の液体洗浄剤。 The liquid cleaning agent for wiping according to claim 1, wherein a mass ratio represented by [the component (A) + the component (B)] / the component (D) is 0.5 to 30.
- (E)成分:下記一般式(e1)で表される非イオン性界面活性剤をさらに含有し、
[前記(A)成分+前記(B)成分]/前記(E)成分で表される質量比が2~30である請求項1又は2に記載の拭き取り用の液体洗浄剤。 (E) component: It further contains a nonionic surfactant represented by the following general formula (e1),
The liquid cleaning agent for wiping according to claim 1 or 2, wherein a mass ratio represented by [the component (A) + the component (B)] / the component (E) is 2 to 30. - 前記(D)成分/(E)成分で表される質量比が0.5~4.5である請求項3に記載の拭き取り用液体洗浄剤。 The liquid cleaning agent for wiping according to claim 3, wherein a mass ratio represented by the component (D) / component (E) is 0.5 to 4.5.
- 前記二級アルカンスルホン酸塩が、下記一般式(a1)で表される化合物である請求項1から4のいずれか1項に記載の拭き取り用の液体洗浄剤。
(上記(a1)式中、p+q=10~14である。) The liquid cleaning agent for wiping according to any one of claims 1 to 4, wherein the secondary alkane sulfonate is a compound represented by the following general formula (a1).
(In the formula (a1), p + q = 10 to 14)
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