JP2013082845A - Dish detergent composition for hand washing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dish detergent for hand washing, which forms a rich lather upon washing and exhibits sustainability of bubbles during washing, meanwhile, enables bubbles to disappear instantaneously upon rinsing and completes the rinsing with a small amount of water.SOLUTION: The dish detergent composition for hand washing includes: (a) 0.1 to 30 mass% of anionic surfactant [excluding (b)] which is an anionic surfactant having 8-21C hydrocarbon group, sulfuric ester salt group or sulfonic acid salt group and has an area elastic modulus E of 10 to 50 mN/m; (b) 0 to 30 mass% of sulfosuccinic acid alkyl ester having 5-18C alkyl group or its salt; and (c) 0 to 20 mass% of 10-18C fatty acid or its salt. Therein, the component (b) and the component (c) are not turned to be 0 mass% at the sme time.

Description

  The present invention relates to a dishwashing composition for hand washing.

  A dishwashing agent for hand washing is required to have abundant foaming at the time of washing and the persistence of the foam at the time of washing. This foamability / foam persistence is a very important physical property that correlates with the persistence of washing, and until now, the development of a cleaning agent excellent in foamability / foam persistence has been mainly performed.

  Patent Document 1 discloses a technique of a detergent suitable for dishwashing containing sulfosuccinate, having high foamability and excellent detergency. Patent Document 2 discloses a technique of a dishwashing composition containing dialkylsulfosuccinates and amine oxides, and it is described in detail that fatty acids can be contained as a builder. Patent Document 3 discloses a surfactant composition containing a specific alkyl sulfate ester derivative, having a low Kraft point, excellent hard water resistance, and excellent foamability and foam persistence. Patent Document 4 describes that a fatty acid can be used as a foam inhibitor for a liquid detergent composition that can use an ethylene oxide condensate of a sulfoalkyl succinate dialkyl salt and a fatty alcohol.

JP-A-62-215699 Special table 2008-507611 JP 2009-35714 A Japanese Unexamined Patent Publication No. 3-207799

  In recent years, it is preferable to reduce the amount of water used for hand-washing and washing, and it is desired to reduce the rinse water after washing with a dishwashing agent as much as possible for the purpose of reducing environmental burden and effectively using water resources. However, detergents that are generally excellent in foamability / foam persistence require a large amount of water to complete rinsing. Accordingly, there is a strong demand for a dishwashing detergent for hand washing that exhibits abundant foaming and foam persistence during washing, but disappears instantly during rinsing and is rinsed with a small amount of water. In this respect, in Patent Documents 1 to 3, no consideration is given to the disappearance of bubbles during rinsing. In addition, the fatty acid as an antifoaming agent as listed as “Foaming Inhibitor” in Patent Document 4 is intended to make the foam low when washing, and maintains a very rich foam during washing. It does not suggest a relationship between the formation of the liquid and the technology of instant defoaming at the time of rinsing.

  Accordingly, an object of the present invention is to provide a dishwashing agent for hand washing that exhibits abundant foaming at the time of washing and the persistence of the foam at the time of washing, but the foam disappears instantly at the time of rinsing and is rinsed with a small amount of water. is there.

  The present invention is (a) an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester base or a sulfonate group, and has an area elastic modulus E of 10 mN / m or more and 50 mN / m. Anionic surfactants [excluding (b)] [hereinafter referred to as component (a)] 0.1 to 40% by mass, (b) a sulfosuccinic acid alkyl ester having an alkyl group having 5 to 18 carbon atoms or 0 to 30% by mass of the salt (hereinafter referred to as component (b)) and (c) a fatty acid having 10 to 18 carbon atoms or a salt thereof (hereinafter referred to as component (c)) 0 to 20% by mass ( The present invention relates to a dishwashing composition for hand-washing, in which the contents of the component b) and the component (c) are not 0% by mass at the same time.

  The present invention also relates to (a) an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester base or a sulfonate group, having an area elastic modulus E of 10 mN / m or more and 50 mN. / M or less anionic surfactant (except (b)), (b) a sulfosuccinic acid alkyl ester having an alkyl group having 5 to 18 carbon atoms or a salt thereof, and (c) a fatty acid having 10 to 18 carbon atoms Or a cleaning solution containing a salt thereof, wherein the concentration in the cleaning solution is (a) 0.01-2% by mass, (b) 0-1% by mass, and (c) 0-1% by mass, (b ) And (c) are related to the cleaning liquid in which the concentration does not become 0 mass% at the same time.

  Moreover, this invention relates to the washing | cleaning method of the tableware which wash-washes tableware with the washing | cleaning liquid using the dishwashing agent composition for hand-washing of the said invention, and then rinses using water.

  According to the present invention, there is provided a dishwashing agent for hand-washing that exhibits abundant foaming at the time of washing and the persistence of the foam at the time of washing, but the foam disappears instantly at the time of rinsing and the rinsing is completed with a small amount of water.

It is the schematic of the apparatus which measures the surface pressure of surfactant aqueous solution. FIG. 2A is a graph showing the relationship between the surface pressure and time, and FIG. 2B is a graph showing the relationship between the surface pressure and the amount of change in surface area. It is the schematic which shows the evaluation method of the foam extinction property performed in the Example. It is the schematic which shows the piercing | piercing state of the introduction means (joro) of the hard water used by the foam extinction evaluation of the Example.

1 trough 2 barrier 3 surface pressure sensor

<(A) component>
The component (a) of the present invention is an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group, and has an area elastic modulus E of 10 mN / m or more and 50 mN / m. m or less. Here, the area elastic modulus E is preferably 45 mN / m or less, more preferably 40 mN / m or less. On the other hand, it is preferably 15 mN / m or more, more preferably 20 mN / m or more, more preferably 25 mN / m or more, and more preferably 30 mN / m or more.

The area elastic modulus E can be calculated from physical properties measured using a commercially available Langmuir trough capable of analyzing the interface rheology of a Gibbs adsorbed film and capable of measuring by reciprocating the barrier. As an example, in the present invention, as shown in FIGS. 1 (a) and 1 (b), a trough 1 (water tank) for containing a surfactant aqueous solution, and the front and back of the trough 1 in contact with the surfactant aqueous solution (in FIG. 1) An apparatus including a barrier 2 that can move in the direction of the arrow and a surface pressure sensor 3 (for example, a Wilhelmy plate) can be used. FIG. 1A is a schematic perspective view of the apparatus, FIG. 1B is a schematic plan view of the apparatus, and the other end of the trough is omitted. In the apparatus of FIG. 1, the trough 1 is filled with an aqueous solution of component (a). Since the surfactant Gibbs adsorption monomolecular film formed at the gas-liquid interface is an adsorption film similar to the foam film, physical properties are analyzed as a model foam film. The barrier 2 is reciprocated at a constant speed to change the area of the adsorption film from the 0 second time point to the t second time (this is defined as the surface area change amount A from 0 to t seconds), and the mechanical response at that time Is measured as the surface pressure response (this is defined as the surface pressure π _{t of the} component aqueous solution (a) after t seconds). Further, the surface pressure π ₀ of the surfactant at the time of 0 second (when the barrier is stationary) is also measured. From these results, the area elastic modulus E is obtained by the following formula (1). In this case, the concentration of the component (a) aqueous solution is preferably selected in the range from the critical micelle concentration (CMC) of the surfactant to 1/1000 of CMC.

[In the formula, π ₀ is the surface pressure of the component (a) aqueous solution at time 0 seconds, π _t is the surface pressure of the component (a) aqueous solution after t seconds, and A is the amount of change in surface area from 0 to t seconds. . ]

  Although it does not specifically limit as an anionic surfactant of (a) component, From a foaming viewpoint, for example, it is C8-C18, Preferably it has C8-C15 alkyl group. Sulfuric acid ester salt, polyoxyalkylene alkyl ether having an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, and an average addition mole number of oxyalkylene groups having 2 to 3 carbon atoms being 0.1 to 6 An anionic surfactant selected from a sulfate ester salt, an alkylbenzene sulfonate having an alkyl group having 8 to 15 carbon atoms, and an alkane sulfonate having 8 to 15 carbon atoms is a preferred example. Preferred examples of the salt include inorganic salts selected from sodium salts, ammonium salts, potassium salts, and magnesium salts, and organic amine salts selected from monoethanolamine salts, diethanolamine salts, triethanolamine salts, and monophorin salts.

As the component (a), an anionic surfactant represented by the following general formula (a1) is particularly preferable from the viewpoints of foamability at the time of washing, foam persistence, and foam disappearance at the time of rinsing.
R ^1a —O— (R ^2a O) _n —SO ₃ M (a1)
[Wherein, R ^1a is an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, R ^2a is an ethylene group and / or a propylene group, preferably a propylene group, and n is an average added mole number. A number from 0 to 6, preferably from 0 to 2, more preferably from 0.1 to 2, more preferably from 0.2 to 1.5, still more preferably from 0. The number is 3 or more and 1 or less, and more preferably 0.4 or more and 0.8 or less. M is a cation, preferably an inorganic or organic cation. ]

In the case where R ^2a is an ethylene group, n is preferably a number of 1.5 or less, more preferably a number of 1 or less, and further a number of 0.8 or less, and a number of 0.1 or more, more preferably 0.2 or more. More preferably, the number is 0.3 or more. Further, when R ^2a is a propylene group, n is preferably 1.5 or less, more preferably 1.0 or less, further 0.8 or less, and further 0.6 or less. The above number, a number of 0.2 or more, and a number of 0.3 or more are preferable. Further, when R ^2a is an ethylene group or a propylene group, n can be selected from these ranges.

In the general formula (a1), when n is 0, a compound containing alkyl in which R ^1a has a branched structure can also be used. When n is 0, the compound of the general formula (a1) preferably has a branching rate [ratio of the total number of moles of the compound having a branched alkyl group to the total number of moles of the compound of the general formula (1)]. 15-100 mol%, more preferably 40-100 mol%, still more preferably 70-100 mol%, still more preferably 90-100 mol% of the compound is suitable.

  M in the general formula (a1) is an organic cation selected from an inorganic cation selected from sodium ion, ammonium ion, potassium ion and magnesium ion, monoethanolamine, diethanolamine, triethanolamine and morpholine acid salt. , Preferably sodium ion, ammonium ion, potassium ion, magnesium ion.

The method for preparing the compound of the general formula (a1) is not particularly limited. For example, after adding a predetermined amount of ethylene oxide and / or propylene oxide to the fatty alcohol represented by R ^1a —OH depending on the purpose. It is produced by sulfuric esterification with a sulfating agent selected from sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid and chlorosulfonic acid, and neutralization with a predetermined alkali. The addition reaction of ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO) requires a catalyst, and an alkali hydroxide such as NaOH or KOH can be used. Moreover, the catalyst which has a magnesium oxide as a main component as described in Unexamined-Japanese-Patent No. 8-323200 can be used, The former can obtain polyoxyethylene alkyl ether with comparatively wide addition mole number distribution, The latter is comparison. A compound having a narrow addition mole number distribution can be obtained. Further, as disclosed in JP-A-10-158384, it is also possible to control the added mole number distribution by using an alkali catalyst and a metal oxide catalyst in combination.

In the case of obtaining a compound in which R ^1a, which is suitable when n is 0 in the general formula (a1), contains an alkyl group having a branched structure, the alcohol represented by R ^1a —OH as a raw material has 8 to 8 carbon atoms. 14 alcohols obtained by hydroformylation of 1-alkene (contains 15 to 70 mol% of an alkyl group having a methyl group branched at the β-position with respect to the OH group) and an aldehyde having 4 to 8 carbon atoms were condensed. Subsequently, a gel-form alcohol obtained by reduction (containing 100 mol% of a structure in which an alkyl group having 3 to 6 carbon atoms is branched at the β-position relative to the OH group) and a dimer of isobutene are hydroformylated. The resulting 3,5,5-trimethylhexanol and isobutene trimer are hydroformylated to obtain a multibranched tridecanol (branch rate is 100 mol%), petroleum and coal. And synthetic alcohols (branched index of about 20 to 100 mole percent of the alkyl group) can be exemplified.

In the present invention, the component (a) is a compound represented by the general formula (a1), wherein R ^2a is a propylene group, n is 0.1 to 1.5, further 0.2 to 1, Most preferred are compounds having a number of 0.3 to 0.8, more preferably 0.5 to 0.6.

<(B) component>
The component (b) used in the present invention is a sulfosuccinic acid alkyl ester having an alkyl group having 5 to 18 carbon atoms or a salt thereof, preferably a sulfosuccinic acid monoalkyl ester having an alkyl group having 5 to 18 carbon atoms, an alkyl group. One or more surfactants selected from sulfosuccinic acid dialkyl esters having 5 to 18 carbon atoms and salts thereof, specifically, compounds of the following general formula (b1) are preferred.

[Wherein, R ^1b and R ^2b are each an alkyl group having 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 10 carbon atoms, or a hydrogen atom, preferably an alkyl group having a branched structure; ^At least one of ^1b and R ^2b is an alkyl group having 5 to 18 carbon atoms. That is, the case where R ^1b and R ^2b are hydrogen atoms at the same time is excluded. A ¹ and A ² are each independently an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, x and y are average added mole numbers, and are each independently 0 to 6, preferably 0 to 3, more preferably 0. M ¹ is a cation, preferably an inorganic or organic cation. ]

When the component (b) is a sulfosuccinic acid dialkyl ester or a salt thereof, R ^1b and R ^2b in the general formula (b1) may be the same or different, and foamability at the time of washing and foam at the time of rinsing From the viewpoint of disappearance, it is an alkyl group having 5 to 18, preferably 6 to 14, more preferably 7 to 10 carbon atoms, and preferably an alkyl group having a branched structure. When the number of carbons is 5 or more, good foam disappearance at rinsing is obtained, and when the number of carbons is 18 or less, good foaming at washing is obtained. In addition, when the component (b) is a sulfosuccinic acid monoalkyl ester or a salt thereof, one of R ^1b and R ^{2b in} the general formula (b1) is a viewpoint of foamability during washing and foam disappearance during rinsing. To an alkyl group having 5 to 18 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 7 to 10 carbon atoms, and the other is a hydrogen atom. From the viewpoint of foaming properties at the time of washing and foam disappearance properties at the time of rinsing, the component (b) is one or more kinds of surface activity selected from sulfosuccinic acid dialkyl esters each having 5 to 18 carbon atoms in the alkyl group and salts thereof. Agents are preferred.

In general formula (b1), R ^1b and R ^2b are each preferably a group specifically selected from an n-octyl group, a sec-octyl group, a decyl group, an isodecyl group, and a 2-ethylhexyl group. And 2-ethylhexyl group is still more preferred. Examples of M ¹ include inorganic cations selected from hydrogen ions, sodium ions, potassium ions, magnesium ions, and ammonium ions, organic cations selected from monoethanol ammonium ions, diethanol ammonium ions, and triethanol ammonium ions. Preferably, it is a cation selected from sodium ion, potassium ion, magnesium ion, and ammonium ion.

When component (b) is a dialkyl ester of sulfosuccinic acid or a salt thereof, the method for preparing the compound in which R ^1b and R ^2b are the same is not particularly limited, but for example, US Pat. No. 2,028 No. 091, and a method for preparing an asymmetric compound in which R ^1b and R ^2b are different can be produced by referring to, for example, JP-A-58-24555. can do. When a commercially available compound is used, PALEX OT-P (a compound in which R ^1b and R ^2b are both 2-ethylhexyl groups) manufactured by Kao Corporation, and PELEX TR (both R ^1b and R ^2b are tridecyl groups). Compound), Lusit A-BO (compound in which R ^1b and R ^2b are both 2-ethylhexyl groups) manufactured by BASF, and aerosol AY-100 (R ^1b and R ^2b are both amyl groups) available from Mitsui Cytec Co., Ltd. And the same aerosol A-196 (a compound in which R ^1b and R ^2b are both cyclohexyl groups).

<(C) component>
Component (c) of the present invention is a fatty acid having 10 to 18 carbon atoms or a salt thereof, specifically decanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, Mention may be made of linolenic acid and salts thereof. Moreover, it is also possible to use mixed fatty acids, such as an insulator composition fatty acid. Examples of fatty acid salts include inorganic salts selected from sodium salts, ammonium salts, potassium salts, and magnesium salts, and organic amine salts such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and morpholine salts. Salts, ammonium salts, potassium salts, magnesium salts, and more preferably sodium salts, ammonium salts, and potassium salts. The component (c) is more preferably lauric acid, myristic acid, palmitic acid or a salt thereof, more preferably lauric acid, myristic acid or a salt thereof, most preferably myristic acid or a salt thereof. is there. Therefore, from the viewpoint of foaming ability and foam extinction, the component (c) preferably contains myristic acid or a salt thereof. In the component (c), the proportion of myristic acid or a salt thereof is 20 to 100% by mass, 50-100 mass%, and 80-100 mass% are still more preferable.

<Dishwashing composition for hand washing>
The dishwashing detergent composition for hand washing of the present invention comprises an anionic surfactant having an area elastic modulus E of 10 mN / m or more and 50 mN / m or less as the component (a) having foamability / foam persistence, and ( By using the component b) and / or the component (c) in combination, the washing water having a relatively high concentration of the detergent exhibits very high foaming properties and foam persistence, but rinse water is added after the washing is completed. In this way, the foam disappears instantly and rinsing with a small amount of water can be completed. The reason for this is not necessarily clear, but the foam is formed with the surfactant aligned at the gas-liquid interface, but the area elastic modulus, which is the strength of the foam film, differs depending on the surfactant aligned at this time. Those having a small area elastic modulus are considered to be easily broken by the impact and fluctuation of dilution with water. However, in the high concentration region of the surfactant during cleaning, since the surfactant is abundant, the foam film is supplemented instantly, so both foaming during cleaning and foam disappearance during rinsing are compatible. It is thought that you can. The anionic surfactant as component (a) has such a strong tendency, and the effect of specifying the area elastic modulus is more remarkably exhibited.

  In the dishwashing composition for hand washing of the present invention, the component (a) is 0.1 to 40% by mass, preferably 1 to 30% by mass, more preferably from the viewpoint of foaming power, foam extinguishing property and economy. 2-15 mass%, More preferably, 4-10 mass% is contained. The component (b) is 0 to 30% by mass, preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, still more preferably 1 to 5% by mass, and still more preferably 2 to 4%. Preferably, the component (c) is 0 to 20% by mass, preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.4 to 3% by mass. contains. However, (b) component and (c) component do not become 0 mass% simultaneously. That is, the dishwashing composition for hand washing of the present invention contains at least one of the component (b) and the component (c). In the dishwashing composition for hand washing of the present invention, the component (b) and / or the component (c) is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and still more preferably 0.5. -10 mass%, More preferably, it contains 1-5 mass%. In addition, the quantity of (b) component for calculating | requiring mass%, mass ratio, etc. in this invention is the quantity as an acid type compound. In the present invention, the amount of the component (c) for determining mass%, mass ratio, etc. is an amount as an acid type compound.

  Moreover, in the dishwashing agent composition for hand-washing of this invention, when both (b) component and (c) component are included, from a viewpoint of foaming power, (a) component / [(b) component + (c) component ] Is preferably 0.3 or more, preferably 0.5 or more, more preferably 1 or more. On the other hand, from the viewpoint of foam extinction, the mass ratio is 100 or less, preferably 50 or less, more preferably 10 or less, still more preferably 5 or less, and still more preferably 2 or less.

  Moreover, in the dishwashing composition for hand washing of this invention, when it contains (b) component and (c) component, from a foaming viewpoint, (b) component / [(a) component + (c) Component] has a mass ratio of 0.01 or more, preferably 0.1 or more, more preferably 0.15 or more, and more preferably 0.2 or more. On the other hand, from the viewpoint of foam extinction, the mass ratio is 10 or less, preferably 5 or less, more preferably 2 or less, still more preferably 1 or less, and still more preferably 0.8 or less.

  Moreover, in the dishwashing agent composition for hand-washing of this invention, when (b) component is contained, the mass ratio of (a) component / (b) component becomes like this. Preferably it is 0.5-10, More preferably, it is 1. -5, more preferably 1.5-3.

  In the dishwashing detergent composition for hand washing of the present invention, when the component (c) is contained, the mass ratio of the component (c) / the component (a) is preferable from the viewpoint of foaming power and foam extinction. It is 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and still more preferably 0.07 or more. On the other hand, the mass ratio is preferably 3 or less, more preferably 1 or less, still more preferably 0.5 or less, and still more preferably 0.3 or less.

  In the present invention, the total mass of the component (a), the component (b), and the component (c) with respect to the total surfactant content in the composition is 50 to 100% by mass, more preferably 70 to 100% by mass, and even more 80. It is preferable from a viewpoint of foaming power and foam extinction property that it is -100 mass%.

  In the present invention, the behavior of bubbles during washing and rinsing is very important. In a general study of a dishwashing composition for hand washing, a surfactant having a foam increasing effect is used in consideration of foaming property / sustainability of foaming at the time of washing. In such a case, the surfactant having the effect of increasing the foam has a great influence on the foam disappearance at the time of rinsing. In the present invention, as the component (d), a surfactant selected from amine oxide type surfactants, carbobetaine type surfactants and alkanolamide type surfactants, and in particular, handling of amine oxide type surfactants is required. .

  As amine oxide type surfactants, N-alkanoylaminopropyl-N, N-dimethylamine oxide (lauroyl or myristyl as alkanoyl), N-alkyl-N, N-dimethylamine oxide (lauryl or myristyl as alkyl group) Group). Carbobetaine surfactants include N-alkanoylaminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine, N-alkanoylaminopropyl-N, N-dimethyl-N- (2-hydroxysulfopropyl). Examples thereof include ammonium betaine, N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine, and N-alkyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium betaine. Furthermore, examples of the alkanolamide surfactant include amidated products of alkanolamines such as monoethanolamine, diethanolamine, and methylmonoethanolamine with fatty acids such as lauric acid and myristic acid.

  In the present invention, the behavior of the foam is very important, and the use of the component (d) that gives the composition a foam-enhancing effect requires caution. In particular, the content of the component (d) in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and most preferably not contained. is there.

In the present invention, a sulfobetaine surfactant (hereinafter referred to as component (e)) may be used as a surfactant having a foam increasing effect. The sulfobetaine type surfactant improves the foamability / foam persistence at the time of washing, but does not impair the instant foam disappearance at the time of rinsing. Examples of the sulfobetaine surfactant include N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine having an alkyl group having 10 to 18 carbon atoms, N-alkyl-N, N-dimethyl-N- ( 2-hydroxysulfopropyl) ammonium sulfobetaine, N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine having an alkanoyl group of 10 to 18 carbon atoms, N-alkanoylaminopropyl-N, N- Dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine is preferred.
(E) Content of a component becomes like this. Preferably it is 0.5-20 mass% in a composition, More preferably, it is 1-15 mass%, More preferably, it is 2-10 mass%. The mass ratio of (e) component / [(a) component + (b) component + (c) component] is preferably 0.01 to 0.7, more preferably 0.1 to 0.3. Is preferable from the viewpoint of improvement of foamability / foam persistence during washing and foam extinction during rinsing.

  The dishwashing composition for hand washing of the present invention has a magnesium-containing inorganic compound and / or an alkylenediamine compound (the alkylene group has a carbon number as component (f) for the purpose of enhancing the emulsifying power against oil stains and enhancing the cleaning power. 2-6), preferably containing a magnesium-containing inorganic compound. These compounds have the effects necessary for the present invention, that is, relatively weakly interact with at least two molecules of component (a) and other anionic surfactants optionally contained to form a complex, such as emulsifying power. As a compound that improves the surface activity, it has a common effect / action mechanism.

  Examples of the magnesium-containing inorganic compound include magnesium chloride such as magnesium chloride, magnesium salts such as magnesium sulfate and magnesium nitrate, magnesium hydroxide, magnesium oxide, and the like, more preferably a compound selected from magnesium chloride and magnesium sulfate. Even more preferred is magnesium chloride. As the alkylene diamine compound, ethylene diamine, propylene diamine, hexylene diamine and cyclohexane diamine are preferable, but cyclohexane diamine and 1,3-bis (aminomethyl) cyclohexane are more preferable, and 1,3-bis (aminomethyl). ) Cyclohexane is more preferred.

  The content of the component (f) in the composition is preferably 1 to 20% by mass, more preferably 1.5 to 15% by mass, and still more preferably 1.5 to 7% by mass. In addition, although these (f) components may contain crystal water, content shown here is the mass except crystal water.

  In the dishwashing composition for hand washing of the present invention, an inorganic compound other than the component (f) may be used in combination with the component (f). Examples of inorganic compounds include sodium chloride, potassium chloride, sodium iodide, potassium iodide, sodium sulfate, potassium sulfate, alum and the like.

The dishwashing composition for hand-washing of the present invention is instantly free of moisture when rinsed and can be rinsed with a small amount of water, and as a component (g), alkyl glyceryl ether (the carbon number of the alkyl group is 6). -18, preferably 8-12). Specifically, the compound of the following general formula (g1) is suitable.
R ^1g —O— (Gly) _r —H (g1)
Wherein, R ^{1 g} is an alkyl group having 6 to 18 carbon atoms, Gly represents a residue obtained by removing two hydrogen atoms from glycerol, r is the number of 1 to 4 average addition molar number. ]

In the general formula (g1), R ^1g is an alkyl group having 6 to 18 carbon atoms, preferably 7 to 12 carbon atoms, more preferably 8 to 10 carbon atoms such as a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Although a straight-chain alkyl group can be used, in the present invention, a compound having a branched structure is preferable from the viewpoint of reducing the dullness at the time of rinsing. As a specific alkyl group having a branched structure of R ^1g , 2- A group selected from an ethylhexyl group, a sec-octyl group, an isononyl group, and an isodecyl group is more preferable, a 2-ethylhexyl group or an isodecyl group is still more preferable, and a 2-ethylhexyl group is still more preferable. In the general formula (g1), r is preferably 1 to 3, more preferably 1 to 2, and still more preferably a compound of r = 1. A more preferable compound is a compound in which R ^1g is a 2-ethylhexyl group and r = 1. (G) Content of a component is 0.5-20 mass% in a composition, Furthermore, 1-15 mass%, Furthermore, 2-10 mass% is more preferable.

  The dishwashing detergent composition for hand washing of the present invention preferably contains a hydrotrope [hereinafter referred to as component (h)] for the purpose of improving storage stability. As the hydrotrope, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid or a sodium, potassium or magnesium salt thereof is preferable, and p-toluenesulfonic acid or a salt thereof is more preferable. (H) Content of a component becomes like this. Preferably it is 0.5-15 mass% in a composition, More preferably, it is 1-10 mass%, More preferably, it is 1.5-5 mass%.

  The dishwashing composition for hand washing of the present invention can contain a solvent [hereinafter referred to as component (i)] for the purpose of improving storage stability and adjusting viscosity. Specific examples of the solvent include ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, A water-soluble organic solvent selected from phenoxyethanol, phenyl glycol, phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene glycol, and benzyl alcohol is preferred. Among these, one or more water-soluble organic solvents selected from butyl diglycol, ethanol, and propylene glycol are preferable, and one or more water-soluble organic solvents selected from ethanol and propylene glycol are more preferable. Here, the water-soluble organic solvent refers to a solvent having an octanol / water partition coefficient (LogPow) of 3.5 or less. (I) Content of a component becomes like this. Preferably it is 3-30 mass% in a composition, More preferably, it is 5-20 mass%, More preferably, it is 10-15 mass%.

  The dishwashing detergent composition for hand washing of the present invention includes a polymer for preventing gelation (hereinafter referred to as component (j)), for example, a gelation-preventing polymer described in JP-T-11-513067. In particular, it is preferable to blend polyalkylene glycol from the viewpoint of viscosity control and storage stability. Specific examples of the polyalkylene glycol as a polymer for preventing gelation include polypropylene glycol having a weight average molecular weight of 200 to 3,000 determined by gel permeation chromatography using polyethylene glycol as a standard, and Examples include polyethylene glycol having a weight average molecular weight of 200 to 3,000.

  Moreover, the alkylene oxide adduct of glycerol can also be used as (j) component. The alkylene oxide adduct of glycerin is effective in suppressing the formation of a surfactant film that can be formed at the gas-liquid interface of the detergent composition, and an average of 5 to 120, preferably 10 to 50 mol of ethylene oxide is added to glycerin. Further, it is preferable to use an ethylene oxide adduct of glycerin having a weight average molecular weight of 500 to 4000.

  (J) Content of a component becomes like this. Preferably it is 0.05-10 mass% in a composition, More preferably, it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%.

  The dishwashing composition for hand washing of the present invention is preferably in the form of a liquid composition in which the above components are dissolved / dispersed / emulsified in water, and more preferably an aqueous solution. As the water to be used, ion-exchanged water or distilled water from which a minute amount of dissolved metal components are removed, or hypochlorous acid sterilized water in which about 0.5 to 10 ppm of hypochlorous acid is dissolved can be used.

  The pH at 25 ° C. of the dishwashing composition for hand washing of the present invention is preferably 4-9, more preferably 5-8, and such adjustment to pH is selected from sulfuric acid, hydrochloric acid, and phosphoric acid. It is carried out using an inorganic alkaline agent such as an organic acid selected from inorganic acids, citric acid, malic acid, maleic acid, fumaric acid and succinic acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, etc. . In the present invention, it is preferable that the composition has a buffering ability from the viewpoint of foamability / foam persistence, and it is preferable to use the organic acid, preferably citric acid, and an inorganic alkaline agent in combination. The organic acid may be added to the composition in the form of sodium salt or potassium salt. Of the compounds used for pH adjustment, those corresponding to component (f), such as magnesium hydroxide, are handled as component (f).

  The viscosity at 20 ° C. of the dishwashing composition for hand washing of the present invention is preferably 5 to 500 mPa · s, more preferably 10 to 300 mPa · s. The viscosity can be adjusted by the component (h), the component (i), the component (j), and the like.

  The dishwashing composition for hand-washing of this invention can contain components, such as a fragrance | flavor, dye, and a pigment.

<Hand-washing method>
The dishwashing composition for handwashing of the present invention is used for handwashing dishes. The cleaning liquid used for hand-washing is obtained using the dishwashing detergent composition for hand-washing of the present invention, and a stock solution of the composition or a diluted solution containing water is used.

  In addition, as a specific hand washing washing method, for example, the composition of the present invention is adhered to a flexible material such as a sponge containing water to hold the washing liquid, and the dish is whipped while squeezing several times by hand. Rub. The total concentration of the component (a), the component (b), and the component (c) in the cleaning liquid retained by the flexible material is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass. More preferably, the content is 0.2 to 5% by mass from the viewpoint of high foamability and foam persistence. After completion of washing, water is added to perform rinsing. For example, in the present invention, 100 to 300 parts by mass of rinsing water sufficiently disappears with respect to 3 parts by mass of the cleaning concentration used, and the rinsing is completed quickly. be able to. The dilution ratio with this rinsing water is about 1/30 to 1/100 when a conventional hand washing detergent composition is used.

  Here, from the viewpoint of foaming power, foam extinguishing property and economic efficiency, the cleaning liquid used for hand-washing is 0.01 to 2% by mass, preferably 0.03 to 2% by mass, more preferably from component (a). Is contained in an amount of 0.1 to 1.5% by mass, more preferably 0.5 to 1% by mass. The component (b) is 0 to 1% by mass, preferably 0.03 to 1% by mass, more preferably 0.06 to 0.5% by mass, and the component (c) is 0 to 1% by mass, preferably 0. 0.003 to 0.3% by mass, more preferably 0.006 to 0.15% by mass, and still more preferably 0.01 to 0.1% by mass. However, (b) component and (c) component do not become 0 mass% simultaneously. That is, the cleaning liquid used for hand-washing contains at least one of the component (b) and the component (c). That is, in the cleaning liquid, the component (b) and / or the component (c) is preferably 0.003 to 1% by mass, more preferably 0.006 to 0.5% by mass, and still more preferably 0.015 to 0.3%. It is contained by mass%, more preferably 0.03 to 0.15 mass%.

The following aspects of the present invention will be described.
<1> (a) An anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester base or a sulfonate group, and having an area elastic modulus E of 10 mN / m or more and 50 mN / m or less. , Preferably 45 mN / m or less, more preferably 40 mN / m or less, preferably 15 mN / m or more, more preferably 20 mN / m or more, more preferably 25 mN / m or more, more preferably 30 mN / m or more. 0.1-30% by mass of an anionic surfactant, (b) 0-30% by mass of a sulfosuccinic acid alkyl ester having 5 to 18 carbon atoms or a salt thereof, preferably 0.1-20% by mass, More preferably 0.2 to 10% by mass, more preferably 1 to 5% by mass, and (c) 0 to 20% by mass of a fatty acid having 10 to 18 carbon atoms or a salt thereof, preferably 0.1 to 0.1% by mass. 10% by mass, more preferably 0.2 to 5% by mass, 0.4 to 3% by mass, and the contents of the component (b) and the component (c) are not 0% by mass at the same time. Tableware detergent composition.

<2> The mass ratio of (a) component / [(b) component + (c) component] is 0.3 or more and 100 or less, preferably 1 or more and 30 or less, more preferably 1.5 or more and 10 or less, <1> The dishwashing detergent composition for hand-washing.

<3> The dishwashing detergent composition for hand washing according to <1> or <2>, wherein (a) is an anionic surfactant represented by the following general formula (a1).
R ^1a —O— (R ^2a O) _n —SO ₃ M (a1)
[Wherein, R ^1a is an alkyl group having 8 to 18 carbon atoms, R ^2a is an ethylene group and / or a propylene group, preferably a propylene group, and n is an average number of added moles of 0.1 or more. The number is 2 or less, preferably 0.2 or more and 1.5 or less, more preferably 0.3 or more and 1 or less, and even more preferably 0.4 or more and 0.8 or less. M is a cation, preferably an inorganic or organic cation. ]

<4> The above <1> to <3>, wherein the total mass of the component (a), the component (b), and the component (c) is 50 to 100% by mass with respect to the total surfactant content in the composition. The dishwashing agent composition for hand-washing any one of Claims.

<5>
(A) An anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester base or a sulfonate group, and having an area elastic modulus E of 10 mN / m or more and 50 mN / m or less. An ionic surfactant (except (b)), (b) a sulfosuccinic acid alkyl ester having an alkyl group having 5 to 18 carbon atoms or a salt thereof, and (c) a fatty acid having 10 to 18 carbon atoms or a salt thereof. The cleaning liquid has a concentration in the cleaning liquid of (a) 0.01 to 2% by mass, (b) 0 to 1% by mass, and (c) 0 to 1% by mass, and (b) and (c) A cleaning solution whose concentration does not become 0% by mass at the same time.

<6> A method for washing dishes, wherein the dishes are washed by hand with a cleaning solution using the dishwashing composition for washing hands according to any one of <1> to <4>, and then rinsed with water. .

<7> Washing | cleaning of the tableware as described in said <6> whose density | concentration in the said washing | cleaning liquid is (a) 0.01-2 mass%, (b) 0-1 mass%, and (c) 0-1 mass%. Method.

  A dishwashing detergent composition for hand washing was prepared according to the molar fraction of Table 1 using the following blending ingredients, and concentrations corresponding to the surfactant concentration in a general hand washing washing method [(a) to (c) components A total wash concentration of 34 mM] was diluted with water (magnification 30 times) to prepare a washing solution for hand washing, and each evaluation was performed. The results are shown in Table 1. In Table 1, for convenience, a'-1 also indicates the area elastic modulus E and mass% as the component (a).

<Blending ingredients>
A-1: 0.4 mol of PO per 1 mol of natural alcohol having 12 carbon atoms in the alkyl chain, then sulfated with sulfur trioxide and neutralized with sodium hydroxide (diluted 10% with water) Neutralized until the pH of the product was 11. Area elastic modulus of 43.3 mN / m.
A-2: 0.6 mol of PO per 1 mol of natural alcohol having 12 carbon atoms in the alkyl chain, then sulfated with sulfur trioxide and neutralized with ammonia water (those diluted 10% with water) Neutralized until pH is 11. Area modulus of elasticity 31.4 mN / m.
A-3: 0.3 mol of EO is added to 1 mol of the natural alcohol having 12 carbon atoms in the alkyl chain, then 0.3 mol of PO is added, and further sulfated with sulfur trioxide, and with aqueous ammonia. Summed (10% diluted with water and neutralized until pH is 11). Area modulus of elasticity 43.4 mN / m.
A-4: linear / branched mixed alcohol [Isalchem 123 manufactured by Sasol Co., which contains an alkyl group having 12 carbon atoms and an alkyl group having 13 carbon atoms (the ratio is 12 carbon atoms / 13 carbon atoms = 42/58 ), The branching ratio is 94 mol%)] and sulfated with sulfur trioxide and neutralized with sodium hydroxide. Area modulus of elasticity 23.3 mN / m.
A′-1: After adding 0.4 mol of PO to 1 mol of natural alcohol having 12 carbon atoms, 15 mol of EO is added, and further sulfated with sulfur trioxide and neutralized with aqueous ammonia. (10% diluted with water and neutralized until pH is 11). Area modulus of elasticity 61.5 mN / m.
B-1: sodium di-2-ethylhexyl sulfosuccinate c-1: fatty acid sodium salt having 14 carbon atoms c-2: fatty acid sodium salt having 12 carbon atoms c-3: fatty acid sodium salt having 18 carbon atoms In Table 1, the blending ratios (b) and (c) indicate Na salt equivalent values.

<Measurement of Area Elastic Modulus E of (a) Component>
In the present invention, the area elastic modulus E based on the surface pressure measured under the following conditions using the apparatus of FIG.
・ Reference area of membrane: 4900 mm ² (dimension at trough 50 mm × 98 mm)
-Area strain: 10%
・ Barrier moving speed: 1 mm / s (normally 1 mm / s)
・ Temperature: 25 ℃
・ Measured concentration range: 1 / 1000th CMC of CMC (critical micelle concentration)

After moving the barrier 2 in FIG. 1 to a measurement start position where the reference area of the membrane is 4900 mm ² (dimension 50 mm × 98 mm in the trough 1), the trough 1 is filled with a surfactant aqueous solution (200 ml) for 10 minutes to 1 After standing for a period of time, the surface pressure was measured. Here, the value of the surface pressure is obtained by measuring the surface pressure at which the Wilhelmy plate senses the gas-liquid interface of the aqueous solution filled in the trough so as to measure the normal surface pressure (surface tension). The numerical value on the vertical axis in FIG.

Next, for the area elastic modulus E, the surface pressure of the surfactant at the time of 0 seconds (when the barrier is stationary) is π ₀ , and the surface pressure of the surfactant aqueous solution t seconds after the start of the barrier movement is π _t , The change amount of the surface area in 0 to t seconds is set as A, and is obtained by the above formula (1). The slope of the straight line in FIG. 2B corresponds to this. Moreover, since the change of the bubble film | membrane by rinse water corresponds to the expansion | swelling process of the film | membrane in this test method, the area elastic modulus E will be calculated from the expansion | swelling process of an initial film | membrane. It is preferable to obtain the area elastic modulus E [mN / m] from the slope of the linear response of the strain and the surface pressure in a region where the strain is sufficiently small in order to obtain a more accurate measurement value. The concentration range of the measurement is a range of 1/1000 of CMC to CMC. When the area elastic modulus is plotted against logC (concentration), the value having the highest area elasticity is regarded as the maximum value, and is defined as the area elastic modulus of the component (a). At that time, the maximum value of the area elasticity value is determined by measuring 7 or more points so that the log C is approximately equal in the range of 1/1000 times CMC to CMC, and then 5 times to 5 times the maximum value. The final maximum value was determined from the logC measured at 7 or more points at almost equal intervals in the range of 1 / minute.

<Foaming and foam disappearance>
The dishwashing agent composition in Table 1 was diluted to 3.2% by mass with 3.5 ° DH hard water and filled into a pump former container described in FIG. 1 of JP-A-2008-260852. Here, a single mesh having a mesh size of 200 / inch was attached to the foam discharge mechanism. Next, 3 g of foam was produced in a 500 ml graduated cylinder by continuously pushing out the pump head at the top of the container for 3 pushes. Note that the speed of pushing out was 1 second per push. At this time, the volume was recorded from the scale of the graduated cylinder and used as the initial amount of foam. If the initial amount of foam was 30 ml or more, it was judged as “◯” because the foamability was good, and if it was less than 30 ml, it was judged as “x” because the foamability was poor.

  Next, 100 ml of 3.5 ° DH hard water is added to the foam through hard water introduction means (handmade watering) installed at the top of the graduated cylinder, and then 100 ml of hard water is added every 1 minute after the start of the test. (100 ml of hard water was added three times in total, the total amount added was 300 ml), and the amount of foam 30 seconds after the addition of hard water was measured.

  FIG. 3 shows how hard water is added to the graduated cylinder. In FIG. 3, 31 is a graduated cylinder, 32 is a foam, 33 is a hard water introduction means (handmade watering), 34 is an opening of the introduction means, and FIG. 4 is a perforation of the opening 34 of the hard water introduction means 33. It is the schematic which shows a state. A method for producing a handmade water fountain as means for introducing hard water is as follows. First, from the bottom of a 250 ml polypropylene wide-mouthed bottle (manufactured by ASONE: I-boy wide-mouthed bottle) to the main body part having a height of about one third was excised. Next, as shown in FIG. 4, a polyethylene perforated plate having 13 holes of 2 mm in diameter at 9 mm intervals was prepared for a thin circular polyethylene plate having a diameter of 4 cm. Finally, the polyethylene perforated plate was fixed as the opening 34 with respect to the lid opening (diameter 4 cm) at the top of the excised wide-mouth bottle to produce hard water introducing means 33 (handmade watering device). The hard water introducing means 33 (manufactured by hand) thus produced was fitted into the opening of the graduated cylinder 31 while being kept in an inverted state as shown in FIG. Hard water was introduced from the excised side of the wide-mouth bottle.

From the initial amount of foam and the amount of foam after addition of 300 ml of hard water (100 ml three times), the rate of change of the amount of foam represented by the following formula was determined to evaluate the foam extinction property. As for the foam disappearance, when 300 ml of hard water is added, if the rate of change in the amount of foam is 70% or more, it is judged as “◎” that rapid foam disappearance by dilution (rinsing) can be achieved. If it was present, “○” was judged as being able to achieve foam disappearance by dilution (rinsing), and “x” was judged if it was less than 50%.
Foam amount change rate (%) = [1− (foam amount after addition of 300 ml of hard water / initial foam amount)] × 100

Claims (7)

  (A) An anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester base or a sulfonate group, and having an area elastic modulus E of 10 mN / m or more and 50 mN / m or less. Ionic surfactants (excluding (b)) 0.1 to 40% by mass, (b) 0 to 30% by mass of sulfosuccinic acid alkyl ester having 5 to 18 carbon atoms or a salt thereof, and (c) carbon A dishwashing composition for hand-washing comprising 0 to 20% by mass of a fatty acid of several 10 to 18 or a salt thereof, and the contents of (b) and (c) are not 0% by mass at the same time.   The dishwashing composition for hand-washing of Claim 1 whose mass ratio of (a) component / [(b) component + (c) component] is 0.3-100. The dishwashing composition for hand-washing according to claim 1 or 2, wherein (a) is an anionic surfactant represented by the following general formula (a1).
R ^1a —O— (R ^2a O) _n —SO ₃ M (a1)
[Wherein, R ^1a is an alkyl group having 8 to 18 carbon atoms, R ^2a is an ethylene group and / or a propylene group, n is an average number of added moles, and a number of 0.1 or more and 2 or less. is there. M is a cation. ]   The total mass of (a) component, (b) component, and (c) component with respect to content of all the surfactants in the composition is 50 to 100% by mass. A dishwashing composition for hand washing.   (A) An anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester base or a sulfonate group, and having an area elastic modulus E of 10 mN / m or more and 50 mN / m or less. An ionic surfactant (except (b)), (b) a sulfosuccinic acid alkyl ester having an alkyl group having 5 to 18 carbon atoms or a salt thereof, and (c) a fatty acid having 10 to 18 carbon atoms or a salt thereof. The cleaning liquid has a concentration in the cleaning liquid of (a) 0.01 to 2% by mass, (b) 0 to 1% by mass, and (c) 0 to 1% by mass, and (b) and (c) A cleaning solution whose concentration does not become 0% by mass at the same time.   A method for washing dishes, wherein the dishes are washed by hand with a cleaning liquid using the dishwashing composition for washing hands according to any one of claims 1 to 4, and then rinsed with water.   The dishwashing | cleaning method of the tableware of Claim 6 whose density | concentration in the said washing | cleaning liquid is (a) 0.01-2 mass%, (b) 0-1 mass%, and (c) 0-1 mass%.

Images