JP2843112B2 - Detergent composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a detergent composition, and more particularly to a detergent composition having excellent detergency against inorganic stains on clothing.

[Conventional technology and its problems]

Clothing stains are broadly divided into organic and inorganic stains.
Organic dirt is mainly sebum dirt derived from the human body in clothing such as underwear. A detergent containing a nonionic surfactant exhibits excellent detergency against oil stains such as sebum stains. On the other hand, inorganic soil is mainly composed of dust floating in the air and mud derived from soil. In general, the stains on clothing are a mixture of organic stains and inorganic stains, and conventional detergents still have insufficient cleaning power on inorganic stains, especially mud adhering to socks and the like.

[Means for solving the problem]

The present inventors have assiduously studied and obtained a cleaning composition in which the detergency against inorganic dirt is significantly increased by using a specific nonionic surfactant and a special anionic surfactant in combination. And completed the present invention.

That is, the present invention relates to (a) a specific nonionic surfactant and (b) an anionic surfactant having at least one hydrophobic group having 6 to 24 carbon atoms and at least two anionic groups. And a specific weight ratio of: 1) an anionic surfactant having a chelate stability constant of 2 or more for calcium ions and 2) a Kraft point of 5 ° C. or less when chelating calcium ions. A cleaning composition is provided.

The component (a) of the present invention is a nonionic surfactant selected from the following (1) to (4).

(1) A polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms and having 1 to 20 mol of ethylene oxide added thereto.

(2) having an alkyl group having an average of 6 to 12 carbon atoms,
Polyoxyethylene alkyl phenyl ether to which moles of ethylene oiside has been added.

(3) Nonionic surfactants having an alkyl group or an alkenyl group having an average of 10 to 20 carbon atoms and having a total of 1 to 30 mol of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added thereto (ethylene oxide and The ratio with propylene oxide or butylene oxide is 0.1 / 9.9 to 9.9 / 0.1).

(4) An alkyl glycoside represented by the following general formula.

During _{R '6 (OR' 7)} x G y formula, R _'6 represents a linear or branched chain alkyl group having 8 to 18 carbon atoms, an alkenyl group or an alkylphenyl group, _{R' 7} is 2 carbon atoms Represents an alkylene group of 4, and G is a residue derived from a reducing sugar having 5 to 6 carbon atoms. x
Has an average value of 0 to 5, preferably 0 to 2, and y has an average value of 1 to 10, preferably 1.1 to 3. Examples of the reducing sugar having 5 to 6 carbon atoms include glucose, fructose, maltose, and sucrose.

Usually, those nonionic surfactants (a) having an HLB of 6 to 19, preferably 8 to 17 are used. Above all,
Nonionic surfactants represented by (1), (2), (5) and (10) are particularly desirable. The nonionic surfactant (a) is incorporated in the composition at 1 to 90%.

The anionic surfactant used as the component (b) in the present invention is an anionic surfactant having at least one hydrophobic group having 6 to 24 carbon atoms and at least two anionic groups, Chelate stability constant for calcium ion is 2
As described above, the kraft point when chelating calcium ions is 5 ° C. or higher.

The anionic surfactants having the above characteristics are different from the anionic surfactants such as linear alkylbenzenesulfonic acid Na salt and polyoxyethylene alkyl ether sulfate sodium salt in the following points.

One is a chelating action on calcium ions. In the actual dirt, polyvalent cations such as calcium, magnesium, iron, and aluminum exist in the dirt component, and intervene between the negatively charged fiber and the negatively charged dirt particles to combine them. It is considered to be playing a role. Although such multivalent cation bridges are considered to be a very important cause of fouling, the anionic surfactants of the present invention have the property of chelating these metal ions, and Ca ²⁺ chelate Those having a stability constant of 2 or more contribute significantly to improvement of the detergency.

Furthermore, ^ions such as Ca ⁺² and Mg ²⁺ existing in water, especially Ca ²⁺
If is not chelated, it is considered to have an adverse effect such as recontamination of soil, and the anionic surfactant of the present invention is also useful in this respect.

If the surfactant is 5 ° C. or less, preferably 0 ° C. or less of the Kraft point when chelating calcium ions,
Even under low-temperature washing conditions such as in Japan, such anionic surfactants act as surfactants as they are even if they chelate calcium, so that a detergency that is not adversely affected by the hardness component can be obtained.

Further, since the anionic surfactant according to the present invention has a plurality of (two or more) anionic groups, it is adsorbed to solid particles to increase the negative zeta potential, and repulsion between solid particles having the same charge. Increase. Since these charges are hardly lost even under ordinary cleaning conditions, dirt is separated from the surface to be cleaned.

From the above, the anionic surfactant according to the present invention is a cleaning agent for inorganic soil, particularly mud adhering to socks and the like, which has been insufficient with a conventional cleaning agent containing an anionic surfactant. It can be said that this is a surfactant that can significantly increase the power.

The chelate stability constant for calcium ion of the anionic surfactant of the component (b) of the present invention and the Krafft point when chelating calcium ion are values measured by the following measuring methods.

Ca ion trapping ability measurement method using calcium ion electrode All solutions are prepared using the following buffers. Buffer;
Create a _{0.1M-NH 4 Cl-NH 4} OH buffer (pH10.0) (1) Creating a calibration curve standard calcium ion solution, a calibration curve showing the relationship between the logarithm and the potential of the calcium ion concentration, such as Figure 1 create.

(2) Measurement of Capturing Ability of Calcium Ions About 0.1 g of a sample (anionic surfactant) is weighed in a 100 ml volumetric flask and made up with the above buffer solution. To this, a CaCl ₂ aqueous solution (pH 10.0) equivalent to 20000 ppm (calculated as CaCO ₃ ) is dropped from the burette (blanks are also measured).

Dropping is performed by adding 0.1 to 0.2 ml of CaCl ₂ aqueous solution at a time, the potential at that time is read, and the calcium ion concentration is determined from the calibration curve in FIG.

The calcium ion concentration at the dropping amount A of the sample in FIG. 2 is the calcium ion trapping ability of the sample.

(3) Calculation of calcium ion chelate stability constant The calcium ion chelate stability constant (pKCa ²⁺ ) is Ca
^Use the results from ²⁺ capture ability measurement. Calculated as forming a one-to-one complex when equimolar calcium is added to the sample (anionic surfactant).

The stability rate number of the complex can be determined according to the following equation.

Stability constant of complex pKM ^{n +} = logK _NL Method for measuring Kraft point when chelating calcium ion Anionic surfactant is equimolarly equivalent to CaCl _{2 in} 0.1 wt% aqueous solution of anionic surfactant. And the temperature is raised to 0 ° C or less for 1 minute at a rate of 1 ° C or less. If there is no insoluble matter, the kraft point is set to 0 ° C or less. And

The anionic surfactant used in the present invention has a chelate stability constant (pKCa ²⁺ ) for calcium ions of 2 or more, preferably 3 or more, more preferably 4 or more,
The craft point when chelating calcium ions is 5 ° C
Or less, preferably 0 ° C or less. The anionic surfactant having such physical properties effectively captures the hardness component in tap water and, when used in combination with the nonionic surfactant, effectively improves the detergency.

In the present invention, the anionic surfactant has a calcium ion capturing ability of 50 mg / g or more in terms of CaCO ₃ , preferably 100
It is desirable to use those having a concentration of at least mg / g, more preferably at least 200 mg / g.

Further, the anionic group contained in the anionic surfactant according to the present invention is a carboxylic acid group, a sulfonic acid group or the like, and may have at least one, preferably two or more carboxylic acid groups. desirable. In addition, it is used for conventional cleaning agents such as alkyl benzene sulfonate, alkyl ether sulfonate, olefin sulfonate, α-sulfo fatty acid ester salt, alkane sulfonate, higher fatty acid salt, alkenyl succinate and sulfosuccinate. Some anionic surfactants do not have such physical properties.

Next, the anionic surfactant used in the present invention will be exemplified, but the present invention is not limited thereto.

(A) An anionic surfactant represented by the following general formula (I).

More specifically, diethylenetriaminepentaacetic acid (hereinafter referred to as “diethylenetriaminepentaacetic acid”)
DTPA), triethylenetetramine hexaacetic acid (hereinafter TTPA)
HA) is an ester or amide derivative. Among them, DTPA mono or di, especially diester derivatives, mono or di, especially diamino derivatives, TTHA di or triester derivatives, di or triamide derivatives are desirable. Specifically, DTPA dioctyl ester, DTPA didecyl ester, DTPA dioctylamide, DTPA didodecylamide, DTPA
Examples thereof include PA distearylamide, DTPA di (triethylene glycol dodecyl) ester, TTHA didecyl ester, TTHA tridodecylamide, and salts thereof.

(B) Anionic surfactant represented by the following general formula (II) [Wherein, R ₁ : an alkyl group, a hydroxyalkyl group, an alkylphenyl group, a hydroxyalkylphenyl group, an alkylbenzyl group, a polyoxyalkylenealkyl ether group or a polyoxyalkylenealkylphenyl ether group (the alkyl group has 8 to carbon atoms) 18) _{C n H 2n O) l -} (R 7 is H or an alkyl group having 1 to 3 carbon atoms, n represents 2 or 3, l is 1 to 7) m: 0 or 1 Y: CH _{2 p (p} is 1 3) n: 0 or 1 R ₂ , R ₃ , R ₄ , R ₅ , R ₆ : one of these is an —OH group and 1
One or two is —CH ₂ —N (CH ₂ COOM) ₂ groups, and the rest are —H or —SO ₃ M (M is H, an alkali metal, an alkaline earth metal, ammonium or alkanol ammonium).

Means The anionic surfactant represented by the general formula (II) can be synthesized from a commercially available phenol or phenol derivative by a one-step Mannich reaction. Specifically, Helv. Chim. Acta 35, 1785 (1952) or Keihei Ueno, "Chemistry of EDTA Complexes," Nankodo, pp. 99-105 (1
977).

Specific examples of typical compounds represented by the general formula (II) are shown below.

(C) Anionic surfactants represented by the following formulas.

In the above, the Kraft point of each compound indicates a value when chelating calcium ions.

In the present invention, the anionic surfactant (b) is incorporated in the composition in an amount of 0.1 to 90%.

In order to enhance the cleaning effect, the components (a) and (b) are (a) / (b) in a weight ratio of 100/1 to 1/20, preferably 100/1.
11/10, more preferably 10/1 to 1/10. When the weight ratio is less than 100/1, the effect of improving the detergency against inorganic dirt is not sufficient.

In addition to the above essential components, the cleaning composition of the present invention may contain, for example, the following amphoteric surfactants and anionic surfactants generally used in the related art.

(1) An amphoteric surfactant represented by the following general formula.

[Where R '₈Is an alkyl or alkenyl having 8 to 20 carbon atoms
Group, R '₉Is an alkyl group having 1 to 3 carbon atoms, R '_TenIs charcoal
Alkylene group of 1 to 6 or hydroxyalkylene
Group, X is COO Or SO_Three It is. (2) a linear or linear alkyl group having an average of 10 to 16 carbon atoms;
Is a branched-chain alkylbenzene sulfonate.

(3) It has a linear or branched alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and has an average of 0.5 to 8 mol of ethylene oxide or propylene oxide or ethylene oxide / propylene oxide = 0.1 /
Alkyl or alkenyl ether sulfates added at a ratio of 9.9 to 9.9 / 0.1.

(4) An alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms.

(5) An olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.

(6) Alkanesulfonates having an average of 10 to 20 carbon atoms in one molecule.

(7) An α-sulfofatty acid salt or ester represented by the following formula.

Wherein Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z
Is a counter ion. R _'11 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. (8) Higher fatty acid salts having an average carbon number of 10 to 20.

Here, the counter ion of the anionic surfactant is an alkali metal ion such as sodium or potassium, an alkaline earth metal ion such as magnesium, an ammonium ion, an alkanol having 1 to 3 alkanol groups having 2 or 3 carbon atoms. Examples include amines (eg, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, and the like).

The cleaning composition of the present invention may contain an inorganic or organic alkali agent such as silicate, carbonate, bicarbonate, caustic, and ethanolamine.

The detergent composition of the present invention may contain an inorganic divalent metal ion sequestering agent such as synthetic zeolite and layered silicate, or an organic divalent metal ion sequestering agent as described below.

(1) Salts of amino acids such as aspartic acid and glutamic acid.

(2) Aminopoly such as nitrilotriacetic acid salt, iminodiacetic acid salt, ethylenediaminetetraacetic acid salt, diethylenetriaminepentaacetic acid salt, glycol ether diaminetetraacetic acid salt, hydroxyethyliminodiacetic acid salt, triethylenetetramine hexaacetic acid salt, diencoric acid salt, etc. Acetate.

(3) polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymesaconic acid, poly-α-hydroxyacrylic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, Maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-ethylene crosslink copolymer, maleic anhydride-
Vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, maleic anhydride and Poly-β-ketocarboxylic acid derived from carbon monoxide, itaconic acid-ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malon Salts of high molecular compounds such as acid-methylene copolymer and mesaconic acid-fumaric acid copolymer.

(4) oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Salts of dicarboxylic acids such as decane-1,10-dicarboxylic acid; salts of diglycolic acid, thiodiglycolic acid, oxalacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyltartronic acid and the like; malic acid, tartaric acid, Citric acid, itaconic acid, methylsuccinic acid, 3-methylglutaric acid, 2,2-dimethylmalonic acid, maleic acid,
Fumaric acid, 1,2,3-propanetricarboxylic acid, aconitic acid, 3-butene-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, ethanetetracarboxylic acid, ethenetetracarboxylic acid Carboxylic acid, n-alkenylaconitic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, phthalic acid, trimesic acid, hemi-mellitic acid, pyromellitic acid, benzenehexacarboxylic acid, tetrahydrofuran-
1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,
Salts of 2,5,5-tetracarboxylic acid and the like; Salts of sulfonated carboxylic acids such as sulfotricarballylic acid and sulfone succinic acid; Carboxymethylated products of sucrose, lactose, raffinose and the like, and carboxymethylated products of pentaeristol Carboxymethylated glyconic acid, condensates of polyhydric alcohols or saccharides with maleic anhydride or succinic anhydride, condensates of oxycarboxylic acids with maleic anhydride or succinic anhydride, CMOS, builder M, builder U, etc. Organic acid salts.

When the detergent composition of the present invention is used as a liquid detergent, particularly when the component (b) content is low, the solubilizing agents used to enhance the viscosity lowering action and the anti-caking action at low temperatures include ethanol and isopropanol. Lower alcohols such as ethylene glycol, propylene glycol, etc.
Polyhydric alcohols such as glycerin and sorbitol; benzenesulfonate, acetylbenzenesulfonate, p
-Aromatic sulfonates such as toluenesulfonate and m-xylenesulfonate; acetamides, pyridinedicarboxylic amides, benzoates and urea. Among the above-mentioned solubilizers, the use of ethanol is particularly preferable because it also helps to prevent the growth of bacteria that occur during long-term storage of the liquid detergent.

The basic formula of a heavy liquid detergent containing a divalent sequestering agent and a solubilizing agent is shown below.

(A) Nonionic surfactant (b) Anionic surfactant according to the present invention (c) Divalent sequestrant 0.5 to 10% by weight, preferably 1 to 7% by weight (d) Solubilizer 1 to 10% by weight, preferably 3 to 7% by weight In the above formulation, the mixing ratio of the component (a) and the component (b) is preferably 20/1 to 1/10 by weight ratio of (a) / (b). Is
10/1 to 1/5, (a) + (b) in a total amount of 5 to 60% by weight, preferably 20 to 60% by weight.

The heavy liquid cleaning composition contains a saturated or unsaturated fatty acid or a salt thereof having 10 to 20 carbon atoms such as coconut oil, tallow fatty acid, and palm fatty acid in order to further improve the cleaning performance without impairing the storage stability. Can be blended. These fatty acids or salts thereof are also desirable components for improving rinsing properties, and are preferably incorporated in the composition in an amount of 0.5 to 5% by weight.

In addition, the heavy liquid detergent composition has good storage stability even when a divalent metal ion sequestering agent is blended in more than the conventional product.

The liquid detergent composition of the present invention further comprises, as optional components, a filler such as sodium sulfate, carboxymethyl cellulose,
Antistaining agents such as polyethylene glycol, polyacrylate, copolymers of maleic anhydride and acrylic acid or olefin; bleaching agents such as percarbonate and perborate: oxygen such as protease, lipase, cellulase and amylase;
An oxygen stabilizer such as calcium chloride; a bleach activator; a fluorescent dye; a coloring agent; a preservative;

〔The invention's effect〕

The great advantage of the cleaning composition of the present invention is that it has a particularly effective cleaning effect on inorganic solid stains, for example, fine mud stains, which cannot be sufficiently removed by the conventional detergents, and also has a stain on the collar and cuffs. It is also effective against stains such as oil stains, and is very useful for improving the detergency of a phosphorus-free detergent.

A cleaning agent containing phosphate was effective in removing fine stains penetrated between the fibers. However, due to the problem of eutrophication, the amount of phosphate in detergents and the like has been gradually decreasing, and as a result of having to remove phosphorus, it has become difficult to remove mud stains. In particular, it is well known that mud dirt penetrated into cotton cloth is completely removed. Mud stains stuck on cotton blended socks were also a worry for housewives.

The cleaning composition of the present invention brings a bright light to solving such a problem. That is, when washing mud stains that have penetrated cellulose fibers and blended fabrics thereof with other fibers, for example, by applying the composition of the present invention to an alkaline phosphorus-free detergent, a weak alkaline solution containing a sufficient amount of phosphate is used. A detergent having excellent detergency equal to or higher than that of a detergent can be obtained.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Various cleaning compositions having the component compositions shown in Table 1 were prepared.
Each detergency was evaluated by the following method.

Mud dirt-contaminated cloth (artificial-contaminated cloth) Akatama soil for Kanuma horticulture is dried at 120 ° C ± 5 ° C for 4 hours, and then crushed.
After drying the 0 Mesh (100μm) pass at 120 ℃ ± 5 ℃ for 2 hours,
± 150 g is dispersed in 1000 perch-lens, and a # 2023 cloth is contacted with this liquid and brushed to remove the dispersion and remove excessively adhered dirt (Japanese Patent Laid-Open No. 55-26473).

Sebum stained cloth (artificially stained cloth) * Model sebum stain composition Cottonseed oil 60% Cholesterol 10% Oleic acid 10% Palmitic acid 10% Liquid and solid paraffin 10% 10 x 10cm Cotton cloth with 2g of the above model sebum stain Apply evenly.

Washing conditions and evaluation method Five pieces of 10 cm × 10 cm cotton soiled soiled cloth or sebum soiled cloth (artificial soiled cloth) were put into the cleaning aqueous solution for evaluation 1 and washed at 100 rpm with a tergotometer under the following conditions. The washing conditions are as follows.

<Washing conditions> Washing time 10 minutes Washing concentration 0.133% Water hardening 4 ゜ DH or 8 ゜ DH Water temperature 20 ℃ Sugi Tap water 5 minutes Washing power is 460mμ of original cloth before and before and after cleaning.
Was measured with a self-colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was determined by the following equation (the average value of the measurements on the five sheets is shown in the table).

Table 1 shows the evaluation results.

In addition, the pKCa ²⁺ and the Kraft point when chelating calcium ions of the component (b) in Table 1 and the calcium trapping ability (mg / g, CaCO ₃ conversion) are as follows.

pKCa ²⁺ Kraft point Ca capture ability 8.8 0 ° C or less 218mg / g 9.30 ° C or less 212mg / g 8.70 ° C or less 213mg / g 2.6 0 ° C or less 101mg / g 10.1 0 ° C or less 280mg / g Example 2 Table 2 Prepare various detergent compositions of the component composition shown,
Each detergency was evaluated under the following cleaning conditions.

Washing conditions Five pieces of 10 cm × 10 cm cotton soiled soiled cloth or sebum soiled cloth (artificial soiled cloth) were put into the aqueous detergent solution 1 for evaluation and washed at 100 rpm with a tergotometer under the following conditions. The washing conditions are as follows.

<Washing conditions> Washing time 10 minutes Washing concentration 0.133% Water hardness 2 ゜ DH or 4 ゜ DH Water temperature 20 ℃ Sugi 5 minutes with tap water The evaluation results are shown in Table-2.

In addition, (b) components II-5, II-9, II-10, and
The pKCa ²⁺ and the Kraft point and the ability to capture Ca (calculated in mg / g and CaCO ₃ ) of pKCa ²⁺ and calcium ions of II-15, III-3, III-5 and III-6 are as follows.

pKCa ²⁺ Kraft point Ca capture ability II-5 3.4 0 ° C or less 136 mg / g II-9 8.60 ° C or less 404 mg / g II-10 8.40 ° C or less 373 mg / g II-15 9.30 ° C or less 482 mg / g III-3 3.20 ° C or less 153.6mg / g III-5 2.90 ° C or less 151.0mg / g III-6 3.20 ° C or less 112.2mg / g Example 3 Liquid detergent composition with the component composition shown in Table-3 Prepare things,
Each storage stability was evaluated by the following method.

<Storage stability> A sample was put into a screw tube (diameter 4 cm, height 10 cm), stored at 40 ° C and -5 ° C, and solidification, separation, and precipitation one month after storage were visually determined.

 The evaluation criteria at this time are as follows.

 ；: Transparent liquid.

 ×: solidification, separation or precipitation occurred.

 Table 3 shows the evaluation results.

In addition, the component (b) in Table 3, pKCa ²⁺ , the Kraft point when chelating calcium ions and the ability to capture Ca (mg / g, converted into CaCO ₃ ) are as follows.

pKCa ²⁺ Kraft point Ca capture ability 9.30 ° C. or less 212mg / g 8.80 ° C. or less 218mg / g 8.70 ° C. or less 213mg / g Example 4 A liquid detergent composition having a component composition shown in Table 4 was prepared.
Each storage stability was evaluated in the same manner as in Example 3 for cleaning performance by the following method.

Washing condition Put 5 pieces of 10 cm x 10 cm cotton mud stained cloth (artificially stained cloth) into the detergent aqueous solution 1 for evaluation, and measure with a targotometer.
Washing was performed at 0 rpm under the following conditions. The washing conditions are as follows.

Washing condition Washing time 10 minutes Washing concentration 0.133% Water hardness 0 ゜ DH, 4 ゜ DH or 8 ゜ DH Water temperature 20 ℃ Sugi Tap water 5 minutes These evaluation results are shown in Table-4.

In Table 4, the (b) component, the pKCa ²⁺ , the Krafft point when chelating calcium ions and the Ca-capturing ability (mg / g, converted into CaCO ₃ ) are as follows.

pKCa ²⁺ Kraft point Ca-capturing ability 9.3 0 ° C or less 212mg / g 10.1 0 ° C or less 280mg / g Example 5 A powder detergent composition having the component composition shown in Table 5 was prepared, and the cleaning performance of each was evaluated. The evaluation was performed in the same manner as in Example 2.

 The results are shown in Table-5.

In addition, the component (b) in Table 5, pKCa ²⁺ , the Kraft point when chelating calcium ions, and the ability to capture Ca (mg / g, converted into CaCO ₃ ) are as follows.

pKCa ²⁺ Kraft point Ca capture ability 8.70 ° C or less 213mg / g 9.30 ° C or less 212mg / g 8.80 ° C or less 218mg / g

[Brief description of the drawings]

FIG. 1 is a calibration curve for obtaining the calcium ion concentration from the potential, and FIG. 2 is a graph showing the relationship between the calcium ion concentration and the amount of the CaCl ₂ aqueous solution dropped.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C11D 1/722 C11D 1/722 (72) Inventor Shoji Nakagawa 1130 Nishihama, Wakayama City, Wakayama Prefecture (56) References JP-A-54-146809 ( JP, A) JP-A-58-222196 (JP, A) JP-A-53-114790 (JP, A) JP-A-62-30546 (JP, A) JP-B-48-32402 (JP, B1) (58 ) Surveyed field (Int.Cl. ⁶ , DB name) C11D 1/00-19/00

Claims (4)

(57) [Claims] (1) a nonionic surfactant selected from the following (1) to (4): and (1) an alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and Polyoxyethylene alkyl or alkenyl ether to which ethylene oxide has been added. (2) having an alkyl group having an average of 6 to 12 carbon atoms,
Polyoxyethylene alkyl phenyl ether to which moles of ethylene oxide have been added. (3) Nonionic surfactants having an average alkyl group or alkenyl group of 10 to 20 carbon atoms and having a total of 1 to 30 mol of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added thereto (ethylene oxide and propylene The ratio to oxide or butylene oxide is 0.1 / 9.9 to 9.9 / 0.1). (4) An alkyl glycoside represented by the following general formula. R ′ ₆ (OR ′ ₇ ) _x G _{y wherein} R ′ ₆ represents a linear or branched alkyl group, alkenyl group or alkylphenyl group having 8 to 18 carbon atoms, and R ′ ₇ represents 2 carbon atoms. Represents a 4 to 4 alkylene group, and G is a residue derived from a reducing sugar having 5 to 6 carbon atoms. x
Has an average value of 0 to 5, and y has an average value of 1 to 10
It is. (B) an anionic surfactant having at least one hydrophobic group having 6 to 24 carbon atoms and at least two anionic groups, and 1) a chelate stability number with respect to calcium ions of 2
And 2) an anionic surfactant having a Krafft point of 5 ° C. or less when chelating calcium ions is contained at a weight ratio of (a) / (b) of 100/1 to 1/20. A cleaning composition comprising: 2. The detergent composition according to claim 1, wherein the anionic surfactant has a calcium ion-scavenging ability of 50 mg (calculated as CaCO ₃ ) / g or more. 3. The cleaning composition according to claim 1, further comprising an alkali agent and / or a divalent metal ion scavenger. 4. The cleaning composition according to claim 1, which does not contain a phosphorus component.