JP6051111B2 - Liquid detergent for kitchen - Google Patents

Description

  The present invention relates to a liquid cleaning agent for kitchens.

  As a method of cleaning kitchen utensils such as tableware and cooking utensils, a kitchen liquid cleaning agent is dispersed in water to form a cleaning liquid, and a cleaning tool such as a sponge is used to rub the object to be cleaned in this cleaning liquid. Dipping method) or a method of immersing water in a cleaning tool such as a sponge, removing a liquid cleaning agent for kitchen, and scrubbing the object to be cleaned with the cleaning tool (non-immersion method). In recent years, a non-immersion method in which a kitchen liquid cleaning agent is taken in a sponge soaked with water and the object to be cleaned is scrubbed while foaming the sponge has become the mainstream. For this reason, the liquid detergent for kitchens is required to have good foaming (good foaming property) in addition to excellent cleaning power.

In the past, the objects to be cleaned were washed with a liquid cleaning agent for kitchens and rinsed with water, and then water drops adhering to the dishes were wiped off with a cloth or the like, and the dishes were often stored in a cupboard or the like. In recent years, due to the reduction in the labor of housework and changes in hygiene, it has become more common for wet tableware after rinsing to stand against a watering basket for tableware and to dry naturally.
However, when the tableware or the like to which the water droplets are attached is naturally dried, the moisture of the water droplets attached to the tableware or the like evaporates, and calcium salt or the like is deposited, so that waterdrop marks (water spots) are easily formed on the surface of the tableware or the like. Among kitchen utensils, for example, there are dishes dyed in dark colors such as black, dark blue, dark red, and dark green to improve the appearance of the prepared dishes. In these dark-colored tableware, the water spot is easily noticeable, and the beauty of washing is remarkably impaired.

In order to solve these problems, a cleaning agent has been proposed for the purpose of preventing the formation of water spots in tableware and cooking utensils.
For example, a hard surface cleaning containing a specific amount of polyoxyethylene alkyl ether or higher aliphatic alkanolamide, an amphoteric surfactant, a polyalkylene glycol having a weight average molecular weight of 300 to 6000, and a specific tea leaf extract in a specific ratio An agent composition has been proposed (Patent Document 1).
Alternatively, a specific alcohol, a specific polymer compound containing a cationic monomer, a specific anionic surfactant, and a surfactant selected from amine oxides, amphoteric surfactants and alkanolamide surfactants. The liquid detergent composition to contain is proposed (patent document 2).

JP-A-7-228890 JP 2005-264209 A

However, the technique of Patent Document 1 assumes that the object to be cleaned is cleaned by an immersion method. For this reason, in the technique of patent document 1, when wash | cleaning the washing | cleaning target by the non-immersion method, foaming property was not satisfied. The technique of Patent Document 2 uses a specific polymer compound containing a cationic monomer. Since this polymer compound has extremely high adsorptivity on the electronegative surface, it is adsorbed on the finger during washing and rubbed. It was easy to perceive a slimy feeling at the time of washing, rinsing or after rinsing.
Therefore, the present invention has an object of a liquid detergent for kitchen that has good foaming property, little sliminess, and hardly forms a water spot on the object to be cleaned.

  As a result of intensive studies, the present inventors have a specific anionic surfactant, an amine oxide type semipolar surfactant, a specific polyethylene glycol, and a specific water-soluble solvent in a specific ratio. Thus, the present inventors have found that the foamability is good, the slime feeling can be reduced, and it is difficult to form a water spot on the object to be cleaned, and the present invention has been completed.

  That is, the liquid detergent for kitchen of the present invention comprises (A) component: at least one anionic surfactant selected from component (A): sulfonic acid type anionic surfactant and sulfate ester type anionic surfactant; Component: Amine oxide type semipolar surfactant, Component (C): Polyethylene glycol having a weight average molecular weight of 400,000 to 4,000,000, Component (D): having 2 to 10 carbon atoms and one hydroxyl group in the molecule It contains a water-soluble solvent and (E) component: water, and the mass ratio represented by (D) component / (C) component is 5-150, {(A) component + (B) component} / (C The mass ratio represented by the component is 10 to 150, and the mass ratio represented by the {(A) component + (B) component} / (D) component is 1 to 5.

  According to the liquid detergent for kitchens of the present invention, foamability is good, there is little sliminess, and it is difficult to form a water spot on the object to be cleaned.

(Liquid cleaner for kitchen)
The kitchen liquid cleaning agent of the present invention (hereinafter sometimes simply referred to as a liquid cleaning agent) is at least one selected from component (A): a sulfonic acid type anionic surfactant and a sulfate ester type anionic surfactant. Anionic surfactants, (B) component: amine oxide type semipolar surfactant, (C) component: polyethylene glycol having a weight average molecular weight of 400,000 to 4 million, and (D) component: 2 to 2 carbon atoms. 10 contains a water-soluble solvent having one hydroxyl group in the molecule and component (E): water.

When the pH of the liquid cleaning agent changes, the charge of the component (B) may change, and the interaction between the component (A) and the component (B) may change. For this reason, the pH of the liquid detergent is preferably 5.5 to 8.5, and more preferably 6.0 to 8.0. If the amount is less than the lower limit, the interaction between the component (A) and the component (B) becomes too strong and the liquid detergent is easily solidified. If the amount exceeds the upper limit, the mutual relationship between the component (A) and the component (B) There exists a possibility that a cleaning power may fall because an effect | action becomes weak too much.
pH is a value measured according to JIS K3362-1998, using a glass electrode pH meter (model: HM-30R, manufactured by Toa DKK Corporation) with a liquid detergent adjusted to 25 ° C.

Although the viscosity of a liquid detergent is not specifically limited, For example, 10-300 mPa * s is preferable. If the viscosity is within the above range, the handling of the liquid detergent is good.
The viscosity of the liquid detergent was measured at 25 ° C. with a B-type viscometer (digital viscometer VDA2 type, manufactured by Shibaura Semtec Co., Ltd.) (measurement conditions: rotor No. 3, rotation speed 60 rpm, viscosity after 30 seconds) ).

<(A) component: at least one anionic surfactant selected from sulfonic acid type anionic surfactants and sulfate ester type anionic surfactants>
The component (A) is at least one anionic surfactant selected from sulfonic acid type anionic surfactants and sulfate ester type anionic surfactants. A liquid detergent can exhibit the outstanding detergency by containing (A) component. In addition, the component (A) can uniformly disperse the component (C) in the component (E). When the component (C) is uniformly dispersed in the component (E), the transparency of the liquid cleaning agent is increased, and the water spot (water drainage) from the object to be cleaned after cleaning is improved to suppress the formation of water spots. it can.

Examples of the sulfonic acid type anionic surfactant include linear alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonate, α-sulfo fatty acid ester salt, alkane sulfonate having an alkyl group, and the like.
Examples of the sulfate type anionic surfactant include linear or branched alkyl sulfate ester salts, alkyl ether sulfate ester salts, and alkenyl ether sulfate ester salts.
Examples of the salt in component (A) include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the α-sulfo fatty acid ester salt, fatty acid residues having 10 to 20 carbon atoms are preferable.
As the alkane sulfonate, those having 10 to 20 carbon atoms in the alkyl group are preferable, and those having 14 to 17 are more preferable. Among these, those in which the alkyl group is a secondary alkyl group (that is, secondary alkane sulfonate) are particularly preferable.

The alkyl sulfate ester salt is preferably an alkyl group having 10 to 20 carbon atoms.
As the alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt, a polyoxyalkylene sulfate type surfactant represented by the following general formula (a1) (hereinafter sometimes referred to as component (a1)) is preferable.

^{_{R 1 O- (PO) p /}} (EO) q -SO 3 M ··· (a1)

In the formula (a1), R ¹ is a linear hydrocarbon group having 8 to 24 carbon atoms, and the carbon atom bonded to the oxygen atom is the first carbon atom. R ¹ may be an alkyl group or an alkenyl group, and is preferably an alkyl group.
R ¹ has 8 to 24 carbon atoms, preferably 8 to 16, more preferably 10 to 14, and still more preferably 12 to 14. If it is more than the said lower limit, the further improvement of the detergency with respect to oil stains can be aimed at, and if it is below the said upper limit, the further improvement of drainage property and foamability can be aimed at.
In the formula (a1), PO represents an oxypropylene group, and EO represents an oxyethylene group.
p represents the average number of repetitions of PO (that is, the average number of moles of propylene oxide added), and 0 ≦ p ≦ 1.
q represents the average number of EO repeats (that is, the average number of moles of ethylene oxide added), 0 ≦ q ≦ 10, preferably 0.5 ≦ q ≦ 5, more preferably 0.5 ≦ q ≦ 1.5. preferable.
(A1) In the formula, 0 <p + q.
If p and q are in the said range, the detergency with respect to oil dirt will further increase, and the further improvement of drainage property and foamability can be aimed at.
The component (a1) is an assembly of molecules having different p and q (including molecules having no PO and EO).
Further, (a1) component, to the number of carbon atoms of R ¹ may consist only of the same molecule may the number of carbon atoms of R ¹ is also a collection of different molecules.
PO and EO may be block polymers or random polymers.
M is a cation, and examples of M include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions.
Examples of the alkali metal that provides the alkali metal ion include sodium and potassium.
Examples of alkali metals that provide alkaline earth metal ions include calcium and magnesium.
Ammonia can be cited as one that provides ammonium ions.
Examples of those that provide alkanol ammonium ions include monoethanolamine, diethanolamine, and triethanolamine.
M is preferably a sodium ion, a potassium ion, a magnesium ion or an ammonium ion from the viewpoint of detergency.

Among the components (A) described above, alkyl ether sulfates or alkenyl ether sulfates are preferable, and component (a1) is more preferable. By using the component (a1), the cleaning power can be further improved, and the component (C) can be more uniformly dispersed in the component (E).
The (A) component mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.

  Content of (A) component in a liquid detergent is determined in consideration of the kind of (A) component, etc., for example, 5-40 mass% is preferable and 8-25 mass% is more preferable. If it is less than the said lower limit, there exists a possibility that the cleaning power with respect to oil stains may fall. If it exceeds the upper limit, the content of the component (E) in the liquid cleaning agent becomes relatively small, and the component (C) becomes difficult to uniformly disperse. For this reason, (C) component may adhere nonuniformly with respect to the washing | cleaning object, and there exists a possibility that the drainage property may fall.

<(B) component: amine oxide type semipolar surfactant>
The component (B) is an amine oxide type semipolar surfactant. The semipolar surfactant is a surfactant having a semipolar bond (a bond having a property intermediate between a nonpolar bond and a polar bond), and is a solution in which the semipolar surfactant is dissolved or a dispersed dispersion. It refers to those that become cationic, anionic, or bipolar depending on the pH.
The component (B) is used in combination with the component (A), thereby increasing the detergency against oil stains, enhancing the foaming property, improving the water drainage property, and suppressing the formation of water spots.

  Examples of the component (B) include compounds represented by the following general formula (b1) (hereinafter sometimes referred to as the component (b1)).

In the formula (b1), R ¹¹ is a linear or branched alkyl group or a linear or branched alkenyl group.
The number of carbon atoms of R ¹¹ is from 8 to 18, preferably 8 to 16, 10 to 14 is more preferable. If it is more than the said lower limit, the further improvement of the detergency with respect to oil stains can be aimed at, and if it is below the said upper limit, the further improvement of drainage property and foamability can be aimed at.
R ¹² and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
R ¹² and R ¹³ are preferably each independently an alkyl group, and more preferably an alkyl group having 1 carbon atom (that is, a methyl group). If such a R ¹² and R ^13, increase more detergency and foaming property, and attained the further improvement of drainage.
m is 0 or 1, and 0 is preferable. If m is 0, it is possible to further improve the detergency against oil stains, foamability, and foam persistence.
When m is 1, X is a group selected from —CONH—, —NHCO—, —COO—, —OCO— or —O—, and among them, —CONH— is preferable from the viewpoint of liquid stability.
R ¹⁴ is an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. If it is in the said range, a synergistic effect with (A) component is high.
From the viewpoint of further improving the detergency, the component (b1) is preferably alkyldimethylamine oxide, more preferably alkyldimethylamine oxide in which R ¹¹ has 10 to 14 carbon atoms.

  Although content of (B) component in a liquid cleaning agent is not specifically limited, For example, 1-20 mass% is preferable and 3-15 mass% is more preferable. If it is less than the said lower limit, there exists a possibility that the detergency with respect to oil stains may fall, or water drainage may fall. If it exceeds the upper limit, the content of the component (E) in the liquid cleaning agent becomes relatively small, and the component (C) becomes difficult to uniformly disperse. For this reason, (C) component may adhere nonuniformly with respect to the washing | cleaning object, and there exists a possibility that the drainage property may fall.

  10-50 mass% is preferable and, as for the sum total of (A) component and (B) component in a liquid detergent, 15-35 mass% is more preferable. If it is less than the said lower limit, there exists a possibility that detergency and foamability may fall, and when it exceeds the said upper limit, there exists a possibility that other components may become relatively few and a liquid cleaning agent may isolate | separate.

  In the liquid cleaning agent, the mass ratio represented by component (A) / component (B) (hereinafter sometimes referred to as A / B ratio) is preferably 0.5 to 15, and more preferably 0.5 to 10. 0.5 to 5 is more preferable, and 1 to 3 is particularly preferable. When the A / B ratio is within the above range, the foamability and the cleaning power against oil stains can be further enhanced.

<(C) component: polyethylene glycol having a weight average molecular weight of 400,000 to 4,000,000>
Component (C) is polyethylene glycol having a weight average molecular weight (MW) of 400,000 to 4 million. By containing the component (C), the liquid cleaning agent has good drainage properties and can suppress the formation of water spots on the object to be cleaned.

  The weight average molecular weight of the component (C) is 400,000 to 4 million, preferably 1 million to 4 million. If it is less than the above lower limit value, water drainage is insufficient and water spot formation cannot be sufficiently suppressed, and if it exceeds the upper limit value, there is a possibility that the slimy feeling cannot be sufficiently suppressed. In addition, if the value exceeds the upper limit, the liquid cleaning agent may become turbid or separated.

The weight average molecular weight of the component (C) is a value measured in the same manner as in the method described in JP2011-256385A. Hereinafter, the measuring method of the weight average molecular weight of (C) component is demonstrated.
≪Raw materials used≫
Deionized water (DI water): Filtered with a 0.0002 mm nylon cartridge.
Sodium azide (NaN ₃ ): purity 99.99 mass% or more, manufactured by Sigma-Aldrich.
Pullulan: reference material.
Toluene: HPLC grade, manufactured by Fisher Science.
Bovine serum albumin (BSA): purity of 98% by mass or more (analyzed value by gel electrophoresis), manufactured by Sigma-Aldrich.
Eluent: 0.05 mass% NaN ₃ aqueous solution (solvent is DI water). After dissolving NaN ₃ through a cartridge (0.1 μm cellulose acetate), it was circulated through the cartridge for 5 hours to reach a refractive index of 1.3365 to ensure the purity of the eluent. The refractive index is a value measured by a Wyatt Optilab rEX Dri detector.

≪Sample preparation≫
Samples are prepared in pre-cooled eluent to minimize interference. The measurement object (polyethylene glycol) is added to the eluent, which is shaken for 3 hours and then stored at 4 ° C. overnight. After storage, the eluent containing the measurement target is shaken for 2 hours (25 ° C.) and filtered through a 0.45 μm nylon syringe filter to obtain a sample.
The standard (target concentration) of the concentration of the measurement target in the sample is as follows.
[Target concentration]
Weight average molecular weight to be measured (g / mol) Target concentration (mg / mL)
1.00 × 10 ⁵ 0.5-1
3.00 × 10 ⁵ 0.3
5.00 × 10 ⁵ 0.2
7.00 × 10 ⁵ 0.1-2
1.00 × 10 ⁶ 0.1
This target concentration is a measure of keeping the concentration to be measured below the entanglement concentration (C ^* ) of the polymer chain to ensure that the entanglement of the polymer chain is minimized. C ^* is defined as 1 / [n], where [n] is estimated according to 2 wt% Brookfield solution viscosity data using K = 2.216 × 10 ⁻⁴ dL / g and alpha = 0.849. Calculated according to the approximate weight average molecular weight.

≪Measurement equipment≫
Size exclusion chromatography (SEC) is used for the measuring device. An example of the structure of SEC is given.
Pump: Waters 2690 pump. A filter equipped with two layers of 0.2 μm nylon membrane installed in front of the injection valve.
Pump injection: Capable of injecting 100 μL of sample.
Column: Two TSK-Gel GMPW columns (7.5 mm ID × 30 cm, 17 μm particles, nominal: 100-1000 angstrom pores).
Detector: A Wyatt Dawn DSP MALLS detector connected to a Wyatt Optilab rEX Dri detector.

≪Measurement conditions≫
Measurement temperature: 28 ° C.
Measurement wavelength of Wyatt DAWN DSP: 632.8 nm.
Calibration: The Wyatt DAWN DSP MALLS detector is calibrated with HPLC grade toluene filtered through a 0.05 μm syringe filter. For the Wyatt Optilab rEX Dri detector and the Wyatt Dawn DSP MALLS detector, normalize to a 90 ° light scattering detector using the monodisperse BSA monomer as the isotropic peak at the BRI DRI peak.

≪Software and data processing≫
Signals from MALLS detector and DRI detector are analyzed by ASTRA V software.
Specifically, the polymer solution is irradiated with laser light (632.8 nm), and Rayleigh scattered light from the colloidal particles is measured. The intensity of scattered light (K · c / Rθ) at the scattering angle θ is expressed by the following Zimm equation (the following equation (i)). Plotting K · c / Rθ on the vertical axis and sin ² (θ / 2) on the horizontal axis (Debye plot) gives a linear relationship, rotating from the intercept of the vertical axis to Mw (weight average absolute molecular weight) and the slope of the straight line The radius (weighted average value of the distance from the center of gravity of the polymer molecule) is calculated.

Zim's formula: weight average molecular weight (Mw) = 1 / [K · c / Rθ] (i)
(Because the intercept θ = 0 and sin0 = 0 on the vertical axis of Mw = P (θ) / [K · c / Rθ], P (θ) can be calculated as 1 by the following equation (ii).)

Symbols in the above formula (i) are as follows.
Mw: weight average molecular weight K: optical constant = 4π ² n ₀ ² (dn / dc) ² / (λ ₀ ⁴ N) (ii)
c: Polymer concentration (g / mL)
Rθ: Relative intensity of scattered light at scattering angle θ P (θ): Factor representing angle dependence of scattered light P (θ) = 1− <r ² > {(4π / λ) sin (θ / 2)} ² / 3 (iii)

The symbols in the above formulas (ii) and (iii) are as follows.
n ₀ : refractive index of solvent dn / dc: change in refractive index with respect to change in polymer concentration λ ₀ : wavelength of laser light in vacuum (nm)
N: Avogadro number = 6.022 × 10 ²³
r ² : Mean square rotation radius λ: Wavelength of laser light in solution (nm)
For polymers, dn / dc (inherent refractive index increment) = 0.140 mL / g is applied.

Although the viscosity of (C) component is not specifically limited, 15-5000 mPa * s is preferable and, as for the viscosity of 1 mass% aqueous solution of (C) component, 40-5000 mPa * s is more preferable.
The viscosity of the component (C) is a standard for predicting the weight average molecular weight of the component (C). Accordingly, when the viscosity of the 1% by mass aqueous solution is equal to or higher than the lower limit, the weight average molecular weight of the component (C) is sufficiently large, water drainability is improved, and formation of water spots can be suppressed satisfactorily. If it is below the said upper and lower limit, a slime feeling can be suppressed more favorably.

  The viscosity of the 1 mass% aqueous solution of component (C) is measured at 25 ° C. with a Brookfield RVF viscometer. However, when the viscosity of the 1% by mass aqueous solution is 200 mPa · s or less, the rotor no. 1. A value read after 1 minute at a rotation speed of 20 rpm. When the viscosity of the 1 mass% aqueous solution exceeds 200 mPa · s, the rotor No. 2. It is a value read after 5 minutes at 2 rpm.

  Although content of (C) component in a liquid cleaning agent is not specifically limited, 0.1-2 mass% is preferable and 0.2-2 mass% is more preferable. If it is not less than the above lower limit value, it is possible to improve water drainage and better suppress the formation of water spots, and if it is not more than the above upper limit value, it can suppress the slime feeling better and make the liquid detergent more transparent. The appearance can be made.

  In the liquid detergent, the mass ratio represented by {(A) component + (B) component} / (C) component (hereinafter sometimes referred to as (A + B) / C ratio) is 10 to 150, 15 -120 are preferable and 30-100 are more preferable. When the (A + B) / C ratio is less than the above lower limit, the amount of the component (C) is excessively large and the slimy feeling cannot be sufficiently suppressed, the foamability is lowered, and the transparency of the liquid detergent is lowered. When the (A + B) / C ratio exceeds the above upper limit, the component (C) is too small, the water drainage is reduced, and the formation of water spots cannot be sufficiently suppressed.

<(D) component: a water-soluble solvent having 2 to 10 carbon atoms and one hydroxyl group in the molecule>
The component (D) is a water-soluble solvent having 2 to 10 carbon atoms and having one hydroxyl group in the molecule. The liquid detergent can improve water drainage by containing the component (D).
The water-soluble solvent is a liquid at normal temperature (20 ° C.), and the amount of ion-exchanged water required to dissolve 1 mL is less than 50 mL.

  As the component (D), a compound represented by the following general formula (d1) (hereinafter sometimes referred to as the (d1) component), a monovalent alcohol having 2 to 3 carbon atoms (hereinafter referred to as the (d2) component) Among them, the component (d1) is preferable, and the combination of the component (d1) and the component (d2) is more preferable. Such component (D) can further improve the drainability of the liquid cleaning agent by more uniformly dispersing the component (C) in the liquid cleaning agent.

R ²¹ —O— (EO) r—H (d1)

[In the formula (d1), R ²¹ represents a linear or branched alkyl group having 2 to 6 carbon atoms or a phenyl group, EO represents an oxyethylene group, and r represents an average number of EO repeats 1 to 3. Is the number of ]

As the component (d1), an ethylene glycol solvent is preferable, and an ethylene glycol phenyl ether solvent and an ethylene glycol alkyl ether solvent are more preferable.
Examples of the ethylene glycol phenyl ether solvent include ethylene glycol monophenyl ether (phenoxyethanol) and diethylene glycol monophenyl ether.
Examples of the ethylene glycol alkyl ether solvent include diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and ethylene glycol monoisopropyl ether. Among them, butyl carbitol Is preferred.
These (d1) components may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the component (d2) include ethanol and isopropanol. These (d2) components may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the component (D), either the component (d1) or the component (d2) may be used, or both may be used, and both the component (d1) and the component (d2) are used. Is preferred. When both the component (d1) and the component (d2) are used, a combination of butyl carbitol and ethanol is preferable.

  For example, the content of the component (D) in the liquid detergent is preferably 5 to 25% by mass, and more preferably 8 to 15% by mass. If it is less than the said lower limit, it becomes difficult to disperse | distribute (C) component uniformly to (E) component, and there exists a possibility that the water drainage property may fall. If it exceeds the upper limit, the foamability may be reduced.

  In the liquid detergent, the mass ratio represented by component (D) / component (C) (hereinafter sometimes referred to as D / C ratio) is 5 to 150, preferably 10 to 50, and preferably 15 to 40. More preferred. When the D / C ratio is less than the above lower limit, the detergency against oil stains is insufficient, and the appearance of the liquid detergent is impaired. If it exceeds the above upper limit value, the adsorption of the component (C) to the object to be washed becomes insufficient, the water drainage becomes insufficient, and the formation of water spots cannot be sufficiently suppressed.

  In the liquid detergent, the mass ratio represented by {(A) component + (B) component} / (D) component (hereinafter sometimes referred to as (A + B) / D ratio) is 1 to 5, and 1 -4 are preferable and 1.3-3.5 are more preferable. When the (A + B) / D ratio is less than the lower limit, foaming properties are insufficient, and when the ratio exceeds the upper limit, the transparency of the liquid detergent may be impaired.

<(E) component: water>
(E) A component is water. The component (E) functions as a dispersion medium in the liquid cleaning agent.
The content of the component (E) in the liquid detergent is, for example, preferably 30 to 85% by mass, and more preferably 40 to 75% by mass. If the amount is less than the lower limit, the components (A) to (D) may not be dispersed well. If the amount exceeds the upper limit, the content of the components (A) to (D) decreases, and a large amount of liquid is used during washing. A cleaning agent is required, which is not preferable.

<Optional component>
The liquid detergent is a surfactant other than the components (A) to (B) (arbitrary surfactant), hydrotrope agent, pH adjuster, chelating agent, antioxidant, You may contain arbitrary components, such as a coloring agent, an enzyme, disinfectant (water-soluble silver salt, water-soluble copper salt, water-soluble zinc salt), a fragrance | flavor.

  As the optional surfactant, conventionally known ones are used, for example, polyoxyalkylene alkyl ether, ester type polyoxyalkylene alkyl ether, alkyl polyglycoside, alkyl glucoside, alkyl monoglyceryl ether; fatty acid alkanolamide, alkyl methyl gluca Fatty acid amide derivatives such as amides; Nonionic surfactants such as long-chain fatty acid ester compounds such as sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, fatty acid glycoside esters, and fatty acid methyl glycoside esters; Di-long chain alkyl type quaternary ammonium salts And cationic surfactants such as mono long chain alkyl type quaternary ammonium salts, and amphoteric surfactants such as alkylcarboxybetaines and alkylsulfobetaines. These arbitrary surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the hydrotrope include toluene sulfonic acid, toluene sulfonate, cumene sulfonic acid, cumene sulfonate, benzoic acid, benzoate and the like. These hydrotropes may be used individually by 1 type, and may be used in combination of 2 or more type.

(Production method)
As a manufacturing method of the liquid detergent of this invention, what is necessary is just the method which can disperse | distribute (A)-(D) component to (E) component, for example, (A)-(D) component and arbitrary as needed. Examples include a method in which the component is dispersed in the component (E) and then adjusted to an arbitrary pH using a pH adjuster.

  As described above, according to the present invention, the components (A) to (E) are contained, and the D / C ratio, (A + B) / C ratio, and (A + B) / D ratio are in specific ranges. It has good foaming property, has little sliminess, and hardly forms water spots on the object to be cleaned.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(A) component>
A-1: Sodium polyoxyethylene lauryl sulfate (AES) in which the carbon number of the alkyl group is 12 to 14 and the average number of repeating oxyethylene groups is 1. Sinoline SPE-1100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.).
A-2: Secondary alkanesulfonic acid sodium (SAS) having 14 to 17 carbon atoms. HOSTAPUR SAS 30A (trade name, manufactured by Clariant Japan Co., Ltd.).
A-3: Sodium linear alkylbenzene sulfonate (LAS-Na) having 10 to 14 carbon atoms in the linear alkyl group. Teka Power L124 (trade name, manufactured by Teika Co., Ltd.) neutralized with sodium hydroxide.
<(A ′) component: Comparative product of component (A). >
A′-1: potassium laurate (lauric acid K). NAA-122 (trade name, manufactured by NOF Corporation) neutralized with liquid caustic potash (trade name, manufactured by Asahi Glass Co., Ltd.).
A′-2: Polyoxyethylene lauryl ether (POE-C12EO7) having an average number of repeating oxyethylene groups of 7. EMALEX 707 (trade name, manufactured by Nippon Emulsion Co., Ltd.).

<(B) component>
B-1: Alkyldimethylamine oxide (AX) having 12 carbon atoms in the alkyl group. Aromox DM12D-W (trade name, manufactured by Lion Akzo Corporation).
B-2: Amidopropyldimethylamine oxide (APAX) laurate. GENAMINOX AP (trade name, manufactured by Clariant Japan KK).
<(B ′) component: Comparative product of component (B)>
B′-1: Lauryl hydroxysulfobetaine (HSB). Anhitoru 20HD (trade name, manufactured by Kao Corporation).

<(C) component>
C-1: Polyethylene glycol (PEG) having a weight average molecular weight of 400,000 (PEG 400,000). POLYOX WSR-N3000 (trade name, manufactured by Dow Chemical Co., Ltd.). The viscosity of the 1% by mass aqueous solution is 20 mPa · s (the viscosity of the 5% by mass aqueous solution is 3,950 mPa · s (No. 1 rotor, 2 rpm, after 5 minutes)).
C-2: PEG having a weight average molecular weight of 1 million (PEG 1 million). POLYOX WSR-12K (trade name, manufactured by Dow Chemical Co., Ltd.). The viscosity of the 1% by mass aqueous solution is 40 mPa · s (the viscosity of the 2% by mass aqueous solution is 640 mPa · s (No. 1 rotor, 10 rpm, after 1 minute)).
C-3: PEG having a weight average molecular weight of 4 million (PEG 4 million). POLYOX WSR-301 (trade name, manufactured by Dow Chemical Co., Ltd.). The viscosity of the 1% by mass aqueous solution is 4,800 mPa · s.
<(C ′) component: Comparative product of component (C)>
C′-1: PEG having a weight average molecular weight of 6000 (PEG 6000). PEG6000S (trade name, manufactured by Sanyo Chemical Industries, Ltd.). The viscosity of the 1% by mass aqueous solution is 4 mPa · s.
C′-2: PEG having a weight average molecular weight of 300,000 (PEG 300,000). POLYOX WSR-750 (trade name, manufactured by Dow Chemical Co., Ltd.). The viscosity of the 1% by mass aqueous solution is 12 mPa · s (the viscosity of the 5% by mass aqueous solution is 800 mPa · s (No. 1 rotor, 10 rpm, after 1 minute)).
C′-3: PEG having a weight average molecular weight of 8 million (PEG 8 million). POLYOX WSR-308 (trade name, manufactured by Dow Chemical Co., Ltd.). The viscosity of the 1% by mass aqueous solution is 12,500 mPa · s.

<(D) component>
D-1: Ethanol (special reagent grade, manufactured by Junsei Chemical Co., Ltd.).
D-2: Isopropanol (special reagent grade, manufactured by Junsei Co., Ltd.).
D-3: 2-phenoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd.).
D-4: Butyl carbitol. Butyl diglycol (95) (trade name, manufactured by Nippon Emulsifier Co., Ltd.).
<(D ′) Component: Comparative Product of (D) Component>
D′-1: Propylene glycol (special reagent grade, manufactured by Junsei Chemical Co., Ltd.).

<(E) component>
E-1: Ion exchange water.

<Optional component>
“Mass%” described at the end of each component is the blending amount in the liquid detergent.
Paratoluenesulfonic acid: Teikatox 300 (manufactured by Teika Corporation) 2 mass%.
Polyoxyethylene lauric acid monoethanolamide having an average oxyethylene group repeating number of 2: Amidette 2L-Y (trade name, Kawaken Fine Chemical Co., Ltd.) 2 mass%.
Sodium hydroxide: CLEACUT-S 48% (trade name, manufactured by Tsurumi Soda Co., Ltd.) ... appropriate amount (amount necessary for adjusting the liquid detergent to pH 7.5).

(Evaluation method)
<Liquid appearance>
A cylindrical glass container having a diameter of 4 cm and a height of 7 cm was filled with 30 g of the liquid cleaning agent in each example, and sealed with a lid. In this state, the appearance of the liquid detergent after standing for 1 day in a thermostatic chamber adjusted to 25 ° C. was visually observed after standing still and lightly shaken by hand. Based on the evaluation.

≪Evaluation criteria≫
○ (Pass): No separation was observed, and it remained uniform and transparent after shaking.
X (failed): A separated product was observed or it became cloudy when shaken.

<Drainability>
Take 13.5cm x 7.5cm x 3cm dishwashing sponge with 38g of tap water and 2g of liquid detergent and squeeze it 5 times by hand, then a 21cm diameter dish (green pottery dish by WAECHTERSBACH) ) Were washed 10 times each. After that, the dish is sufficiently rinsed with tap water (hardness, about 4 ° DH) and placed on a commercial tableware basket so that the dish is almost vertical. evaluated. The above evaluation method was repeated 5 times, and the respective evaluation points were averaged. If the average score is 3 or more, it can be said that the water drainage is good.

≪Evaluation criteria≫
4 points: The line where the water was cut off flowed in a horizontal line and did not remain as water droplets.
3 points: The line where the water runs out runs almost horizontally, but the water drops remain slightly.
2 points: The line that drains water was slightly disturbed, and water drops remained in some places.
1 point: The line where water runs out is considerably disturbed, and many water droplets remain.
In addition, water spots were formed after the water droplets were left to dry naturally.

<Smoothness>
The dish was scrubbed and rinsed thoroughly with tap water in the same manner as in the evaluation of “<Drainability>”. The slime feeling when the surface of the dish after rinsing was rubbed with a finger was evaluated according to the following evaluation criteria. In this evaluation method, five female evaluators evaluated and averaged the evaluation points of each evaluator. If the average score is 3 or more, it can be said that the slime feeling is sufficiently suppressed.

≪Evaluation criteria≫
4 points: I did not feel any slime.
3 points: There was almost no slimy feeling.
2 points: I felt a little slimy.
1 point: I felt quite slimy.

<Detergency>
5 g of olive oil (trade name: AJINOMOTO olive oil extra virgin, manufactured by J-Oil Mills Co., Ltd.) was applied to a round plate made of polypropylene having a diameter of 16 cm to obtain a contaminated dish.
38 g of water and 2 g of a liquid detergent were taken in a 11.5 cm × 7.5 cm × 3 cm dishwashing sponge, and this sponge was rubbed by hand 5 times, and then the surface of the contaminated dish was rubbed 10 times and washed. Then, after thoroughly rinsing with tap water, the feel when the surface of the dish was traced with fingers was evaluated according to the following evaluation criteria. In this evaluation method, five female expert evaluators evaluated and averaged the evaluation points of each evaluator. If the average score is 3 or more, it can be said that the detergency against oil stains is sufficient.

≪Evaluation criteria≫
4 points: I did not feel any oiliness at any part of the dish.
3 points: I felt a slight oil spill on a part of the dish.
2 points: A little oily oil was felt in most parts of the dish.
1 point: I felt oily scum in most parts of the dish.

<Foamability>
38 g of water and 2 g of liquid detergent were taken in a dishwashing sponge measuring 11.5 cm × 7.5 cm × 3 cm, and how to make bubbles after gently squeezing 5 times by hand was determined according to the following criteria. If evaluation was "(circle)", it was judged that foamability was favorable.
○: Foam covered 2/3 or more of the upper surface of the sponge.
Δ: Foam covered 1/3 or more and less than 2/3 of the upper surface of the sponge.
X: The foam did not cover 1/3 or more of the sponge upper surface.

(Examples 1-20, Comparative Examples 1-16)
According to the compositions shown in Tables 1 to 3, the liquid detergents of each example were prepared by the following production method (when there are unblended components, the components are not blended).
The unit of the blending amount in the table is “mass%”, and all the components indicate the amount in terms of pure content.
In addition, the “balance” of the blending amount of water in the table is an amount necessary for the liquid detergent of each example to be 100% by mass.
First, the (A) component or (A ′) component and the (D) component or (D ′) component are put into a 200 mL beaker, and a stirrer (three-one motor (trade name) TYPE 600G type propeller R type general-purpose stirring) The mixture was agitated with a wing-attached one (manufactured by Shinto Kagaku Co., Ltd.).
Next, add (B) component or (B ′) component, optional component excluding sodium hydroxide and a part of water (tap water) to 90% by mass of the total amount (100% by mass), and stir did. Then, it adjusted to pH7 (25 degreeC) with sodium hydroxide, and added (C) component or (C ') component, stirring. The remainder of water was added so that the whole amount might be 100 mass%, and the liquid cleaning agent of each case was obtained.
About the obtained liquid cleaning agent, a liquid external appearance, a water drainage property, a slime feeling, a cleaning power, and foaming property were evaluated, and the result is shown in a table | surface.

As shown in Tables 1 to 3, Examples 1 to 20 to which the present invention was applied had a foaming property of “◯”, a water drainage of 3.0 points or more, and a slime feeling of 3.0 points or more. In addition, in Examples 1 to 20, the detergency was 3.2 points or more, and the liquid appearance was “◯”.
Especially, the drainage property of Example 4 using D-1 and D-4 in combination as the component (D) was higher than that of Example 1 using only D-1.
In contrast, Comparative Example 1 containing no component (B), Comparative Example 2 containing no component (A), Comparative Example 7 containing no component (C), Comparative Example 13 containing no component (D), D / In Comparative Examples 3 to 6, 8, and 16 in which any of the C ratio, (A + B) / C ratio, and (A + B) / D ratio was outside the scope of the present invention, the water drainability was less than 3 points.
Comparative Example 11 using component (A ′) instead of component (A), Comparative Example 12 using component (B ′) instead of component (B), Component (C ′) replacing component (C) In Comparative Examples 10, 14, and 15, and Comparative Example 10 using the component (D ′) instead of the component (D), at least one of water drainage, slime feeling, and cleaning power was less than 3 points. .
From these results, it was found that by applying the present invention, foamability is good, there is little sliminess, and it is difficult to form a water spot.

Claims (1)

(A) component: at least one anionic surfactant selected from a sulfonic acid type anionic surfactant and a sulfate ester type anionic surfactant; and (B) component: an amine oxide type semipolar surfactant. (C) component: polyethylene glycol having a weight average molecular weight of 400,000 to 4 million, (D) component: water-soluble solvent having 2 to 10 carbon atoms and one hydroxyl group in the molecule, and (E) component: water Containing
The mass ratio represented by (D) component / (C) component is 5-150, the mass ratio represented by {(A) component + (B) component} / (C) component is 10-150, {(A ) Component + (B) component} / (D) component mass ratio represented by the component is 1-5.