JPH09132794A - Laundry method and laundry detergent composition - Google Patents

Abstract

(57) Abstract: A surfactant, an alkali metal silicate, and a sequestering agent other than the alkali metal silicate are contained, and a weight ratio of the alkali metal silicate to the sequestering agent is included. A method of laundering clothes using a phosphorus-free laundry detergent composition having a ratio of 5/1 or less, wherein the pH of the washing liquid is 10.60 or more when no clothes are put in, and the hardness of the washing water is calculated. A substance having an ion-capturing ability necessary to keep the temperature below 0.5 ° DH is present in the washing liquid, and the concentration of the surfactant in the washing liquid is 0.07 to 0.17 g / L.
A method for washing clothes, which comprises using a washing liquid that provides washing conditions, and a detergent composition for clothes used in the method. [Effect] According to the present invention, the detergent is excellent in detergency even when the concentration of the surfactant is low, so that the standard amount of the detergent can be smaller than that of the usual compact detergent composition for clothes.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a washing method and a phosphorus-free detergent composition for clothes. More specifically, the present invention relates to a laundry method in which the concentration of a surfactant in a washing liquid is low and an excellent detergency can be obtained with a small amount of use, and a laundry detergent composition which can obtain the washing condition with a low amount of use.

[0002]

2. Description of the Related Art To date, many chelating agents, ion-exchange agents, alkali agents, dispersants and the like have been reported as builders to be incorporated into detergents. Previously, for the reason that it was water-soluble and had good detergency, etc., a compound containing a phosphoric acid-based chelating agent mainly containing tripolyphosphate was mainly used.

However, in recent years, tripolyphosphate has been
Due to concern over eutrophication of closed waters such as lakes and marshes, their use has decreased, and crystalline aluminosilicates (zeolites) as represented by JP-A-50-12381 have come to be widely used. In the case of blending with such a zeolite, the standard amount of detergent used is generally about 40 g / 30 L in Japan. In addition, the powder detergent at that time had a low bulk density (0.20 to 0.45) from the viewpoint of solubility in cold water.
g / ml). As a result, the standard use volume is about 90
It was up to 200 ml / 30 L, and it was very inconvenient in handling in physical distribution, stores, homes, etc.

Therefore, vigorous attempts have been made to study compactification of detergents. For example, JP-A-62-1
67396, JP-A-62-167399,
As seen in JP-A-62-253699, a crystalline inorganic salt which is a powdering aid conventionally contained in detergents,
For example, the amount of Glauber's salt is greatly reduced, and further, JP-A-61-6989
No. 7, JP-A-61-69899, JP-A-61.
-69900, JP-A-5-209200, etc., the bulk density is 0.60 to 1.00 g / ml due to the invention of a manufacturing technique for increasing the bulk density of a detergent.
In addition, the standard amount of detergent used is 25-30g / 30L,
As a result, the standard working volume was compacted to 25 to 50 ml / 30 L.

However, since the conventional idea for cleaning was focused on achieving it by solubilizing the oil content in the soil with a surfactant, it was necessary to blend a large amount of the surfactant. . That is, taking the example of human body-derived sebum stains (which are easily observed on collars and sleeves), which is the most typical stain that adheres to clothing, sebum stains are
Containing oils such as free fatty acids and glycerides in soil as high as 70% or more (Kashiichiro et al., Oil chemistry, 19 ,
1095 (1969) etc.), these are carbon and mud in the dust,
The exfoliated keratin is trapped and observed as dirt, but in the case of cleaning them, conventionally, these oils are mainly solubilized and removed by micelles of surfactants to remove carbon and mud. , It was designed to wash dead skin cells from the clothes. This idea has been widely established among those skilled in the art, and there was no change in the surfactant concentration in the washing liquid even when the conventional detergent was changed to the compact detergent. These are the p.42 of the first edition (Asakura Shoten, 1990) of detergent and cleaning encyclopedia by Haruhiko Okuyama and others.
As shown in Fig. 8, it can be said that the concentrations of components other than Glauber's salt in the wash liquor are basically almost unchanged.

Based on these washing theories, it is necessary to increase the surfactant concentration in the washing liquid in order to obtain high detergency. Therefore, a large amount of the surfactant should be added to the detergent composition. Therefore, it was virtually difficult to drastically reduce the standard amount of detergent used. Further, the bulk density is also around 1.00 g / ml in a practical production method, and as a result, further reduction of the standard use volume was considered to be a technically very difficult problem.

On the other hand, the crystalline silicates having a specific structure described in JP-A-5-184946 and JP-A-60-74595 have an action of an alkaline agent (alkaline ability) in addition to the ion exchange ability. For the purpose of showing, it is possible to fulfill the functions of two components, a sequestering agent such as zeolite used in conventional detergents, and an alkaline agent such as sodium carbonate, from the idea that these crystalline silicates alone can fulfill the functions, so that it is more compact. Approaches have been made to the possibility of different detergents.

For example, Japanese Patent Laid-Open No. 6-116588 discloses that
It is an invention relating to a detergent composition containing a crystalline silicate.
A more compact detergent is disclosed that can obtain the same cleaning power as before even when the amount is reduced by 5%. However, the composition is based on the conventional cleaning theory, so the surfactant concentration is high,
Alkali ability and ion exchange ability were mostly expressed only by crystalline silicate. In this case, since the function of the crystalline silicate as the alkali agent precedes, the function as the sequestering agent of the crystalline silicate becomes insufficient, and the detergency is not always satisfactory. Therefore, the cleaning power could not be maintained if the amount used was further reduced.

Further, some patent applications relating to crystalline silicates in JP-A-60-74595 have been filed. For example, in Japanese Patent Publication No. 6-502199, there is no film formation on a fiber in which a layered crystalline silicate, zeolite and polycarboxylate are blended at a specific blending ratio.
Detergents have been disclosed that exhibit excellent detergency and bleach stability. However, under these compounding conditions, when the amount added at the time of washing is small, the alkaline ability is insufficient and the detergency cannot be maintained because the compounding amount of silicate in the builder composition is small. Further, there is no idea that the excellent cleaning power is exhibited with a small amount of use.

In addition, Japanese Patent Publication No. 6-500141,
JP-A-2-178398 or JP-A-2-1783
The same applies to patent publications containing crystalline silicates, such as Japanese Patent Publication No. 99, which does not relate to a detergent with a small amount used as in the present invention, and reduces the addition amount of the composition described in Examples of these patent publications. If so, the detergency is reduced.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a washing method which is excellent in detergency even when the concentration of the surfactant is low, by essentially revising the concept of washing as described above. . Further, another object is that the washing condition in such a washing method can be suitably imparted, and as a result, the standard amount of the detergent is less than that of the conventional compact laundry detergent composition (25 to 30 g / 30 L). It is intended to provide a phosphorus-free laundry detergent composition which can be washed with.

[0012]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention found a relationship between the washing condition and the washing property of clothes from an extremely simple washing system, and found that the washing condition under a specific high alkali / low hardness condition. By analyzing the reason of the excellent detergency in, we have developed a detergent that can be used less.

That is, as a result of diligent studies on the effects of the pH of the washing liquid and the hardness of the washing liquid on the washing, the following things have been found out. The higher the pH and the lower the hardness, the less the dependency of the detergency on the surfactant concentration, and the better the detergency. In addition, if the hardness is high even at high pH,
The detergency is extremely reduced. Also, without adding an alkaline agent,
When washing with only the surfactant, the detergency at low hardness is low, however, the dependency of the detergency on the hardness is sufficiently smaller than that of the system containing an alkaline agent. The inventors of the present invention paid attention to the relationship between the washing liquid and the stain for obtaining such a result.

As shown in the section of the prior art, sebum stain, which is a typical stain adhering to clothes, contains fatty acids and glycerides, and these stains are formed by mixing these organic substances with carbon, mud or keratin. It is thought that it was done.
In the case of high pH, the content of fatty acid due to hydrolysis of glyceride increases, while the reaction of fatty acid to salt with alkali proceeds. Alkali metal salts of fatty acids are soaps and promote the release of dirt into the wash liquor. However, this reaction is a competitive reaction with calcium and magnesium in hard water.Since fatty acid alkali metal salts form scum with calcium and magnesium, when the hardness is high, stains solidify without separating from the cloth interface. Resulting in. From the above, it is considered that when the pH is high and the hardness is low, the cleaning power is excellent, and when the hardness is high, the cleaning power is low. When the alkali agent is not added, sebum stains are washed with the force of only the surfactant, and it is considered that the dependency on hardness was smaller than that of the alkali agent-containing system.

From these phenomena, the present inventors have found that one of the reasons why the detergent concentration is lower than that of the conventional detergent and the detergency equal to or higher than that of the conventional detergent can be obtained.
I noticed that the low hardness and high pH promoted the saponification of the fatty acids in the dirt, and that the resulting soap had an effect on the detergency,
We have found a phosphorus-free clothing detergent composition with a lower standard usage than conventional detergents that rely on surfactants.

That is, the gist of the present invention is: (1) a surfactant, an alkali metal silicate, and a sequestering agent other than the alkali metal silicate, and the alkali metal silicate for the sequestering agent. Is a method for washing clothes using a phosphorus-free laundry detergent composition having a weight ratio of 5/1 or less, characterized in that a washing liquid that provides the following washing conditions when no clothes are put is used. A method for washing clothes, a washing liquid having a pH of 10.60 or more, and a substance having an ion-capturing ability necessary for making the hardness of the washing water to be 0.5 ° DH or less in the calculation is present in the washing liquid, And the concentration of the surfactant in the washing liquid is 0.07 to 0.17 g /
L. (2) The concentration of the detergent composition in the washing liquid is 2 to 6 ° DH
The washing method according to (1) above, wherein the washing water content is 0.33 to 0.67 g / L, (3) the concentration of the detergent composition in the washing liquid is 6 to 10 ° D.
The washing method according to (1) above, wherein the concentration is 0.50 to 1.20 g / L for the washing water of H, (4) the concentration of the detergent composition in the washing liquid is 10 to 20 °
The washing method according to the above (1), wherein the washing water has a DH content of 0.80 to 2.50 g / L, (5) the following components a) a surfactant b) an alkali metal silicate, and c) a component b. A sequestering agent other than the above, the total amount of the above components a, b and c accounts for 70 to 100% by weight in the total composition, and the ratio of the component b to a is b / a = 9 by weight ratio. / 1 to 1/2 and the ratio of the b component to the c component is b / c = 5/1 to 1/15, (6) The ratio of the b component to a is by weight. B / a = 9 in ratio
/ 1 to 9/11, and the ratio of the b component to the c component is b / c = 4/1 to 1/15, the laundry detergent composition according to the above (5), (7) in a surfactant Nonionic surfactant is 50-
The detergent composition for clothes according to the above (5) or (6), which contains 100% by weight, (8) the nonionic surfactant has an average of 10 to 18 carbon atoms in the alkyl group and ethylene oxide as an average. The detergent composition for clothes according to (7) above, which is a polyoxyethylene alkyl ether added with 5 to 15 moles, (9) The alkali metal silicate accounts for 50 to 100% by weight of the alkali agent. (5) to (8) The detergent composition for clothing according to any one of (10) SiO ₂ / M ₂ O of alkali metal silicate
(However, M represents an alkali metal) is 0.5-2.
6. The laundry detergent composition according to any one of (5) to (9), which is 6, (11) The clothing according to any one of (5) to (10), wherein the alkali metal silicate is crystalline. Detergent composition, (12) The detergent composition for clothes according to (11) above, wherein the crystalline alkali metal silicate has a composition represented by the following formula (1): xM ₂ O · ySiO ₂ · zMe _m O _n · wH ₂ O (1) (In the formula, M is a group Ia element of the periodic table, Me is IIa, II
b, IIIa, IVa or VIII, represents one or a combination of two or more elements, wherein y / x = 0.5 to 2.
6, z / x = 0.01-1.0, n / m = 0.5-2.
0 and w = 0 to 20. (13) The detergent composition for clothes according to (11) above, wherein the crystalline alkali metal silicate has a composition represented by the following formula (2): M ₂ O · x′SiO ₂ · y′H ₂ O (2) (In the formula, M represents an alkali metal, and x ′ = 1.5 to 2.
6, y ′ = 0 to 20. (14) The above (5) to (1), wherein the metal ion sequestering agent of the component c contains 10% by weight or more of a carboxylate polymer having a Ca ion trapping ability of 200 CaCO ₃ mg / g or more.
3) The detergent composition for clothes according to any one of (1) to (c-i) C in the sequestering agent of component c.
a a carboxylate polymer having an ion-capturing ability of 200 CaCO ₃ mg / g or more, and (c-ii) an aluminosilicate having an ion exchange capacity of 200 CaCO ₃ mg / g or more represented by the following formula (3), x “(M ₂ O) · Al ₂ O ₃ · y” (SiO ₂ ) · w ”(H ₂ O) (3) (In the formula, M is an alkali metal, x ″, y ″, and w ″ are each component. Represents the number of moles, 0.7≤x "≤1.5, 0.8≤y"
≦ 6, w ″ is 0 to 20.) The ratio of the c-i component to the c-ii component is c-i by weight ratio.
/ C-ii = 1/20 to 4/1, and c-i and c-ii
The detergent composition for clothes according to any one of the above (5) to (14), wherein the total amount of 70 to 100% by weight of the sequestering agent of the component c is (16) Any of the above (5) to (15) The laundry method according to (1) above, which comprises using the laundry detergent composition as described above.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The washing method of the present invention comprises a surfactant, an alkali metal silicate, and a sequestering agent other than the alkali metal silicate, and the sequestering agent is an alkali metal silicic acid. The present invention is characterized in that a phosphorus-free clothes detergent composition having a salt weight ratio of 5/1 or less is used to provide the following washing conditions when clothes are not put in. The pH of the washing liquid is 10.60 or more, a substance having an ion-capturing ability necessary for making the hardness of the washing water 0.5 ° DH or less in the calculation is present in the washing liquid, Surfactant concentration is 0.07-0.17g /
L.

By using such washing conditions, even if the concentration of the surfactant is low, the detergency is excellent, and therefore the standard amount of detergent used can be smaller than before. If the weight ratio of the alkali metal silicate to the sequestering agent other than the alkali metal silicate exceeds 5/1, sufficient detergency cannot be obtained even if the above cleaning conditions are satisfied.

In the washing method of the present invention, more preferable washing conditions include the following conditions corresponding to the above conditions (1) to (3). The washing liquid has a pH of 10.85 to 11.00, more preferably 10.90 to 11.00. 'It is preferable that a substance having an ion-capturing ability necessary for making the hardness of the washing water to be 0 ° DH in the calculation is present in the washing liquid, and more preferably -1 (minus 1) ° in the calculation.
This is the case when the amount of DH or less is present in the washing liquid. 'Surfactant concentration in the wash liquor is 0.08-0.14g
/ L is preferable, and 0.08 to 0.11 g / L is more preferable. It is particularly preferable to satisfy all of these preferable ranges, but the effect of the present invention becomes more remarkable by satisfying at least one of these preferable ranges. The weight ratio of the alkali metal silicate to the sequestering agent other than the alkali metal silicate is preferably 4/1 to 1/15, and 3/1 to 1/1
5 is more preferred.

The specific amount used, in other words, the detergent concentration in the wash liquor depends on the hardness of the wash liquor, and the amount of increase or decrease is due to the change in the amount of the sequestering agent. The concentration of the surfactant in the washing liquid is basically unchanged. Standard detergent usage varies by country in the world. This is because tap water hardness varies from country to country. For example, in Japan, water with a high hardness of 6 ° DH or more, and in Europe, having a hardness of more than 10 ° DH is used as washing water, while in Japan, it is usually around 4 ° DH. This changes the absolute amount of sequestering agent, and consequently the standard usage is adjusted accordingly. The addition amount of the sequestering agent in the present invention varies depending on the hardness,
The concentration of the surfactant in the washing liquid is basically the same, and the standard amount used is smaller than before.

Therefore, the detergent concentration when the initial hardness of the washing liquid is different is as follows. 1) For washing water at 2 to 6 ° DH, the concentration of the detergent composition in the washing liquid is 0.33 to 0.67 g / L, preferably 0.33 to 0.50 g / L. 2) The concentration of the detergent composition in the washing liquid is 0.50 to 1.20 g / L, preferably 0.50 to 1.00 g / L for 6 to 10 DH of washing water. 3) For washing water of 10 to 20 ° DH, the concentration of the detergent composition in the washing liquid is 0.80 to 2.50 g / L, preferably 1.00 to 2.00 g / L.

Here, the above cleaning conditions are measured and the like as follows. The pH of the washing liquid is measured at 25 ° C. with a usual glass electrode pH meter or the like. The amount of the substance having an ion-capturing ability to be present in the washing liquid (referred to as an alkali metal silicate and a sequestering agent other than the alkali metal silicate) is calculated as follows. For example, the hardness of washing water is calculated to be 0.5 ° D
The amount corresponding to the ion-capturing ability required for H is calculated by calculating the concentration of Ca and Mg ions corresponding to the hardness difference from the hardness of the washing water used (for example, about 4 ° DH in Japan). The total Ca ion trapping capacity corresponding to the ion concentration is calculated in units of concentration. In this case, the amount of washing water and the amount of detergent composition to be added depend on the surfactant concentration (0.07
The conditions are selected so as to be 0.17 g / L). The DH hardness is determined by the ion coupling plasma method (ICP
Method).

At this time, the method for measuring the ion trapping ability of the sequestering substance depends on whether the sequestering substance used is an ion exchanger or a chelating agent. The measuring method for each substance is as follows.

In the case of an ion exchanger, 0.1 g of a sample was precisely weighed and added to 100 ml of an aqueous calcium chloride solution (concentration: 500 ppm as CaCO ₃ ),
After stirring at 25 ° C. for 60 minutes, the mixture is filtered using a membrane filter having a pore size of 0.2 μm (manufactured by Advantech, nitrocellulose), and the amount of Ca contained in 10 ml of the filtrate is measured by EDTA titration. The calcium ion exchange capacity (cation exchange capacity) of the sample is determined from the value. For example, in the present invention, an inorganic substance such as a crystalline alkali metal silicate or an aluminosilicate (such as zeolite) is measured as an ion exchanger.

In the case of a chelating agent, a calcium ion electrode is used to measure Ca ion capturing ability as follows. In addition, all the solutions are prepared using the following buffers. _{Buffer; 0.1M-NH 4 Cl-NH} 4 OH buff
er (pH 10.0) (1) Preparation of calibration curve A standard calcium ion solution is prepared, and a calibration curve showing the relationship between the logarithm of calcium ion concentration and the potential as shown in FIG. 1 is prepared. (2) Measurement of calcium ion-capturing ability About 0.1 g of a sample is weighed in a 100 ml volumetric flask, and the volume of the sample is adjusted with the above buffer solution. To this, 2000
An aqueous CaCl ₂ solution (pH 10.0) corresponding to 0 ppm (calculated as CaCO ₃ ) is dropped from a buret (a blank is also measured). For dripping, 0.1 to 0.1 CaCl ₂ solution is used.
Add 0.2 ml each, read the potential at that time,
The calcium ion concentration is determined from the calibration curve in FIG. FIG.
The calcium ion concentration at the dropped amount A of the sample in the inside becomes the calcium ion trapping ability of the sample. For example, in the present invention, polycarboxylates such as citrate and carboxylate polymers such as acrylic acid-maleic acid copolymer are measured as chelating agents.

The washing method of the present invention includes any of 1) 2 to 6 ° DH of washing water, 2) 6 to 10 ° DH of washing water, and 3) 10 to 20 ° DH of washing water. Can also be applied in the case of. In this case, the conditions of-are the same, and only the detergent concentration is selected and determined so as to satisfy the conditions of-.

In order to realize a washing liquid having a high pH and a low hardness which can obtain an excellent detergency like the above washing method of the present invention, the following conditions are required. (B) Excessive sequestering agent is present. (B) Presence of an alkaline agent that buffers at high pH. Of these, crystalline silicates satisfying (a) and (b) at the same time are known, but use of crystalline silicate requires caution. The reason is that if the compounding amount of the crystalline silicate is increased in order to lower the hardness, the alkaline ability also increases.
In this case, the exchange rate of Ca or Mg with respect to the fatty acid is inevitably increased, which is not preferable. Therefore, in order to satisfy more preferable conditions, it is necessary to mix the other sequestering agent in a specific ratio, and if it is out of these ranges, it becomes difficult to reduce the amount of detergent used.

Therefore, the phosphorus-free laundry detergent composition of the present invention contains a) a surfactant, b) an alkali metal silicate, and c) a sequestering agent other than the b component, and , The total amount of the c component occupies 70 to 100% by weight in the whole composition, and the ratio of the b component to a is b / a = 9/1 to 1/2, preferably 9 /.
1 to 9/11, and the ratio of the b component to the c component is b
/ C = 5/1 to 1/15, preferably 4/1 to 1/15
It is something that is. More preferably, it contains the above a) to c), and the total amount of the above a, b and c components is 8 in the total composition.
0 to 100% by weight, the ratio of the b component to a is b / a = 9/1 to 1/1 by weight, and the ratio of the b component to c component is b / c = 3/1 to 1 / 15. Most preferably the hardness of the water used is 2-6 °
DH is 3/1 to 3/7, hardness is 6 to 10 ° DH, 4/3 to 1/6, and hardness is 10 to 20 ° DH, 1/1 to 1/15. In the present invention, with such a composition, it is possible to obtain a detergent composition having a smaller standard usage amount for washing water having different hardness.

Each of these components will be described below. a) Surfactant The surfactant used in the present invention is generally a detergent if it contains 50 to 100% by weight of a nonionic surfactant, and more preferably 65 to 100% by weight. What is used can be used without particular limitation. Specifically, it is at least one selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants exemplified below.
For example, the same type may be selected only from a plurality of non-ionic surfactants, or various types from anionic surfactants and non-ionic surfactants. May be selected plurally.

Examples of the nonionic surfactant include the following. That is, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether,
Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene glycol fatty acid alkyl ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid Esters, higher fatty acid alkanolamides, alkyl glucosides, alkyl glucose amides,
And alkylamine oxide.

Of these, particularly nonionic surfactants are ethylene oxide adducts of linear or branched primary or secondary alcohols having 10 to 18 carbon atoms,
It is desirable to use a polyoxyethylene alkyl ether having an average number of added moles of 5 to 15. More preferably, it is an ethylene oxide adduct of a linear or branched primary or secondary alcohol having 12 to 14 carbon atoms, and it is desirable to use a polyoxyethylene alkyl ether having an average addition mole number of 6 to 10. .

The anionic surfactants include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acid salts or ester salts, alkyl or alkenyl ether carboxylates. Examples thereof include acid salts, amino acid type surfactants, N-acyl amino acid type surfactants, and the like, with preference given to alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, and the like. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylamine salts. Examples of the amphoteric surfactant include carboxy type and sulfobetaine type amphoteric surfactants.

The content of the surfactant is preferably 1 to 45% by weight in the whole composition, and particularly 1) when using 2 to 6 ° DH of washing water, 15 to 30%
It is preferable to blend in 2% by weight, and 2) when using 6-10 ° DH of washing water, 8-25
It is preferable to blend in 3% by weight, 3) when using 10 to 20 ° DH of washing water, 5 to 2
It is preferable to add 0% by weight. If it is less than this range, it tends to be difficult to obtain sufficient detergency, and if it exceeds this range, the blending amount of the alkali agent and the sequestering agent is relatively decreased, and it is difficult to obtain sufficient detergency. is there.

The laundry detergent composition of the present invention having such a formulation has a surfactant concentration of 0.0 in the washing liquid.
When the detergent composition is added to the washing water so as to be 7 to 0.17 g / L, the concentration of the detergent composition in the washing liquid is 1) The detergent composition has a concentration of 0.33 to 0.67 g / L, preferably 0.33 to 0.50 g / L, and 2) for 6 to 10 ° DH of washing water, The detergent composition has a concentration of 0.50 to 1.20 g / L, preferably 0.50 to 1.00 g / L, and 3) for 10 to 20 ° DH of washing water, the detergent composition in the washing liquid. The concentration of the product is 0.80 to 2.50 g / L, preferably 1.00 to 2.00 g / L, and the standard amount of the detergent composition for obtaining sufficient detergency is smaller than that of the conventional one. I'm sorry.

B) Alkali metal silicate As the alkali metal silicate used in the present invention, either crystalline or amorphous one can be used. No
It is preferable to use a crystalline one because it is possible to impart an ion exchange ability and the standard amount of the detergent composition can be further reduced.

The crystalline alkali metal silicate used in the present invention is an alkali metal silicate of SiO ₂ / M.
₂ O (provided that M represents an alkali metal) is 0.5 to
What is 2.6 is used. On the other hand, the crystalline silicate used in the patent publications mentioned in the above-mentioned prior art is Si
O ₂ / Na ₂ O ratio (S / N ratio) is from 1.9 to 4.0, but silicate S / N ratio exceeds 2.6 in the present invention can not obtain the effect of the present invention However, it is not possible to make a detergent that can obtain excellent detergency with a small amount of use.

Among the crystalline alkali metal silicates used in the present invention, those having the following composition are preferably exemplified. _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (1) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa or VIII, represents one or a combination of two or more elements, wherein y / x = 0.5 to 2.
6, z / x = 0.01-1.0, n / m = 0.5-2.
0 and w = 0 to 20. _{) M 2 O · x'SiO 2 ·} y'H 2 O (2) ( wherein, M represents an alkali metal, x '= 1.5~2.
6, y ′ = 0 to 20. )

First, the crystalline alkali metal silicate having the above composition will be described. In the general formula (1), M
Is selected from Group Ia elements of the periodic table, and examples of Group Ia elements include Na and K. These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to form the M ₂ O component. Me is selected from Group IIa, IIb, IIIa, IVa or VIII elements of the periodic table, for example, Mg, Ca, Zn,
Y, Ti, Zr, Fe and the like can be mentioned. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These may be used alone or as a mixture of two or more. For example, MgO, CaO
Like are mixed may constitute the Me _m O _n component.
Further, the crystalline alkali metal silicate in the present invention may be a hydrate, and the hydration amount in this case is w.
= 0 to 20.

In the general formula, y / x is 0.5 to
It is 2.6, preferably 1.5 to 2.2. y /
When x is less than 0.5, the water resistance is insufficient and the powder properties of the detergent composition such as caking property and solubility are significantly adversely affected. If y / x exceeds 2.6, the alkalinity becomes low and becomes insufficient as an alkali agent, and the ion exchange ability also becomes low, making it insufficient as an ion exchanger. z
/ X is 0.01 to 1.0, preferably 0.02 to
0.9. When z / x is less than 0.01, the water resistance is insufficient, and when it exceeds 1.0, the ion exchange capacity is lowered and the ion exchange is insufficient. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. As described above, when xM ₂ O is, for example, x′Na ₂ O · x ″ K ₂ O, x is x ′ + x ″. Such a relationship is zMe
The same applies to z in the case _{where m} O _n component consist of two or more kinds. Also, n / m = 0.5 to 2.0
Represents the number of oxygen ions coordinated to the element, and is substantially selected from values of 0.5, 1.0, 1.5, and 2.0.

The crystalline alkali metal silicate according to the present invention comprises M ₂ O and Si as represented by the above general formula.
Has from three components of O _2, Me _m O _n. Therefore, in order to produce the crystalline alkali metal silicate of the present invention, each component is required as a raw material, but in the present invention, a known compound is not particularly limited,
Used as appropriate. For example, M ₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used.
Specifically, for example, the raw material of the M ₂ O component is NaO
H, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO ₄
Etc. is, as a material of Me _m O _n component, CaCO _3, M
gCO ₃ , Ca (OH) ₂ , Mg (OH) ₂ , MgO,
ZrO ₂ , dolomite and the like. As the SiO ₂ component, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.

In the method for preparing a crystalline alkali metal silicate according to the present invention, the above raw material components are mixed in a predetermined quantitative ratio so that x, y and z values of the desired crystalline alkali metal silicate can be obtained. Mixing is generally 300 to 1500 ° C, preferably 500 to 1000 ° C, more preferably 600 to 900.
A method of firing and crystallization in the range of ° C. is exemplified. In this case, if the heating temperature is lower than 300 ° C., the crystallization is insufficient and the water resistance is poor. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

The crystalline alkali metal silicate of the present invention thus obtained exhibits a pH of 11 or more in a 0.1% by weight dispersion and exhibits an excellent alkaline ability.
Also, the alkali buffering effect is particularly excellent, and the alkali buffering effect is superior to that of sodium carbonate or potassium carbonate.

The crystalline alkali metal silicate according to the present invention has an ion exchange capacity of at least 100 CaCO 3.
₃ mg / g or more, preferably 200 to 600 CaCO ₃
It has mg / g and is one of the substances having an ion trapping ability in the present invention. Further, the amount of Si eluted in water is usually 110 mg / g or less in terms of SiO ₂ , and it is substantially insoluble in water. In the present invention, “substantially insoluble in water” means that 2 g of the sample is 100 g of ion-exchanged water.
In addition, it means that the amount of Si leached in the case of stirring at 25 ° C. for 30 minutes is usually less than 110 mg / g in terms of SiO ₂ , but in the present invention, 100 mg / g or less will satisfy the present effect. Is more preferable.

The crystalline alkali metal silicate according to the present invention has the alkaline ability and the alkaline buffering effect as described above, and further has the ion exchange ability. Therefore, by appropriately adjusting the blending amount thereof, the above-mentioned washing can be performed. The conditions can be adjusted appropriately. In the present invention, the crystalline alkali metal silicate preferably has an average particle size of 0.1 to 50 μm, more preferably 1 to 30 μm, and further preferably 1 to 10 μm. If the average particle size exceeds this range, the expression rate of ion exchange tends to be slow,
Deterioration of detergency. Further, when it is less than this range, the hygroscopicity and the CO ₂ absorbing property increase due to the increase in the specific surface area, and the quality tends to be remarkably deteriorated. Here, the average particle size is the median size of the particle size distribution.

The crystalline alkali metal silicate having such an average particle size and particle size distribution can be prepared by pulverizing with a pulverizer such as a vibration mill, a hammer mill, a ball mill, a roller mill. For example, HB
It can be easily obtained by crushing with an -O type vibration mill (manufactured by Chuo Kakoki Co., Ltd.).

The content of the crystalline alkali metal silicate is
It is preferable to add 4 to 75% by weight of the total composition, especially 1) when using 2 to 6 ° DH of washing water, 25 to 55
It is preferable to blend it in an amount of 2% by weight. 2) When using 6-10 ° DH of washing water, 10-4
5% by weight is preferably blended, 3) when using 10 to 20 ° DH of washing water, 5 to 3
It is preferable to add 0% by weight. If the blending amount is outside this range, it becomes difficult to satisfy the above-mentioned washing conditions.

Next, the crystalline alkali metal silicate having the above composition will be described. The crystalline alkali metal silicates have the general formula _{(2) M 2 O · x'SiO} 2 · y'H 2 O (2) ( wherein, M represents an alkali metal, x '= 1.5 to 2.
6, y ′ = 0 to 20. ), X ′ and y ′ in the general formula (2) are 1.7 ≦ x ′ ≦ 2.
2, y ′ = 0 is preferred, and the cation exchange capacity is at least 100 CaCO ₃ mg / g or more, preferably 20
0 to 400 CaCO ₃ mg / g can be used and is one of the substances having an ion trapping ability in the present invention. The crystalline alkali metal silicate in the present invention has the alkaline ability and the alkaline buffering effect as described above, and further has the ion exchange ability. Therefore, by appropriately adjusting the blending amount thereof, the above-mentioned washing conditions are suitably adjusted. Can be adjusted.

The crystalline alkali metal silicate is preferably added in an amount of 4 to 75% by weight based on the total composition, and particularly 1) when using 2 to 6 ° DH of washing water, 25 to 55%.
It is preferable to blend it in an amount of 2% by weight. 2) When using 6-10 ° DH of washing water, 10-4
5% by weight is preferably blended, 3) when using 10 to 20 ° DH of washing water, 5 to 3
It is preferable to add 0% by weight. If the blending amount is outside this range, it becomes difficult to satisfy the above-mentioned washing conditions.

The production method of such a crystalline alkali metal silicate is described in JP-A-60-227895, and generally 200 g of amorphous glassy sodium silicate is used.
It is obtained by firing at ~ 1000 ° C to make it crystalline. For details of the synthesis method, see, for example, Phys. Chem. Glasses.
7, 127-138 (1966), Z. Kristallogr., 129 , 396-404 (19
69) etc. Further, this crystalline alkali metal silicate is, for example, from Hoechst under the trade name "Na-SKS-6"
As (δ-Na ₂ Si ₂ O ₅ ), powdery and granular ones are available. In the present invention, the crystalline alkali metal silicate having a composition of, like the composition of, has an average particle size of
The thickness is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and further preferably 1 to 10 μm.
In the present invention, the crystalline alkali metal silicates having the above compositions and are used singly or in combination of two or more kinds.
It is preferably from 0 to 100% by weight, more preferably from 70 to 100% by weight.

Amorphous alkali metal silicates can also be used in the present invention.
In addition to sodium silicate, Britesil C20,
Britesil H20, Britesil C2
4, Britesil H24 (all are registered trademarks, T
he PQ Corporation) and NABI
ON 15 (registered trademark, RHONE-BOULENC
Commercially available products such as manufactured products) may be used.

C) Sequestering Agents Other Than Alkali Metal Silicates The sequestering agents other than alkali metal silicates of the present invention have a Ca ion scavenging ability of 200 CaCO ₃ mg /
g or more. In particular, a polymer containing 10% by weight or more of a carboxylate polymer is preferable, and specific examples of such a polymer include a polymer or a copolymer having a repeating unit represented by the general formula (4). .

[0052]

Embedded image

(Wherein X ₁ is methyl, H or COOX
₃ , X ₂ represents methyl, H or OH, and X ₃ represents H, an alkali metal, an alkaline earth metal, NH ₄ or ethanolamine. )

In the general formula (4), examples of the alkali metal include Na, K and Li, and examples of the alkaline earth metal include Ca and Mg.

The polymer or copolymer used in the present invention is, for example, a polymerization reaction of acrylic acid, (anhydrous) maleic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid, isocrotonic acid, or a salt thereof, or It is synthesized by a copolymerization reaction of each monomer or a copolymerization reaction with another polymerizable monomer. Examples of other copolymer monomers used for copolymerization at this time include, for example, aconitic acid, itaconic acid, citraconic acid, fumaric acid, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, propylene , Isobutylene, pentene, butadiene, isoprene, vinyl acetate (and vinyl alcohol when hydrolyzed after copolymerization), acrylate, and the like, but are not particularly limited. In addition,
The polymerization reaction is not particularly limited, and a generally known method can be used. Further, a polyacetal carboxylic acid polymer such as polyglyoxylic acid described in JP-A-54-52196 can also be used.

In the present invention, as the above-mentioned polymers and copolymers, those having a weight average molecular weight of 800 to 1,000,000 are used, and those having a weight average molecular weight of 5,000 to 200,000 are preferably used.

The copolymerization rate of the repeating unit of the general formula (4) with another copolymerizable monomer in the case of copolymerization is not particularly limited, but is preferably the repeating unit of the general formula (4) / other copolymerization. Monomer = Copolymerization ratio in the range of 1/100 to 90/10. In the present invention, the above-mentioned polymer or copolymer is contained in the entire composition in an amount of 1 to 50% by weight, preferably 2 to 30% by weight, more preferably 5 to 15% by weight. If it is less than 1% by weight, the effect of the present invention cannot be obtained, and if it exceeds 50% by weight, the effect of addition is saturated and it is meaningless only to unnecessarily increase the cost.

In the sequestering agent of the component c, (c
-I) The above-mentioned Ca ion trapping ability is 200 CaCO ₃ m
g / g or more of carboxylate polymer, and (c-ii)
The ion exchange capacity represented by the following formula (3) is 200 CaC.
Containing O ₃ mg / g or more of aluminosilicate, x ″ (M ₂ O) · Al ₂ O ₃ · y ″ (SiO ₂ ) · w ″ (H ₂ O) (3) (where M is Alkali metals such as sodium and potassium,
x ″, y ″, w ″ represent the number of moles of each component, and generally 0.7 ≦ x ″ ≦ 1.5, 0.8 ≦ y ″ ≦ 6, w ″
Twenty. ) The ratio of the c-i component to the c-ii component is c-i by weight ratio.
/ C-ii = 1/20 to 4/1, preferably 1/9 to 4 /
It is 1 and the total amount of c-i and c-ii occupies 70 to 100% by weight of the sequestering agent of the component c.

Examples of the above-mentioned aluminosilicates include crystalline ones and amorphous ones. As the crystalline ones, those represented by the following general formula are particularly preferable. _{Na 2 O · Al 2 O 3} · ySiO 2 · wH 2 O ( wherein, y is 1.8 to 3.0, w represents a number of 1-6.) As the crystalline aluminosilicate (zeolite) , Type A,
The average primary particle size represented by X-type and P-type zeolite is 0.
A synthetic zeolite of 1 to 10 μm is preferably used. The zeolite may be used as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry or the slurry.

The above crystalline aluminosilicate can be manufactured by a conventional method. For example, JP-A-50-123
81 and JP-A-51-12805 can be used.

On the other hand, the amorphous aluminosilicate represented by the same general formula as the above crystalline aluminosilicate can be produced by a conventional method. For example, SiO ₂ and M ₂ O
(M means an alkali metal) molar ratio of SiO ₂ /
An M ₂ O = 1.0~4.0, the molar ratio of between H ₂ O and M ₂ O is using alkali metal silicate solution is a _{H 2 O / M 2 O =} 12~200, M to The molar ratio of ₂ O and Al ₂ O ₃ is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0, and H
The molar ratio of ₂ O to M ₂ O is H ₂ O / M ₂ O = 6.0 to 50
The aqueous solution of a low alkali alkali metal aluminate, which is 0, is usually added under a strong stirring at a temperature of 15 to 60 ° C, preferably 30 to 50 ° C.

The resulting white precipitate slurry is then heated to a temperature of usually 70 to 100 ° C, preferably 90 to 100 ° C.
It can be advantageously obtained by performing a heat treatment usually for 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. At this time, the addition method may be a method of adding an aqueous solution of an alkali metal silicate to an aqueous solution of a low alkali alkali metal aluminate. According to this method, the ion exchange capacity is 100 CaCO ₃ mg / g or more, and the oil absorption capacity is 80 m.
An amorphous aluminosilicate oil-absorbing carrier of 1/100 g or more can be easily obtained (see JP-A-62-191417 and JP-A-62-191419). Other sequestering agents include aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and salts thereof, -Phosphonobutane-1,2-
Examples include salts of phosphonocarboxylic acids such as dicarboxylic acids, salts of amino acids such as aspartic acid and glutamic acid, and aminopolyacetates such as nitrilotriacetate and ethylenediaminetetraacetate.

As the other components in the present invention, various alkaline agents such as alkali metal salts such as carbonates and sulfites and organic amines such as alkanolamines, in addition to crystalline and amorphous alkali metal silicates, are used. The following are listed.

Further, non-dissociated polymers such as polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone, builders such as salts of organic acids such as diglycolic acid and oxycarboxylic acid salts, and carboxymethyl cellulose can be generally added to detergents. Known anti-fading agents, anti-redeposition agents and the like can be mentioned.

In addition, the detergent composition of the present invention may contain the following components. That is, enzymes such as protease, lipase, cellulase, and amylase, having 1 to 1 carbon atoms
About 4 lower alkylbenzene sulfonate, sulfosuccinate, talc, anti-caking agent such as calcium silicate, tert-butylhydroxytoluene, antioxidant such as distyrenated cresol, bleaching agent such as sodium percarbonate, tetraacetylethylenediamine, etc. The bleaching activator, the fluorescent dye, the bluing agent, the fragrance and the like can be included, but these are not particularly limited and may be blended according to the purpose.

The detergent composition of the present invention contains each of the above components, but the method for producing the detergent composition is not particularly limited, and conventionally known methods can be used. For example, as a method for obtaining a high bulk density detergent,
JP-A-61-69897, JP-A-61-6989
9, JP-A-61-69900, JP-A-5-
The methods described in Japanese Patent Application No. 209200 and Japanese Patent Application No. 7-174440 can be used.

[0067]

EXAMPLES The present invention will be described in more detail with reference to Preparation Examples and Test Examples, but the present invention is not limited to these Preparation Examples and the like. The measured value was measured by the following method.

(1) pH of Washing Liquid The pH of the washing liquid was measured at 25 ° C. with a glass electrode pH meter (manufactured by Horiba Ltd.) by adding a detergent composition to washing water. At this time, the pH shown in the washing liquid was a value at which the indicated value was sufficiently stable.

(2) Amount of substance having ion-capturing ability The ion-capturing ability was measured by the following method, depending on whether the sequestering substance used was an ion exchanger or a chelating agent. As a method of displaying the ion trapping ability of the sequestering agent, CEC (calcium ion exchange capacity) is displayed in the tables of the examples as in the case of alkali metal silicates. The DH hardness was measured by the ion coupling plasma method (ICP method).

In the case of an ion exchanger, 0.1 g of a sample was precisely weighed and added to 100 ml of an aqueous calcium chloride solution (concentration: 500 ppm as CaCO ₃ ),
After stirring at 25 ° C. for 60 minutes, filtration was carried out using a membrane filter having a pore size of 0.2 μm (manufactured by Advantech, nitrocellulose), and the amount of Ca contained in 10 ml of the filtrate was measured by EDTA titration. The calcium ion exchange capacity (cation exchange capacity) of the sample was determined from the value.

In the case of a chelating agent A Ca ion electrode was used to measure the Ca ion capturing ability as follows. All solutions were prepared using the following buffer solutions. _{Buffer; 0.1M-NH 4 Cl-NH} 4 OH buff
er (pH 10.0) (i) Preparation of calibration curve A standard calcium ion solution was prepared and a calibration curve showing the relationship between the logarithm of the calcium ion concentration and the potential as shown in FIG. 1 was prepared. (Ii) Measurement of calcium ion-capturing ability About 0.1 g of a sample is weighed in a 100 ml volumetric flask, and the volume of the sample is raised with the above buffer solution. To this, 2000
An aqueous CaCl ₂ solution (pH 10.0) corresponding to 0 ppm (calculated as CaCO ₃ ) was dropped from a buret (a blank is also measured). For dripping, 0.1 to 0.1 CaCl ₂ solution is used.
Add 0.2 ml each, read the potential at that time,
The calcium ion concentration was determined from the calibration curve in FIG. FIG.
The calcium ion concentration in the dropped amount A of the sample was taken as the calcium ion trapping ability of the sample.

When calculating the amount of the substance having the ion trapping ability, for example, at 4 ° DH used in Test Example 1, the ion concentration is 71.6CaCO ₃ mg / L (2148CaCO ₃
mg / 30 L), 0.5 ° DH is 9.0 CaC
Since it corresponds to O ₃ mg / L (270CaCO ₃ mg / 30L), at least 62.6CaCO ₃ mg / L is calculated in order to reduce the washing water at 4 ° DH to 0.5 ° DH or less.
An amount corresponding to the ion trapping ability of (1878CaCO ₃ mg / 30L) is required. Therefore, in the table showing the results, the amount of the substance having the ion trapping ability is shown in the corresponding unit (CaCO ₃ mg / L).

(3) Average particle size and particle size distribution of alkali metal silicate The average particle size and particle size distribution were measured using a laser diffraction type particle size distribution measuring device. That is, about 200 ml of ethanol was injected into a measurement cell of a laser diffraction type particle size distribution analyzer LA-700 type (manufactured by Horiba, Ltd.), and about 0.5 to 5 mg of a sample was suspended. Subsequently, the mixture was stirred for 1 minute while being irradiated with ultrasonic waves, and after sufficiently dispersing the sample, a He-Ne laser (632.8 nm) was incident, and the particle size distribution was measured from the diffraction / scattering pattern.
The analysis uses both the Fraunhofer diffraction theory and the Mie scattering theory to reduce the particle size distribution of suspended particles in the liquid from 0.04 to
It was measured in the range of 262 μm. The average particle size was the median size of the particle size distribution.

Preparation Example 1 (Crystalline alkali metal silicate A
To E) 2 sodium silicate No. _{(SiO 2 / Na 2 O =} 2.5) 100
Sodium hydroxide (55.9 parts by weight) and potassium hydroxide (8.5 parts by weight) were added to 0 parts by weight, and the mixture was stirred with a homomixer to dissolve sodium hydroxide and potassium hydroxide. 5.23 parts by weight of finely dispersed anhydrous calcium carbonate and 0.13 parts by weight of magnesium nitrate hexahydrate were added thereto and mixed using a homomixer. An appropriate amount of the mixture was placed in a nickel crucible, fired at 700 ° C. in the air for 1 hour, quenched, and the fired body obtained was ground to obtain the alkali metal silicate A in the present invention. The ion exchange capacity of this powder was as high as 305 CaCO ₃ mg / g. In the same manner, alkali metal silicates B, C, D and E having the compositions shown in Table 1 were obtained.

[0075]

[Table 1]

Preparation Example 2 (amorphous aluminosilicate) Sodium carbonate was dissolved in ion-exchanged water to prepare an aqueous solution having a concentration of 6% by weight. 132 g of this aqueous solution and 38.28 g of sodium aluminate aqueous solution (Conc.
Placed in a 00 ml baffled reaction vessel. No. 3 water glass 20 diluted with 2 times water was added to the obtained mixed solution under strong stirring.
The reaction was carried out at 40 ° C. while dropping 1.4 g over 20 minutes. At this time, the pH of the reaction system was controlled by blowing CO ₂ gas (pH = 10.5) to optimize the reaction rate. Then, the reaction system was heated to 50 ° C. and stirred at the same temperature for 30 minutes. After that, CO is added to the reaction system.
₂ Gas was blown in to neutralize excess alkali (pH =
9.0). The obtained neutralized slurry was filtered under reduced pressure using filter paper (Toyo Roshi Kaisha, Ltd. No. 5C). The filter cake is washed with 1000 times water and filtered and dried (105
C., 300 torr, 10 hours) and the rest was dried under the same conditions (without washing). Furthermore, it crushed and obtained the amorphous aluminosilicate powder of this invention. The sodium aluminate aqueous solution was prepared by adding 243 g of Al (OH) ₃ and a 48% NaOH aqueous solution 2 to a 1000 cc four-necked flask.
98.7 g was added and mixed, heated to 110 ° C. with stirring, and dissolved for 30 minutes to prepare.

The composition of the obtained amorphous aluminosilicate is
As a result of atomic absorption analysis and plasma emission analysis, Al ₂ O ₃
= 29.6% by weight, SiO ₂ = 52.4% by weight, Na ₂
O = 18.0% by weight (1.0Na ₂ O.Al ₂
O ₃ · 3.10 SiO ₂ ). Further, the Ca ion trapping ability is 185 CaCO ₃ mg / g, and the oil absorbing ability is 285 ml / 10.
0 g, the ratio of the pore volume having a pore diameter of less than 0.1 μm is 9.4%, the ratio of the pore volume having a pore diameter of 0.1 μm or more and 2.0 μm or less is 76.3%, the water content Is 11.
It was 2% by weight.

Preparation Example 3 (detergent composition) Crystalline alkali metal silicate A obtained in the above Preparation Example
To E, amorphous aluminosilicate, and other components shown in Tables 2 to 11 were used to produce detergent compositions having the compositions shown in Tables 2 to 11 by the following method. That is, Example 1-1
15 to Examples 1 to 17 to 20, aqueous components (LAS-Na, AS-Na, sodium silicate No. 1,
Acrylic acid maleic acid copolymer, polyglyoxy acid N
a, Na polyacrylate, Na citrate, sodium carbonate, sodium sulfate, sodium sulfite) into a 60% solid content slurry, and the particles obtained by spray-drying this are put into a Loedige mixer, and the remaining powder raw material. The mixture was granulated by gradually adding a liquid nonionic surfactant. In Example 1-16, a 60% solids slurry containing components other than zeolite was spray-dried, the obtained particles were placed in a high speed mixer, and a zeolite in an amount corresponding to the blending amount was further placed therein for granulation. In addition, TA in each example
For ED, PC and enzymes, granular raw materials were blended. In this way, the average particle size is 300 to 600
A powder detergent composition having a bulk density of 0.6 to 1.0 g / ml was obtained.

Test Example 1 Using the detergent composition obtained in the above Preparation Example, a cleaning test was conducted under the following conditions. (Preparation of artificially contaminated cloth) An artificially contaminated cloth was prepared by adhering an artificially contaminated liquid having the following composition to the cloth. The artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater. The step of making the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth is performed using a gravure roll having a cell capacity of 5
The drying was performed at 8 cm ³ / cm ² , a coating speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. Cloth is cotton gold width 20
03 cloth (manufactured by Tanigami Shoten) was used. [Composition of artificial contamination liquid] Lauric acid 0.44% by weight Myristic acid 3.09% by weight Pentadecanoic acid 2.31% by weight Palmitic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57% by weight Oleine Acid 7.75 wt% Triolein 13.06 wt% n-Hexadecyl palmitate 2.18 wt% Squalene 6.53 wt% Egg white lecithin liquid crystal 1.94 wt% Kanuma red clay 8.11 wt% Carbon black 0.01 Weight% Tap water balance

(Washing conditions) Using a tergotometer, the rotation speed is 100 rpm, the washing time is 10 minutes, and the temperature is 20.
C, water used 4 ° DH (Ca / Mg = 3/1), Table 2
Laundry was performed with the detergents and detergent concentrations shown in Table 11. The hardness component of washing water is typically represented by Ca ²⁺ and Mg ²⁺ , and the weight ratio thereof is Ca / Mg = (60 to 85) / (40
Approximately 15), but here as model water Ca /
Mg = 3/1 was used. 4 ° DH is the hardness when the equimolar amount of Mg ions is replaced with Ca.

(Calculation of washing ratio) 55 before and after the original cloth and washing
The reflectance at 0 μm was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate D (%) was calculated by the following equation. The results are also shown in Tables 3, 5, 7, 9, and 11. D = (L ₂ −L ₁ ) / (L ₀ −L ₁ ) × 100 (%) L ₀ : reflectance of original cloth L ₁ : reflectance of contaminated cloth before cleaning L ₂ : reflectance of contaminated cloth after cleaning

The abbreviations in Tables 2 to 15 are as follows. POE: average number of moles of ethylene oxide added LAS-Na: sodium linear alkylbenzene sulfonate AS-Na: sodium alkylsulfate acrylic acid maleic acid copolymer: "Sokalan
CP5 "(manufactured by BASF Akchengeshell Shaft,
Acrylic acid-copolymer having maleic acid as a monomer, average molecular weight 70,000, polyacrylic acid Na: sodium acrylate polymer,
Average molecular weight 10000 Na citrate: Trisodium citrate TAED: Tetraacetylethylenediamine PC: Sodium percarbonate Protease: Alkaline protease K-16 described in JP-A-5-25492 Cellulase: described in JP-A-63-264699 Alkaline Cellulase K Lipase: Lipolase NOVO Nordisk Bioindustry LTD

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

[Table 9]

[0091]

[Table 10]

[0092]

[Table 11]

As shown by the above results, a washing liquid which gives the above-mentioned washing conditions when no clothes are put therein (Example 1-
1, Examples 1-9 to 1-15, 1-20), a high cleaning rate was obtained. In particular, the ratio of the crystalline alkali metal silicate to the other sequestering agent is 5/1 to 1 /
No. 15 showed a high cleaning rate of 60% or more.
Further, for example, as shown in Example 1-1 of Table 3, it was shown that the detergent composition concentration maintained a cleaning rate of 60% or more even at a low concentration of 0.33 to 0.67 g / L. This means that the standard amount used once is 25 to 30 g / 3 for conventional products.
Since it is 0L, it is about 0.4 of the conventional compact detergent.
This shows that the size has been further reduced by 0.7 times. On the other hand, the washing liquids that do not give the washing conditions (1) to (2) to (1) to (8) to (1) to (1) to (1) to (1) to (1) to (19) as described above.
In the case where the detergent composition concentration was as low as 0.33 to 0.67 g / L, only a low cleaning rate was obtained.

Test Example 2 Using the detergent compositions shown in Table 12, a cleaning test was conducted under the following conditions. In Test Example 1, except that the washing temperature was changed to 30 ° C. and the water used was 8 ° DH (Ca / Mg = 3/1), washing was carried out at the detergent concentration shown in Table 13 in the same manner as in Test Example 1. went. Table 13 shows the results.

[0095]

[Table 12]

[0096]

[Table 13]

As is clear from Table 13, a washing liquid which gives the above-mentioned washing conditions when no clothes are put therein (Example 2)
When -1) was used, a high cleaning rate was obtained. On the other hand, a washing liquid that does not give the above-mentioned washing conditions (Example 2-
In 2), the detergent composition concentration is 0.50 to 1.20 g /
At a low concentration of L, only a low cleaning rate was obtained.

Test Example 3 Using the detergent compositions shown in Table 14, a cleaning test was conducted under the following conditions. In Test Example 1, the washing time was changed to 30 minutes, the washing temperature was changed to 40 ° C., and the water used was 15 ° DH (Ca / M
g = 3/1) except that the same as in Test Example 1
Laundry was performed at the detergent concentration shown in FIG. The results are shown in Table 15.
Shown in

[0099]

[Table 14]

[0100]

[Table 15]

As is clear from Table 15, a washing liquid which gives the above-mentioned washing conditions when no clothes are put therein (Example 3)
When -1) was used, a high cleaning rate was obtained. On the other hand, a washing liquid that does not give the above-mentioned washing conditions (1)
In 2), the detergent composition concentration is 0.80 to 2.50 g /
At a low concentration of L, only a low cleaning rate was obtained.

[0102]

EFFECTS OF THE INVENTION According to the laundry method and the laundry detergent composition of the present invention, since the detergent is excellent even in the case where the concentration of the surfactant is low, the standard amount of the detergent is more than that of the usual compact laundry detergent composition. It needs less. Further, since the detergent composition is phosphorus-free, there are few environmental problems.

[Brief description of the drawings]

FIG. 1 is a diagram showing a calibration curve showing a relationship between a logarithm of calcium ion concentration and a potential.

FIG. 2 is a diagram showing a relationship between a drop amount of a sample and a calcium ion concentration.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location C11D 3:08 3:37) (72) Inventor Katsuhiko Kasai 1334 Minato Minato, Wakayama Kao Research Institute (72) Inventor Masaki Tsumadori 1334 Minato, Wakayama City Kao Co., Ltd. (72) Inventor Hiroyuki Yamashita 1334 Minato, Wakayama City Kao Co., Ltd.

Claims (16)

[Claims] 1. A surfactant, an alkali metal silicate, and a sequestering agent other than the alkali metal silicate, wherein the weight ratio of the alkali metal silicate to the sequestering agent is 5/1 or less. A method for washing clothes using the phosphorus-free detergent composition for clothes, which comprises using a washing liquid that provides the following washing conditions when the clothes are not put in. The pH of the washing liquid is 10.60 or more, the substance having the ion-capturing ability necessary for making the hardness of the washing water 0.5 ° DH or less in the calculation is present in the washing liquid, and Surfactant concentration is 0.07-0.17g /
L. 2. The concentration of the detergent composition in the washing liquid is 2 to 6
The washing method according to claim 1, wherein the washing water has a water content of 0.33 to 0.67 g / L. 3. The concentration of the detergent composition in the washing liquid is 6 to 1
0.50 to 1.20 g / L for 0 ° DH washing water
The washing method according to claim 1, wherein 4. The concentration of the detergent composition in the washing liquid is 10 to 10.
0.80 to 2.50 g / for 20 ° DH washing water
The washing method according to claim 1, wherein the washing method is L. 5. The following components: a) a surfactant, b) an alkali metal silicate, and c) a sequestering agent other than the b component, wherein the total amount of the a, b, and c components is in the total composition. 70 to 100% by weight, the ratio of the b component to the a is b / a = 9/1 to 1/2 by weight, and the ratio of the b component to the c component is b / c = 5/1 to A phosphorus-free clothing detergent composition which is 1/15. 6. The weight ratio of the component b to a is b /
The detergent composition for clothes according to claim 5, wherein a = 9/1 to 9/11 and the ratio of the b component to the c component is b / c = 4/1 to 1/15. 7. A nonionic surfactant in the surfactant,
The detergent composition for clothes according to claim 5, wherein the detergent composition is contained in an amount of 50 to 100% by weight. 8. The detergent for clothes according to claim 7, wherein the nonionic surfactant is a polyoxyethylene alkyl ether obtained by adding an average of 5 to 15 mol of ethylene oxide to an alcohol having an alkyl group having an average carbon number of 10 to 18. Composition. 9. The detergent composition for clothes according to claim 5, wherein an alkali metal silicate accounts for 50 to 100% by weight of the alkali agent. 10. Alkali metal silicate SiO ₂ / M
₂ O (provided that M represents an alkali metal) is 0.5 to
It is 2.6, The detergent composition for clothes in any one of Claims 5-9. 11. The laundry detergent composition according to claim 5, wherein the alkali metal silicate is crystalline. 12. The laundry detergent composition according to claim 11, wherein the crystalline alkali metal silicate has a composition represented by the following formula (1). _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (1) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa or VIII, represents one or a combination of two or more elements, wherein y / x = 0.5 to 2.
6, z / x = 0.01-1.0, n / m = 0.5-2.
0 and w = 0 to 20. ) 13. The laundry detergent composition according to claim 11, wherein the crystalline alkali metal silicate has a composition represented by the following formula (2). _{M 2 O · x'SiO 2 · y'H} 2 O (2) ( wherein, M represents an alkali metal, x '= 1.5~2.
6, y ′ = 0 to 20. ) 14. The metal ion sequestering agent of component c contains 10% by weight or more of a carboxylate polymer having a Ca ion trapping ability of 200 CaCO ₃ mg / g or more.
3. The detergent composition for clothes according to any one of 3 above. 15. In the sequestering agent of component c, (c-
i) a carboxylate polymer having a Ca ion trapping ability of 200 CaCO ₃ mg / g or more, and (c-ii) an ion exchange capacity represented by the following formula (3) of 200 CaCO ₃ m
containing g / g or more _{aluminosilicate, x "(M 2 O)} · Al 2 O 3 · y" (SiO 2) · w "(H 2 O) (3) ( wherein, M is an alkali metal , X ″, y ″, w ″ represent the number of moles of each component, and 0.7 ≦ x ″ ≦ 1.5, 0.8 ≦ y ″.
≦ 6, w ″ is 0 to 20.) The ratio of the c-i component to the c-ii component is c-i by weight ratio.
/ C-ii = 1/20 to 4/1, and c-i and c-ii
The detergent composition for clothes according to any one of claims 5 to 14, wherein the total amount of occupies 70 to 100% by weight of the sequestering agent of the component c. 16. The washing method according to claim 1, wherein the laundry detergent composition according to any one of claims 5 to 15 is used.