JP2013082846A - Dishwashing detergent composition for hand washing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dishwashing detergent for hand washing that exerts superior detergency to stains on a sink, shows rich foaming and foam sustainability in washing while foams disappear immediately in rinsing, and allows hand washing to be completed with a small amount of water.SOLUTION: The dishwashing detergent composition for hand washing includes: (a) a specific sulfosuccinic acid alkyl ester or the salt thereof; (b) a specific alkylsulfate ester or the salt thereof; and (c) 2 to 8 mass% of one or more selected from a hydroxycarboxylic acid, an amino polycarboxylic acid and the salts thereof.

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 describes a liquid detergent composition that can use a sulfosuccinic acid dialkyl ester salt and a chelating agent as an anionic surfactant. Patent Document 2 describes a composition in which a sulfosuccinic acid monoalkyl ester salt and a chelating agent can be used. Patent Document 3 describes a liquid detergent composition containing a chelating agent at a high concentration.

JP 2002-513853 A JP 2005-530857 A JP 2007-23210 A

  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.

  The dishwashing detergent composition may be used for washing around a sink made of stainless steel or resin, in addition to washing the main dish to be washed. However, it is desirable to have excellent detergency against dirt around the sink, such as scale dirt.

  However, a cleaning agent that is generally excellent in foamability / foam persistence requires a large amount of water in order to complete rinsing particularly when cleaning a wide area such as in a sink. Accordingly, there is a strong need for a dishwashing detergent for hand washing that exhibits abundant foaming and foam persistence during washing, and scale washability, 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. Moreover, in these patent documents, there is no Example which mix | blended the sulfosuccinic-acid dialkyl ester salt, and the effect has not been confirmed. Patent Document 3 describes a composition containing a high concentration of a chelating agent and having excellent detergency around the sink, but does not suggest the contribution of the chelating agent to foaming properties during dishwashing.

  The problem of the present invention is that it has excellent cleaning power against dirt around the sink and shows abundant foaming during cleaning and persistence of foam during cleaning, but the foam disappears instantly during rinsing and is rinsed with a small amount of water. The object is to provide a dishwashing agent for hand washing.

  The present invention includes (a) a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof (hereinafter referred to as component (a)), (b) an alkyl sulfate represented by the following general formula (2) Or a salt thereof (hereinafter referred to as component (b)), and (c) one or more compounds selected from hydroxycarboxylic acid, aminopolycarboxylic acid, and salts thereof (hereinafter referred to as component (c)) 2 to 8 mass % Dishwashing composition for hand-washing.

[Wherein, R ¹ and R ² are each an alkyl group having 5 to 18 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group having 5 to 18 carbon atoms. A ¹ and A ² are each independently an alkylene group having 2 to 4 carbon atoms, x and y are average addition mole numbers, and are each independently 0 to 6. M is an inorganic or organic cation. ]
R ³ —O— (R ⁴ O) _n —SO ₃ M ² (2)
[Wherein R ³ is an alkyl group having 8 to 18 carbon atoms, R ⁴ is an ethylene group and / or a propylene group, n is an average number of added moles, and is a number of 0 or more and 6 or less, preferably The number is from 0.1 to 3. M ² is an inorganic or organic cation. ]

  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, it exhibits excellent detergency against dirt around the sink, and exhibits abundant foaming during washing and persistence of foam during washing, but the foam disappears instantly when rinsed and rinsed with a small amount of water. A dishwashing agent for hand washing is provided.

Schematic showing the evaluation method of foam extinction performed in the examples Schematic showing the perforated state of the hard water introduction means (water) used in the evaluation of foam extinction of the example

<(A) component>
The component (a) of the present invention is a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof.

[Wherein, R ¹ and R ² are each an alkyl group or a hydrogen atom having 5 to 18, preferably 6 to 14, more preferably 7 to 10 carbon atoms, preferably an alkyl group having a branched structure. , R ¹ , R ² is an alkyl group having 5 to 18 carbon atoms. 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 2, more preferably Is 0 to 1, more preferably 0. M is an inorganic or organic cation. ]

When the component a) is a sulfosuccinic acid dialkyl ester or a salt thereof, R ¹ and R ² in the general formula (1) may be the same or different, and the foaming property at the time of washing and the disappearance of the foam at the time of rinsing From the viewpoint of properties, it is an alkyl group having 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, 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 (a) is a sulfosuccinic acid monoalkyl ester or a salt thereof, one of R ¹ and R ^{2 in} the general formula (1) is a foaming property during washing and a foam disappearance property during rinsing. From the viewpoint, it is an alkyl group having 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 10 carbon atoms, preferably an alkyl group having a branched structure, and the other is a hydrogen atom.

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 the average number of moles added, and are each 0 to 6, preferably 0 to 2, more preferably 0 to 1, from the viewpoints of foamability during washing and foam extinction during rinsing. Yes, more preferably 0.

R ¹ and R ² in the general formula (1) each have 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 7 carbon atoms, from the viewpoints of foamability during washing and foam disappearance during rinsing. It is preferably 10 alkyl groups, that is, the component (a) is a sulfosuccinic acid dialkyl ester or a salt thereof.

In the general formula (1), R ¹ and R ² are hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, 2-ethylhexyl, n-octyl, sec-octyl, isopentyl, respectively. Group, isononyl group, isodecyl group, and cyclohexyl group, and more preferably a group selected from n-octyl group, sec-octyl group, decyl group, isodecyl group, and 2-ethylhexyl group. M ¹ is an organic cation selected from an inorganic cation selected from hydrogen ion, sodium ion, ammonium ion, potassium ion and magnesium ion, monoethanolamine, diethanolamine, triethanolamine and morpholine acid salt, preferably Is a cation selected from sodium ion, ammonium ion, potassium ion, and magnesium ion.

The method for preparing a compound in which R ¹ and R ^{2 of the} component (a) are the same is not particularly limited. For example, referring to the method described in US Pat. No. 2,028,091 An asymmetric compound in which R ¹ and R ² are different can be produced with reference to, for example, JP-A No. 58-24555. When using a commercially available compound, PALEX OT-P (a compound in which R ¹ and R ² are both 2-ethylhexyl groups) manufactured by Kao Corporation, and PELEX TR (both R ¹ and R ² are tridecyl groups) Compound), LusitA-BO (compound in which R ¹ and R ² are both 2-ethylhexyl groups) manufactured by BASF, and aerosol AY-100 (R ¹ and R ² are both amyl groups) available from Mitsui Cytec Co., Ltd. And the same aerosol A-196 (a compound in which R ¹ and R ² are both cyclohexyl groups). (A) As a raw material of a component, what added the alkylene oxide to the alcohol of predetermined carbon number can also be used.

<(B) component>
The component (b) of the present invention is an alkyl sulfate ester represented by the general formula (2) or a salt thereof. The compound of the general formula (2) is preferable from the viewpoints of foamability at the time of washing, foam persistence, and foam disappearance at the time of rinsing.
R ³ —O— (R ⁴ O) _n —SO ₃ M ² (2)
[In the formula, R ³ is an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, R ⁴ is an ethylene group and / or a propylene group, n is an average added mole number, and is 0 or more and 6 or more. It is the following number, preferably 0.1 or more and 3 or less, more preferably 0.3 or more and 1.5 or less. M ² is an inorganic or organic cation. ]

When R ⁴ is an ethylene group, n is preferably a number of 1.5 or less, more preferably 1 or less, more preferably a number of 0.3 or more, and even more preferably a number of 0.5 or more. In addition, when R ⁴ is a propylene group, n is preferably 1.5 or less, more preferably 1 or less, and even more preferably 0.8 or less, and a number of 0.1 or more and further 0.3 or more. A number, more preferably a number of 0.5 or more is preferred. When R ⁴ is an ethylene group or a propylene group, n can be selected from these ranges.

In the general formula (2), when n is 0, R ³ is preferably a compound containing an alkyl group having a branched structure. When n is 0, the compound of the general formula (2) preferably has a branching ratio [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 (2)]. A compound of 15 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 70 to 100 mol% is suitable.

M ² in the general formula (2) 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. Are preferably sodium ion, ammonium ion, potassium ion and magnesium ion.

The method for preparing the compound of the general formula (2) is not particularly limited. For example, after a predetermined amount of ethylene oxide and / or propylene oxide is added to the fatty alcohol represented by R ³ —OH depending on the purpose. It is produced by sulfate formation 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 agent. 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 ³ is an alkyl group having a branched structure, which is suitable when n is 0 in the general formula (2), the alcohol represented by R ³ —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 form a multibranched tridecanol (branching rate is 100 mol%), petroleum and coal. Synthetic alcohol (branch index of about 20 to 100 mole percent of the alkyl group) can be exemplified.

In the present invention, as the component (b), the compound represented by the general formula (2), wherein R ⁴ is a propylene group, n is 0, 1 to 1.5, further 0.3 to 1, Most preferred are compounds having a number between 0.5 and 0.8.

<(C) component>
Component (c) of the present invention is one or more compounds selected from (c) hydroxycarboxylic acids, aminopolycarboxylic acids, and salts thereof. Specific examples of the component (c) include citric acid, malic acid, ethylenediaminetetraacetic acid (EDTA), tartaric acid, gluconic acid, and aminopolycarboxylic acid in which one or more carboxymethyl groups are bonded to the nitrogen atom of the amino acid compound [ For example, the compound chosen from methylglycine diacetic acid (MGDA)] and these salts is mentioned. Component (c) is preferably one or more compounds selected from citric acid, malic acid, gluconic acid, ethylenediaminetetraacetic acid, methylglycine diacetate, and salts thereof. (C) The compound of a component can also combine 2 or more types. Of these, citric acid and its salts are preferred.

  Citric acid salts include trisodium citrate, disodium hydrogen citrate, sodium dihydrogen citrate, tripotassium citrate, dipotassium hydrogen citrate, potassium dihydrogen citrate, triammonium citrate, dihydrogen citrate Examples thereof include ammonium, ammonium dihydrogen citrate, calcium citrate, magnesium citrate, and zinc citrate.

  Examples of the malic acid salt include sodium malate, disodium malate, sodium hydrogen malate, dimethyl malate, and diethyl malate.

  As salts of EDTA, EDTA tetrasodium, EDTA trisodium, EDTA disodium, EDTA dihydrogen disodium, EDTA tripotassium, EDTA dipotassium, EDTA zinc disodium, EDTA calcium disodium, EDTA diammonium, EDTA magnesium disodium And so on.

  Examples of the tartaric acid salt include sodium tartrate, potassium tartrate, calcium tartrate, ammonium tartrate, ethylenediamine tartrate, sodium potassium tartrate, diethyl tartrate, dimethyl tartrate, ammonium hydrogen tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate and the like.

  Examples of the salt of gluconic acid include zinc gluconate, potassium gluconate, sodium gluconate, magnesium gluconate and the like.

  Examples of the MGDA salt include MGDA sodium, MGDA disodium, MGDA tripotassium, MGDA dipotassium, MGDA ammonium and the like.

<Dishwashing composition for hand washing>
The dishwashing composition for hand washing of the present invention is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and still more preferably (a) component from the viewpoints of foaming power, foam disappearance and economy. Contains 3 to 15% by mass. Moreover, (b) component becomes like this. Preferably it is 1-50 mass%, More preferably, 4-30 mass%, More preferably, 8-15 mass% is contained. 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 addition, from the viewpoint of washing around the sink, foaming at the time of dishwashing, and storage stability, the component (c) is 2 to 8% by mass, preferably 2.5 to 7% by mass, more preferably 3 to 6% by mass. %contains.

  In the dishwashing composition for hand washing of the present invention, the mass ratio of the component (a) / the component (b) is preferably 0.1 to 10, more preferably 0.3 to 5, and still more preferably 0.8. 4-3.

  In the present invention, the total mass of the component (a) and the component (b) with respect to the total surfactant content in the composition is 50 to 100% by mass, further 60 to 100% by mass, and further 70 to 100% by mass. It is preferable from the viewpoint of foaming power and foam extinction.

  In the present invention, as the other surfactant, an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group (excluding the component (a) and the component (b)). Can be contained. As such an anionic surfactant, an anionic surfactant selected from alkylbenzene sulfonates having an alkyl group having 8 to 18 carbon atoms and 8 to 15 carbon atoms, and alkane sulfonates having 8 to 15 carbon atoms. Agents. As the salt, an inorganic salt selected from a sodium salt, an ammonium salt, a potassium salt, and a magnesium salt, an organic amine salt selected from a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, and a monophorin salt are preferable.

  The dishwashing composition for hand washing of the present invention preferably contains a sulfobetaine type amphoteric surfactant as the component (d) for the purpose of enhancing the emulsifying power against oil stains and enhancing the cleaning power. 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. (D) Content of 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 (d) component / [(a) component + (b) component] is preferably 0.01 from the viewpoint of improvement of foamability / foam persistence during washing and foam extinction during rinsing. It is -0.7, More preferably, it is 0.1-0.5.

The dishwashing composition for hand-washing of the present invention is instantly free of moisture when rinsed, and can be completed with a small amount of water. From the viewpoint of rinsing with a small amount of water, an alkyl glyceryl ether (the carbon number of the alkyl group is 6 -18, preferably 8-12). Specifically, the compound of the following general formula (3) is suitable.
R ⁵ —O— (Gly) _r —H (3)
Wherein, R ⁵ represents 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 (3), R ⁵ 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 hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. 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 ⁵ , 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 (3), r is preferably 1 to 3, more preferably 1 to 2, and still more preferably a compound of r = 1. Even more preferred compounds are those in which R ⁵ is a 2-ethylhexyl group and r = 1.

The structure represented by Gly is the structure represented by —CH ₂ CH (OH) CH ₂ — in which the 1-position and 3-position hydroxy groups of glycerol are bonded, or the 1-position and 2-position hydroxy groups of glycerol are bonded. The structure is represented by —CH (CH ₂ OH) CH ₂ —, which varies depending on the catalyst and reaction conditions.

In order to obtain the compound of the general formula (3), for example, an alkyl alcohol represented by R ⁵ —OH as an alcohol having 6 to 10 carbon atoms is used, and an epoxy compound such as epihalohydrin or glycidol is reacted with an acid catalyst such as BF ₃ , Or the method of manufacturing by making it react using an aluminum catalyst can be used.

  For example, when 2-ethylhexanol is used, the obtained 2-ethylhexyl monoglyceryl ether is a mixture that can contain a plurality of products as described in JP-A No. 2001-49291. (E) Content of a component is 0.5-20 mass% in a composition, Furthermore, 1-15 mass%, Furthermore, 2-10 mass% is more preferable.

  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, attention should be paid to the handling of a surfactant selected from amine oxide type surfactants, carbobetaine type surfactants and alkanolamide type surfactants as the component (f).

  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). Examples of the carbobetaine surfactant include N-alkanoylaminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine and N-alkyl-N, N-dimethyl-N-carboxymethylammonium 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 foam is very important. Care must be taken in using the component (f) that gives the composition a foam-enhancing effect, and the content of the component (f) in the composition is preferably It is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less, Most preferably, it is not containing.

  The dishwashing detergent composition for hand washing of the present invention preferably contains a hydrotrope [hereinafter referred to as component (g)] 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 preferable. (G) 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 (h)] 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. (H) Content of a component becomes like this. Preferably it is 1-30 mass% in a composition, More preferably, it is 3-20 mass%, More preferably, it is 5-12 mass%.

  The dishwashing detergent composition for hand washing of the present invention includes a polymer for preventing gelation (hereinafter referred to as component (i)), for example, a gelling-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 (i) 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.

  (I) 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 the component (c) such as citrus are handled as the component (c).

  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. Viscosity can be adjusted with (g) component, (h) component, (i) component, etc.

  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. As a specific hand-washing method, for example, the composition of the present invention is attached to a flexible material such as a sponge containing water to hold the cleaning liquid, and foamed while squeezing several times by hand to rub the dishes. To do. 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 1,000 to 30,000 ppm, more preferably 1,000 to 20,000 ppm. More preferably, it is 2,000 to 10,000 ppm 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, the foam disappears sufficiently with 3.3 to 133 parts by mass of rinsing water with respect to 1 part by mass of the composition used, and the rinsing is completed quickly. Can do. The amount of the rinsing water is about 2/3 to 1/10 when the conventional hand washing detergent composition is used.

Embodiments of the present invention are exemplified below.
<1> (a) The sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, still more preferably 3 to 15% by mass, (B) The alkyl sulfate represented by the following general formula (2) or a salt thereof is preferably 1 to 50% by mass, more preferably 4 to 30% by mass, still more preferably 8 to 15% by mass, and (c) Dishwashing for hand-washing containing 2 to 8% by mass, preferably 2.5 to 7% by mass, more preferably 3 to 6% by mass of one or more compounds selected from hydroxycarboxylic acids, aminopolycarboxylic acids, and salts thereof Agent composition.

[Wherein, R ¹ and R ² are each an alkyl group having 5 to 18 carbon atoms or a hydrogen atom, preferably an alkyl group having a branched structure, and at least one of R ¹ and R ² has 5 carbon atoms. ˜18 alkyl groups. A ¹ and A ² are each independently an alkylene group having 2 to 4 carbon atoms, x and y are average addition mole numbers, and are each independently 0 to 6. M ¹ is an inorganic or organic cation. ]
R ³ —O— (R ⁴ O) _n —SO ₃ M ² (2)
[In the formula, R ³ is an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, R ⁴ is an ethylene group and / or a propylene group, n is an average added mole number, and is 0 or more and 6 or more. The following number, preferably a number of 0.1 to 3, more preferably a number of 0.3 to 1.5. M ² is an inorganic or organic cation. ]

<2> The dishwashing dish for hand washing according to <1>, wherein (c) is one or more compounds selected from citric acid, malic acid, gluconic acid, ethylenediaminetetraacetic acid, methylglycine diacetate, and salts thereof. Agent composition.

<3> Further, (d) the sulfobetaine-type amphoteric surfactant is preferably contained in an amount of 0.5 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 2 to 10% by mass, <1> Or the dishwashing agent composition for hand-washing as described in <2>.

<4> Any of the above <1> to <3>, wherein the mass ratio of (a) component / (b) component is 0.1 to 10, further 0.3 to 5, and more preferably 0.4 to 3. A dishwashing composition for hand-washing according to claim 1.

<5> The total mass of (a) and (b) with respect to the content of all surfactants in the composition is 50 to 100% by mass, further 60 to 100% by mass, and further 70 to 100% by mass. <1>-<4> The dishwashing composition for hand-washing in any one of <4>.

<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 <5>, and then rinsed with water. .

  A dishwashing composition for hand washing shown in Table 1 was prepared using the following ingredients. At that time, pH (measurement method is as follows) was adjusted using 48 mass% sodium hydroxide aqueous solution or 10 mass% hydrochloric acid. After the pH adjustment, the following evaluations were performed on these dishwashing detergent compositions for hand washing. The results are shown in Table 1. In addition, the mass% of the mixing | blending component in Table 1 is a numerical value based on an effective part altogether [(b) component has shown the quantity as a sodium salt for convenience. ].

<Blending ingredients>
・ Di-2-ethylhexyl sodium sulfosuccinate: trade name Aerol CT-1L, Toho Chemical Co., Ltd.
B-1: 0.6 mol of PO was added to 1 mol of a natural alcohol having 12 carbon atoms in the alkyl chain, and then sulfated with sulfur trioxide and neutralized with sodium hydroxide (those diluted 10% with water) Neutralized until pH is 11.
B-2: Sodium lauryl sulfate ester [trade name Emar 0, Kao Corporation]
・ Sulfobetaine: Lauryldimethylsulfobetaine [Amphitol 20HD, Kao Corporation]
Amine oxide: N-lauryl-N, N-dimethylamine oxide

<Measurement method of pH>
A pH measuring composite electrode (HORIBA glass sliding sleeve type) was connected to a pH meter (HORIBA pH / ion meter F-23), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) was used as the pH electrode internal solution.

  Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were each filled in a 100 ml beaker. It was immersed in a constant temperature bath at 30 ° C. for 30 minutes. The pH measurement electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibration was performed in the order of pH 6.86 → pH 9.18 → pH 4.01.

  The sample was filled in a 100 ml beaker and adjusted to 25 ° C. in a constant temperature bath at 25 ° C. The pH measurement electrode was immersed in a sample adjusted to a constant temperature for 3 minutes, and the pH was measured.

<Foaming power>
In a cylindrical glass container with a diameter of 5 cm and a height of 13 cm containing 20 plastic beads (about 1 g per piece) of about 9 mm in diameter, 0.5 mass% (200 times) with 3.5 ° DH hard water. 40 ml of the diluted composition was added. Furthermore, 0.04 g of butter was added, and the temperature was adjusted to 20 ° C. for 15 minutes after sealing. The glass container whose temperature has been adjusted is set in a laundry tester (Suga Test Instruments Co., Ltd., model: LM-16), stirred for 15 minutes in an environment of 20 ° C. It took out and measured the height (mm) of the foam in a container. Evaluation was performed twice for one composition, and the average value was defined as the foaming power of the composition.

<Bubble 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.

Next, 100 ml of 3.5 ° DH hard water was 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 was added every time after 1 minute. (100 ml of hard water was added a total of 4 times, and the total amount added was 400 ml), and the amount of foam after 30 seconds from the last addition of hard water was measured. The foam amount change rate represented by the following formula was determined, and the bubble amount change rate of 70% or more was determined to be acceptable.
Foam amount change rate (%) = [1-foam amount after addition of 400 ml of hard water (ml) / initial foam amount (ml)] × 100

  FIG. 1 shows the state when hard water is added to the graduated cylinder. In FIG. 1, 1 is a graduated cylinder, 2 is foam, 3 is a hard water introduction means (manufactured by hand), 4 is an opening of the introduction means, and FIG. 2 is a perforation of the opening 4 of the hard water introduction means 3. 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. 2, a polyethylene perforated plate having 13 holes with a diameter of 2 mm at 9 mm intervals was prepared for a thin circular polyethylene plate with a diameter of 4 cm. Finally, the polyethylene perforated plate was fixed as the opening 4 to the lid opening (diameter 4 cm) at the top of the excised wide-mouth bottle to produce hard water introducing means 3 (handmade watering device). The hard water introducing means 3 (manufactured by hand) thus produced was fitted into the opening of the graduated cylinder 1 while being kept in an inverted state as shown in FIG. Hard water was introduced from the excised side of the wide-mouth bottle.

<Descaling performance>
After measuring the mass of the polished SUS304 test piece (size: 75 mm x 30 mm x 1 mm) (initial piece mass), it was placed on the basket in the automatic dishwasher (Matsushita Electric Industrial Co., Ltd .; NP-720). It was clamped and fixed to a clip that had been attached in advance. 23 ml of milk, 15 g of calcium hydroxide and 15 g of calcium carbonate were added to the detergent inlet, and the washing machine was operated in the normal mode. After repeating this operation three times, the operation of operating the washing machine in normal mode with 23 ml of milk, 15 g of sodium orthosilicate and 15 g of calcium chloride was further repeated three times. After the operation was completed, the test piece was taken out of the automatic dishwasher, and the mass was measured after the temperature of the test piece returned to room temperature (piece mass before evaluation). The difference between the pre-evaluation piece mass and the initial piece mass is the amount of dirt adhered to the piece.

  The measurement of the piece mass used for the calculation of the scale removal rate was carried out with reference to the peanut test (JIS K 3370) using the above-mentioned dirty test piece. That is, three model soiled fixed pieces were immersed in the composition of Table 1 diluted to 10% aqueous solution with ion-exchanged water (600 ml), washed for 5 minutes using a 1250 rpm washing motor, and then tap water ( 600 ml) and washed for 1 minute using a washing motor. The mass was measured after natural drying (piece mass after evaluation). The difference between the piece mass after evaluation and the initial piece mass is the amount of dirt remaining on the piece.

  The scale removal rate was defined below as a standard indicating the scale removal performance, and the scale removal rate of each composition was calculated.

Claims (4)

(A) a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof; (b) an alkyl sulfate ester represented by the following general formula (2) or a salt thereof; and (c) a hydroxycarboxylic acid, amino A dishwashing composition for hand-washing containing 2 to 8% by mass of one or more compounds selected from polycarboxylic acids and salts thereof.

[Wherein, R ¹ and R ² are each an alkyl group having 5 to 18 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group having 5 to 18 carbon atoms. A ¹ and A ² are each independently an alkylene group having 2 to 4 carbon atoms, x and y are average addition mole numbers, and are each independently 0 to 6. M ¹ is an inorganic or organic cation. ]
R ³ —O— (R ⁴ O) _n —SO ₃ M ² (2)
[Wherein R ³ is an alkyl group having 8 to 18 carbon atoms, R ⁴ is an ethylene group and / or a propylene group, and n is an average added mole number, which is a number of 0 or more and 6 or less. M ² is an inorganic or organic cation. ]   The dishwashing composition for hand-washing according to claim 1, wherein (c) is one or more compounds selected from citric acid, malic acid, gluconic acid, ethylenediaminetetraacetic acid, methylglycine diacetate, and salts thereof.   The dishwashing composition for hand washing according to claim 1 or 2, further comprising (d) a sulfobetaine type amphoteric surfactant.   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 3, and then rinsed with water.

Images