JP3337194B2 - Powder detergent composition for clothing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder detergent composition for clothing using crystalline sodium silicate which sufficiently exerts its washing performance in a powder detergent composition. More specifically, the present invention relates to a powder detergent composition for clothing capable of obtaining excellent detergency with a small amount of use.

[0002]

2. Description of the Related Art Generally, a powder detergent composition for clothing comprises a surfactant as a main base and three basic components including a sequestering agent (chelating agent and ion exchanger) and an alkali agent.

[0003] Sequestering agents (chelating agents and ion exchangers) are blended in order to remove the influence of hardness components such as calcium and magnesium in tap water on the cleaning system. In the past, tripolyphosphate was widely used in terms of its excellent cost performance, handling properties in manufacturing, etc., but since the late 1970s, its use has been reduced due to concerns about eutrophication of closed water bodies such as lakes and marshes. At present, an ion exchange agent which is a crystalline aluminosilicate (zeolite) as represented by JP-A-50-12381 and a low-molecular-weight chelating agent such as citrate which assists the ion exchange agent The mainstream is a combination of high-molecular builders such as polycarboxylate and polycarboxylate.

[0004] As for the alkali agent, since the above-mentioned chelating agent, tripolyphosphate, is a substance also having an alkali ability, a carbonate such as sodium carbonate or potassium carbonate or amorphous sodium silicate is used as an auxiliary agent. However, as phosphorus-free treatment progressed,
Since almost no alkalinity can be expected from zeolite, which is a substitute for phosphorus compounds, the alkalinity in the detergent has been reviewed, and the amount of alkali metal carbonate and amorphous sodium silicate has been increased. I have.

[0005] The mixing ratio of carbonate and sodium silicate depends on the type and amount of other builders or surfactants and the production method, but amorphous sodium silicate is generally high. Alkaline, but highly hygroscopic and cause caking of powder detergents.Currently, alkali metal carbonate is used as the main alkali agent, and an effective amount of sodium silicate is used as a skeleton constituent of the powder. By doing so, the alkaline capacity is secured.

At relatively high hardness, carbonates and amorphous silicates have the function of sequestering and precipitating metal ions, but from the relation of equilibrium constants during ion exchange,
It is difficult to reduce the hardness to such an extent that the detergency is not affected. For example, under the conditions in Japan using soft tap water, it has almost no sequestering ability.

However, in recent years, Japanese Patent Laid-Open No. 60-227895 has been disclosed.
Patent Document No. 2, since crystalline sodium silicate having a specific structure has a property of having an ion exchange ability in addition to the alkali ability, ion exchange agents such as zeolite used in conventional detergents, sodium carbonate and the like There is a possibility that the function of the two components of the alkaline agent can be fulfilled only by this crystalline sodium silicate, and in addition, from the industrial advantage that the raw material composition is simple and relatively inexpensive to produce, Currently attracting attention as a new detergent builder.

[0008] Many applications have already been made with respect to a detergent containing crystalline sodium silicate described in JP-A-60-227895. For example, Japanese Patent Laid-Open No. 2-1
No. 78398 discloses a composition in which the above-mentioned crystalline sodium silicate [SKS-6 (manufactured by Hoechst)] is applied to a conventional detergent system.
Japanese Patent Application Publication No. JP-A-2002-115139 discloses a detergent which does not remain on fibers in which zeolite and polycarboxylate are blended at a specific blending ratio with crystalline sodium silicate. In addition, Table 6-5
JP-A-02199 discloses a builder composition using a zeolite and a carboxylic acid-based polymer in combination, and JP-A-6-505054 discloses a compounding system not containing an alkali metal carbonate and a carboxylic acid-based polymer. Have been. In addition, JP-A 1-311197,
JP-A-3-37298, JP-A-7-53992 and the like can be cited, and the present applicant also discloses JP-A-5-37992.
Japanese Patent Publication No. 10000 discloses that excellent detergency can be obtained by using a nonionic surfactant in combination with crystalline sodium silicate.

[0009] JP-A-60-2 used in the above publication
The crystalline sodium silicate described in Japanese Patent No. 27895 has many crystal phases such as δ-form, α-form and β-form as isomers in its crystal phase. However, with respect to the crystalline phase of crystalline sodium silicate, there has been no particular attempt to improve the detergency by optimizing the combination of crystalline phases.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a powder detergent composition for clothing which exhibits excellent detergency, and further provides a powder detergent composition for clothing with a small standard amount. To provide.

[0011]

The inventors of the present invention have found that the composition ratio of such a crystal phase varies depending on the firing conditions (temperature, time, etc.), and that even if the composition is the same, the detergency depends on the combination of the crystal phases. Were found to be different, and the difference was particularly remarkable when a large amount of crystalline sodium silicate was added. As a result of further intensive studies, it was found that the ion exchange rate, that is, the hardness reduction rate was different depending on the composition ratio of the crystalline phase of crystalline sodium silicate,
It has been found that the ion exchange rate affects the detergency at high loadings of crystalline sodium silicate. Furthermore, by combining a sequestering agent and a surfactant other than crystalline sodium silicate in a specific ratio, a powder detergent composition for clothing has been developed which can obtain high detergency even with a small amount of use. .

[0012] Namely, the present invention provides [1] The average particle size of below in the range of 1~100μm formula (1), wherein the crystalline sodium silicate _{Na 2 O · xSiO 2 · yH} 2 O (1 (Where x and y represent the number of moles, x = 1.5-2.
2, y = 0-5. ), The crystalline phase of the crystalline sodium silicate is δ phase and α phase, or further β phase and / or NS
And the constituent weight ratio of the α, β and δ crystal phases is 0.05 ≦ α / (α + β + δ) ≦ 0.2
0, 0 ≦ β / (α + β + δ) ≦ 0.12 and 0.78
≦ δ / (α + β + δ) ≦ 0.95, a powder detergent composition for clothing having a bulk density of 0.50 g / mL or more; [2] a crystalline sodium silicate represented by the formula (1): When the constituent weight ratio of the crystal phase is 0.085 ≦ α / (α + β +
δ) ≦ 0.15, 0.01 ≦ β / (α + β + δ) ≦ 0.
10, and the powder detergent composition for clothing according to the above [1], wherein 0.80 ≦ δ / (α + β + δ) ≦ 0.90.

[3] a) a surfactant; b) a crystalline sodium silicate Na ₂ O.xSiO ₂ .yH ₂ O (1) having an average particle size in the range of 1 to 100 μm and represented by the following formula (1): (Where x and y represent the number of moles, x = 1.5-2.
2, y = 0-5. The crystalline phase of the crystalline sodium silicate may be a δ phase and an α phase, or a β phase and / or N phase.
It is composed of a crystalline phase of S phase, and a constituent weight ratio of crystalline phases of α phase, β phase and δ phase is 0.05 ≦ α / (α + β + δ) ≦ 0.2.
0, 0 ≦ β / (α + β + δ) ≦ 0.12 and 0.78
≦ δ / (α + β + δ) ≦ 0.95. ), And c) a sequestering agent other than the component b, wherein the total amount of the components a, b, and c is 70 to 1 of the total detergent composition.
And the ratio of the component b to the component a is b / a = 9/1 to 9/11 by weight, and the ratio of the component b to the component c is b / c = 4/1 by weight. ~ 1/15
The powder detergent composition for clothing according to the above [1] or [2], wherein the ratio of the component b to the component a is b / b in weight ratio.
The powder detergent composition for clothing according to the above [3], wherein a = 9/1 to 1/1 and the ratio of the component b to the component c is b / c = 3/1 to 1/15 by weight. 5] The powder detergent composition for clothing according to the above [3] or [4], wherein 50% by weight or more of the component a is a polyoxyethylene alkyl ether.

[6] When the hardness of the washing liquid is 2 to 6 ° DH, the ratio of the component b to the component c is b / c =
The standard usage amount at the time of 3/1 to 3/7 is 0.33 to
The powder detergent composition for clothing according to any one of the above [1] to [5], which is 0.67 g / L, [7] a case where the hardness of the washing liquid is 6 to 10 ° DH, and B / c = 4/3 to 1
The standard usage amount at the time of / 6 is 0.50 to 1.20 g
The powder detergent composition for clothing according to any one of [1] to [5], wherein the hardness of the washing liquid is 10 to 20 ° DH, and the ratio of the b component to the c component. Is b / c = 1/1 ~
The standard usage at 1/15 is 0.80 to 2.5
0 g / L, the powder detergent composition for clothing according to any one of the above [1] to [5],

[9] The bulk density of the detergent composition is 0.65 to 1.20.
g / mL, which relates to the powder detergent composition for clothing according to any one of the above [1] to [8].

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The powder detergent composition for clothing according to the present invention has a bulk density of 0.50 g / mL or more and an average particle size in the range of 1 to 100 μm. during crystalline sodium silicate _{Na 2 O · xSiO 2 · yH} 2 O (1) ( wherein, x and y represent the number of moles, x = 1.5 to 2.
2, y = 0-5. ), The crystalline phase of the crystalline sodium silicate is δ phase and α phase, or further β phase and / or NS
And the constituent weight ratio of the α, β and δ crystal phases is 0.05 ≦ α / (α + β + δ) ≦ 0.2
0, 0 ≦ β / (α + β + δ) ≦ 0.12 and 0.78
≦ δ / (α + β + δ) ≦ 0.95.

In the present invention, a crystalline sodium silicate having a good ion exchange rate can be obtained by satisfying the above conditions, but preferably 0.085 ≦ α / (α + β).
+ Δ) ≦ 0.15, 0.01 ≦ β / (α + β + δ) ≦
0.10 and 0.80 ≦ δ / (α + β + δ) ≦ 0.90
Are more effective. It is preferable that 5% by weight or more of the crystalline sodium silicate that satisfies such a crystal phase is mixed in the powder detergent composition for clothing, and 10% by weight to 6% by weight.
It is preferable to add 0% by weight. In addition, from the viewpoint of obtaining particularly excellent detergency, it is particularly preferable to mix as follows depending on the hardness of the washing water to be used.

1) When washing water of 2 to 6 ° DH is used, it is preferable to add 20 to 50% by weight of crystalline sodium silicate in the whole composition. 2) Use of washing water of 6 to 10 ° DH. In this case, it is preferable to mix 10 to 45% by weight of crystalline sodium silicate in the whole composition. 3) When washing water of 10 to 20 ° DH is used, 5 to 30% of crystalline sodium silicate in the whole composition is used. It is preferable to mix by weight%.

The average particle size of the crystalline sodium silicate is 1 to
It is 100 μm, preferably 10 to 50 μm. From the viewpoint of preventing an increase in hygroscopicity, the average particle size is preferably 1 μm or more,
It is preferably 100 μm or less from the viewpoint of the ion exchange rate.
Here, the average particle size is the median size of the particle size distribution.

The crystalline sodium silicate having such an average particle size and particle size distribution can be prepared by crushing using a crushing machine such as a vibration mill, a hammer mill, a ball mill, a roller mill and the like. Here, 1 to 100
Crystalline sodium silicate particles adjusted to μm can be granulated and agglomerated for the purpose of improving handling properties and the like. At this time, the granulated / agglomerated substance can exceed 100 μm, but the average primary particle diameter which can be easily confirmed using a scanning electron microscope is 1 to 100 μm.
m.

The α, β and δ phases are described in JP-A-60-22789.
As shown in Japanese Patent Publication No. 5 (1993), this is a crystal phase unique to crystalline sodium silicate. Crystalline sodium silicate has many other crystal phases, but in the present invention, it is particularly preferable to mix the NS phase, and the detergency is further improved. Also, δ
It is preferable that the total composition ratio of the phase, the α phase, the β phase, and the NS phase occupy substantially 100% by weight of the total crystalline phase of the crystalline sodium silicate. In the formula (1), preferably, x
= 1.7 to 1.9, y = 0.

The crystalline sodium silicate of the present invention is disclosed in
The production method described in JP-A-60-227895,
Amorphous glassy sodium silicate at 200-1000 ° C
(For details, for example, Phys. Che
m. Glasses.7, 127-138 (1966), Z. Kristallogr.,12
9, 396-404 (1969) etc.)
The method for baking water glass and its dried material whose composition has been adjusted
Therefore, it is easy to produce a material having a suitable crystal phase composition ratio.
Can be. The firing temperature is preferably 500-900 ° C.
More preferably 650 to 780 ° C.,
Sintering at 680 to 750 ° C is particularly preferred from the viewpoint of suppression.
No. From the viewpoint of sufficiently promoting crystallization, the firing temperature is set to 50.
It is preferably 0 ° C. or higher, and
From the viewpoint of prevention, the firing temperature must be 900 ° C or less
Is preferred. This is because crystallinity decreases when melting begins,
This is because it becomes difficult to obtain an excellent detergency.

For the crystal phase, powder X-ray diffraction measurement was performed.
Standard Committee for Powder Diffraction (JCPDS: Joint Committee of
Powder Diffraction Standard) Diffraction data (PDF-No. 22-1397, 24-1123, 2) described in a powder diffraction data file (PDF)
2-1396 and 16-818), α, β,
The crystal phases of δ and NS can be identified, and the ratio (constitutive weight ratio) can be measured and confirmed by determining the intensity of the main diffraction peak.

As described above, crystalline sodium silicate has ion exchange ability and alkali ability, and it has been suggested that zeolite and carbonate may be replaced by one agent of crystalline sodium silicate. Have been. JP-A-6-505045 mentioned above discloses a detergent which does not contain a carbonate and a polymer carboxylate.
A system in which crystalline sodium silicate is blended as a detergent of 4 to 21 g / 30 L is specifically disclosed. These prior arts have simply replaced some or all of the builders, such as zeolites and sodium carbonate, with crystalline sodium silicate. However, when it was actually replaced and examined, it was not possible to obtain a sufficient detergency when the amount used once was reduced. We considered the reason as follows.

The conventional mainstream approach to cleaning is based on the idea of solubilizing oil in dirt with a surfactant. Taking the human body-derived sebum dirt (easily observed on collars and sleeves), which is the most typical dirt adhering to clothing, as an example, sebum dirt contains 70% by weight or more of oil such as free fatty acid and glyceride in the dirt. (Kashiichiro et al., Oil Chemistry, 19 , 1095 (1969), etc.), which trap carbon and mud in the dust, exfoliated keratin, etc., and are observed as dirt. Therefore, by removing oil in these dirt, carbon, mud, and keratin can also be dropped from clothing. As a method for removing oil, a method of solubilizing in surfactant micelles has been found. A formulation containing a surfactant as a main component has been studied. This concept basically did not change when the detergent was changed from a low bulk density detergent to a high bulk density detergent, and there was no significant change in the surfactant concentration in the washing liquid. These facts are also shown in the encyclopedia of detergents and cleaning by Haruhiko Okuyama et al., P.428 of the first edition (Asakura Shoten, 1990). The concentration of components other than sodium sulfate in the washing liquid is basically Almost unchanged.

The concept of the composition of a detergent containing an alkaline agent such as zeolite and sodium carbonate is based on these washing theories. Therefore, in order to obtain high detergency, the concentration of the surfactant in the washing liquid must be increased. For this purpose, a surfactant is mainly used in the detergent composition, and the surfactant concentration is determined in consideration of the amount of the detergent itself added to the washing liquid.

Therefore, we first obtained a very interesting finding in the washing of clothes from a very simple washing system, starting from basically reviewing the composition of the detergent. That is, the inventors of the present invention diligently studied the effects of the pH of the washing liquid and the hardness of the washing liquid on washing, and found the following. (B) High p
When the hardness is H and the hardness is lower, the dependency of the detergency on the surfactant concentration is lower, and an excellent detergency is obtained.
(B) Even if the pH is high, if the hardness is high, the cleaning power is extremely reduced. (C) When washing is performed only with a surfactant without adding an alkali agent, the washing power at low hardness is low, but the dependency of the washing power on the hardness is sufficiently smaller than that of a system containing an alkali agent. The present inventors have paid attention to the relationship between the washing liquid and the stain regarding the result obtained.

As described above, sebum stains, which are typical stains adhering to clothes, contain fatty acids and glycerides, and the stains are a mixture of these organic substances with carbon, mud or keratin. Conceivable. In the case of a high pH, the fatty acid content increases due to the hydrolysis of glyceride, while the reaction of converting the fatty acid into an alkali salt proceeds. Alkali metal salts of fatty acids are soaps, which promote the release of dirt into the wash liquor. However, an alkali metal salt of a fatty acid ion-exchanges with calcium or magnesium in hard water more easily than a fatty acid, and therefore, the alkali metal salt of a fatty acid easily forms scum with calcium or magnesium. As a result, when the hardness is high, the dirt is solidified without releasing from the interface of the cloth, and as a result, the dirt is not removed. In particular, the scumming rate is extremely faster in the case of alkali metal salts than in fatty acids (unneutralized substances). That is, in a system in which the hardness component has not been completely removed, the higher the alkalinity (pH), the higher the scumming speed and the less dirt is removed. Since crystalline sodium silicate has sufficiently higher alkalinity than sodium carbonate, which is a conventional alkali agent, it is easily affected by scum formation by calcium and magnesium, and lower hardness is required.

From the above, as a compositional requirement for reducing the standard amount of use, in addition to the addition of sodium silicate for maintaining a high alkalinity, it is necessary to reduce the hardness of the washing liquid. Sequestering agents other than crystalline sodium silicate are required. In addition, by reducing the surfactant concentration in the washing liquid at such low hardness and high pH, it is possible to reduce the standard usage amount of the obtained detergent composition without impairing the detergency. And found a specific compounding ratio for that purpose.

Accordingly, the powder detergent composition for clothing of the present invention comprises the following components a) a surfactant, and b) an average particle size in the range of 1 to 100 μm in terms of detergency. sodium crystalline silicate _{Na 2 O · xSiO 2 · yH} 2 O (1) ( wherein, x and y represent the number of moles, x = 1.5 to 2.
2, y = 0-5. The crystalline phase of the crystalline sodium silicate may be a δ phase and an α phase, or a β phase and / or N phase.
It is composed of a crystalline phase of S phase, and a constituent weight ratio of crystalline phases of α phase, β phase and δ phase is 0.05 ≦ α / (α + β + δ) ≦ 0.2.
0, 0 ≦ β / (α + β + δ) ≦ 0.12 and 0.78
≦ δ / (α + β + δ) ≦ 0.95. ), And c) a sequestering agent other than the component b, wherein the total amount of the components a, b, and c is 70 to 1 of the total detergent composition.
And the ratio of the component b to the component a is b / a = 9/1 to 9/11 by weight, and the ratio of the component b to the component c is b / c = 4/1 by weight. ~ 1/15
Is preferred. Particularly preferably, the ratio of the b component to a is b / a = 9/1 to 1/1 in weight ratio, and c
B / c = 3/1 to 1 / in weight ratio
Fifteen. Further, the crystalline sodium silicate has the same average particle size, crystal phase composition weight ratio, composition and the like as described above, and the preferred range is also the same as described above.

The crystalline sodium silicate having the above-described crystalline phase composition is excellent in that the ion exchange rate is high, so that the rate of lowering the hardness of the washing liquid is high, and the amount of the present invention used is small. Although preferable in a detergent composition, in the above-mentioned detergent composition, excellent detergency can be obtained even in a use amount smaller than the conventional standard use concentration.

The standard amount of detergent used varies from country to country in the world. This is because tap water hardness varies from country to country.
For example, in Japan it is usually around 4 ° DH,
In the United States, water with a high hardness of 6 ° DH or more and in Europe exceeding 10 ° DH is used as washing water. This changes the absolute amount of sequestering agent, and consequently the standard usage is adjusted accordingly. Although the amount of the sequestering agent added 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 in the past.

Specifically, when the initial hardness is different for each washing liquid, the standard usage amount represented by the detergent concentration for obtaining excellent detergency is as follows. 1) In the case of Japanese conditions where the hardness of the washing liquid is 2 to 6 ° DH, the ratio of the component b to the component c is b / c =
At 3/1 to 3/7, the standard usage is 0.33 to 0.6
7 g / L is preferred, and more preferably 0.33-0.5.
0 g / L. 2) When the hardness of the washing liquid is 6 to 10 ° DH, b
When / c = 4/3 to 1/6, the standard amount is 0.50 to 0.50.
1.20 g / L is preferred, more preferably 0.50 to
It is 1.00 g / L. 3) When the hardness of the washing liquid is 10 to 20 ° DH,
When b / c = 1/1 to 1/15, the standard amount is 0.8
0 to 2.50 g / L is preferable, and more preferably 1.0 to 2.50 g / L.
0 to 2.00 g / L.

Hereinafter, the cleaning components blended in the present invention will be described. The b component is as described above.

A) Surfactant The surfactant used in the present invention is preferably 50 to 100% by weight of a nonionic surfactant in all the surfactants.
More preferably, those containing 65 to 100% by weight can be used without particular limitation as those generally used for detergents. 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. In addition, from the viewpoint of detergency, 5
Preferably, 0% by weight or more is polyoxyethylene alkyl ether.

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, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alkyl ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid Esters, higher fatty acid alkanolamides, alkylglucosides, alkylglucoseamides, alkylamine oxides, and the like.

Among them, ethylene oxide adducts of linear or branched primary or secondary alcohols having 10 to 18 carbon atoms, particularly as nonionic surfactants,
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. .

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfofatty acid salt or ester salt, and alkyl or alkenyl ether carboxylate. Examples thereof include acid salts, amino acid type surfactants, N-acyl amino acid type surfactants, and the like, preferably alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate and the like. Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylamine salt. 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 of the whole composition, and particularly 1) 12 to 30% when washing water of 2 to 6 ° DH is used.
2) When washing water of 6 to 10 ° DH is used, 8 to 25% is used.
3) When using 10 to 20 ° DH washing water, 5 to 2%
It is preferable to add 0% by weight.

The detergent composition for clothing of the present invention has a surfactant concentration in a washing liquid of 0.0
When the detergent composition is added to the washing water so as to have a concentration of 7 to 0.17 g / L, the standard amount of the detergent composition for obtaining sufficient detergency can be smaller than that of the conventional detergent composition.

C) Sequestering agent other than crystalline sodium silicate The sequestering agent other than crystalline sodium silicate in the present invention has a Ca ion trapping ability of 200 CaCO ₃ mg.
/ G or more. In particular, those containing 10% by weight or more of a carboxylate polymer are preferable, and specific examples of such a polymer include a polymer or a copolymer having a repeating unit represented by the general formula (2). .

[0041]

Embedded image

(Wherein X ₁ is methyl, H or COOX
₃ , X ₂ is methyl, H or OH, X ₃ is H, alkali metal, alkaline earth metal, NH ₄ ion or 2-
Shows hydroxyethylammonium ion. )

In the general formula (2), 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 may be, for example, a polymerization reaction of acrylic acid, (anhydride) maleic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid, isocrotonic acid and salts 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, the above-mentioned polymers and copolymers having a weight average molecular weight of preferably 8 to 1,000,000 are used, and more preferably 5000 to 20
Ten thousand things are used.

The copolymerization ratio between the repeating unit of the general formula (2) and another copolymerizable monomer in the case of copolymerization is not particularly limited, but is preferably the repeating unit of the general formula (2) / 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 preferably 1 to 50 in the total composition.
%, More preferably 2 to 30% by weight, particularly preferably 5 to 15% by weight. If the amount is less than 1% by weight, the effect of the present invention cannot be obtained. If the amount exceeds 50% by weight, the effect of addition is saturated, so that the cost is unnecessarily increased and there is no point.

Further, (c) is contained in the sequestering agent of the component c.
-I) The above-mentioned Ca ion trapping ability is 200 CaCO ₃ m
g / g or more 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 _{aluminosilicate, x "(M 2 O)} · Al 2 O 3 · y" (SiO 2) · w "(H 2 O) (3) ( in the formula, M 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 ″
20. ) The ratio of the ci component to the c-ii component is ci / c-ii = 1/20 to 4/1, preferably 1/9 to 4/1 by weight ratio, and ci and c- Those in which the total amount of ii accounts for 70 to 100% by weight of the sequestering agent of the component c are more preferable.

Examples of the aluminosilicate include crystalline ones and amorphous ones. The crystalline ones are particularly preferably those represented by the following general formula. _{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,
Average primary particle size of 0.1 represented by X-type and P-type zeolites.
1-10 μm synthetic zeolites are 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-mentioned crystalline aluminosilicate can be produced by a conventional method. For example, JP-A-50-123
81 and JP-A-51-12805 can be used.

On the other hand, an amorphous aluminosilicate represented by the same general formula as that of the above-mentioned 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 to Al ₂ O ₃ is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0;
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.

Next, the resulting white precipitate slurry is heated at 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 CaC
An amorphous aluminosilicate oil-absorbing carrier having an O ₃ mg / g or more and an oil absorption capacity of 80 ml / 100 g or more can be easily obtained (Japanese Patent Application Laid-Open Nos. 62-191417 and 62-19).
No. 1419).

Other sequestering agents include aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and the like. Salts, salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, salts of amino acids such as aspartic acid and glutamic acid, and aminopolyacetates such as nitrilotriacetate and ethylenediaminetetraacetate.

As other components in the present invention, in addition to crystalline sodium silicate, various components such as alkali metal salts such as carbonates and sulfites and organic amines such as alkanolamines can be mentioned as alkali agents.

Also, it can be blended with detergents generally such as non-dissociated polymers such as polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone, builders such as salts of organic acids such as diglycolic acid and oxycarboxylate, and carboxymethyl cellulose. Known examples include an anti-fading agent and an anti-redeposition agent.

In addition, the detergent composition of the present invention can also contain the following components. That is, enzymes such as protease, lipase, cellulase, and amylase,
Anticaking agents such as lower alkylbenzene sulfonates, sulfosuccinates, talc, calcium silicate, etc. of about 4, antioxidants such as tertiary butylhydroxytoluene and distyrenated cresol, bleaching agents such as sodium percarbonate and tetraacetylethylenediamine, etc. , A bleach activator, a fluorescent dye, a bluing agent, a fragrance, etc., but these are not particularly limited, and may be blended according to the purpose. In the detergent composition of the present invention having a small amount of use, the total amount of a, b and c is preferably 70 to 100% by weight, more preferably 80 to 100% by weight. From the viewpoint of reducing the standard usage amount of the obtained detergent composition, the case where the total amount of a, b, and c is 70% by weight or more is preferable.

The detergent composition of the present invention contains the above-mentioned components. The method for producing the detergent composition is not particularly limited, and a conventionally known method can be used. The detergent composition of the present invention has a bulk density of 0.50 g /
mL, and particularly preferably 0.65 to 1.20 g / mL. For example, as a method for obtaining a high bulk density detergent, JP-A-61-69897 and JP-A-61-9897
-69899, JP-A-61-69900,
The method described in JP-A-5-209200 can be used.

[0058]

The present invention will be described in more detail with reference to the following Preparation Examples and Examples, which should not be construed as limiting the present invention. The measured value is
It was measured by the following method.

(1) Ion-capturing ability The ion-capturing ability was measured according to the following methods, depending on whether the sequestering substance used was an ion exchanger or a chelating agent. In addition, as a method of indicating the ion-capturing ability of the sequestering agent, it is indicated by CEC (calcium ion exchange capacity) in the table of the examples similarly to the crystalline sodium silicate. The DH hardness was measured by an ion coupling plasma method (ICP method). In the table,
Crystalline sodium silicates A and B and crystalline aluminosilicate are ion exchangers, and AA / MA copolymer and sodium polyacrylate are chelating agents.

In the case of an ion exchanger, 0.1 g of the ion exchanger was precisely weighed, added to 100 ml of an aqueous calcium chloride solution (concentration: 500 ppm as CaCO ₃ ), stirred at 25 ° C. for 60 minutes, and then the pore size was changed to 0.2.
Filtration was performed using a μm membrane filter (manufactured by Advantech, nitrocellulose), and the filtrate was 10 m
The amount of Ca contained in 1 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, using a calcium ion electrode, the ability to capture Ca ions was measured as follows. All the solutions were prepared using the following buffers. _{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 calcium ion concentration and the potential as shown in FIG. 1 was prepared. (Ii) Measurement of Capability of Capturing Calcium Ions About 0.1 g of a chelating agent was weighed into a 100 mL volumetric flask, and the volume was increased with the above buffer solution. In addition, the calcium ion concentration is 20,000 ppm (CaCO ₃ conversion)
Corresponding CaCl ₂ aqueous solution (pH 10.0) was added dropwise from a burette in. For the dropwise addition, use a CaCl ₂ aqueous solution of 0.1 to
The test was performed by adding 0.2 mL each, and the potential at that time was read. Similarly, the buffer containing no chelating agent also has C
An aCl ₂ aqueous solution was added dropwise. This solution is called a blank. The calcium ion concentration was determined from the calibration curve of FIG.
The relationship between the amount of the CaCl ₂ aqueous solution added and the calcium ion concentration is shown in the graph (FIG. 2). In FIG. 2, line P shows data when only a buffer solution was used (blank), and line Q shows data when a chelating agent-containing buffer solution was used. Line Q
A is the intersection of the extension of the graph with the horizontal axis of the graph of FIG.
The calcium ion trapping ability of the chelating agent was determined from the calcium ion concentration of the blank in the above.

(2) Average Particle Size and Particle Size Distribution of Crystalline Sodium Silicate The average particle size and particle size distribution were measured using a laser diffraction type particle size distribution analyzer. 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 crystalline sodium silicate was suspended. Subsequently, the mixture was stirred for 1 minute while being irradiated with ultrasonic waves to sufficiently disperse the crystalline sodium silicate.
An e-laser (632.8 nm) was incident, and the particle size distribution was measured from the diffraction / scattering pattern. Analysis is by Frau
Using both the nofer diffraction theory and the Mie scattering theory, the particle size distribution of suspended particles in the liquid was measured in the range of 0.04 to 262 μm. The average particle size was the median size of the particle size distribution.

(3) X-ray Diffraction Measurement A sample pulverized until it passed through a sieve having an opening of 75 μm was packed in a glass folder, and was subjected to X-ray diffraction using a powder X-ray diffractometer (RAD-C system manufactured by Rigaku Denki). A line diffraction measurement was performed. X-ray monochromatized to Kα radiation by a pyrolytic graphite monochromator using Cu as the target (acceleration voltage, current = 40 kV, 80 mA, wavelength = 1.5407)
I) was used. For the diffraction angle range 2θ = 10 to 40 °, measurement was performed by θ-2θ scanning at a scanning speed of 5 ° / min. The obtained diffraction lines were subjected to smoothing (smoothing point = 15) and background removal, and then the diffraction intensity of each peak was determined. The main diffraction peaks of each of the crystal phases α, β, and δ have d values of 3.31 ± 0.04, respectively.
The ratio of each phase was calculated from the intensity as a peak of {4.15 ± 0.04}, 3.95 ± 0.04 °. The intensities of the diffraction lines used for the calculation are _expressed as I _3.31 , I _4.15 , I
_{As 3.95} , each phase was calculated using the formula of α = I _3.31 β = 4.33 × I _4.15 δ = I _3.95 − (1.33 × I _4.15 ), and the breakdown was determined.

Preparation Example 1 (Crystalline sodium silicate A) No. 3 sodium silicate (Na ₂ O = 9.9%, SiO ₂ = 2)
9.6%) sodium hydroxide 40.4 in 500 parts by weight
An alkaline solution in which parts by weight were dissolved was prepared. This alkaline solution was baked at a temperature of 720 ° C. for 5 hours using a nickel crucible to be crystallized. The obtained fired body was pulverized using a mortar until it passed through a sieve having an opening of 75 μm to obtain a powder of crystalline sodium silicate A. When the ratio of the crystal phase of the obtained powder was measured by X-ray diffraction measurement, the ratio was α = 0.09, β = 0.04,
δ = 0.87. Further, in equation (1), x =
1.9, y = 0, and the average particle size was 30.6 μm.

Preparation Example 2 (Crystalline sodium silicate B) No. 3 sodium silicate (Na ₂ O = 9.9%, SiO ₂ = 2)
9.6%) sodium hydroxide 40.4 in 500 parts by weight
An alkaline solution in which parts by weight were dissolved was prepared. This alkaline solution was baked at a temperature of 650 ° C. for 7 hours using a nickel crucible to be crystallized. The obtained fired body was pulverized using a mortar until it passed through a sieve having an opening of 75 μm to obtain a crystalline sodium silicate B powder. When the ratio of the crystal phase of the obtained powder was measured by X-ray diffraction measurement, the ratio was α = 0.07, β = 0.21,
δ = 0.72. Further, in equation (1), x =
1.9, y = 0, and the average particle size was 29.8 μm.

Preparation Example 3 (Amorphous Aluminosilicate) Sodium carbonate was dissolved in ion-exchanged water to prepare a 6% by weight aqueous solution. 132 g of this aqueous solution and 38.28 g of aqueous sodium aluminate 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. Subsequently, the reaction system was heated to 50 ° C. and stirred at the same temperature for 30 minutes. After that, CO
₂ Gas was blown in to neutralize excess alkali (pH =
9.0). The obtained neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). The filter cake is washed with water 1000 times and filtered and dried (105
C., 300 torr, 10 hours), and the remainder was dried under the same conditions (without washing). Further, crushing was performed to obtain an amorphous aluminosilicate powder of the present invention. The aqueous sodium aluminate solution was placed in a 1000 ml four-necked flask with 243 g of Al (OH) ₃ and 48% by weight of NaOH.
298.7 g of an aqueous solution 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 follows:
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 (1.0 Na 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% by volume in the total pore volume, 0.1 μm or more, 2.0 μm or more.
The ratio of the pore volume having a pore diameter of less than m is 7% of the total pore volume.
The content was 6.3% by volume and the moisture content was 11.2% by weight.

Examples 1-2, Comparative Examples 1-2 Aqueous components (AS-Na, acrylic acid / maleic acid copolymer, sodium polyacrylate, sodium sulfite, sodium sulfate, sodium tallow fatty acid) corresponding to the blending amounts and blending amounts 50% by weight of crystalline aluminosilicate of 1/2 amount of
A solid slurry was formed and spray dried. The obtained particles and the remaining powdery raw material (amorphous aluminosilicate, crystalline sodium silicate A or B) equivalent to the blending amount were mixed with a Loedige mixer (stirring tumbling granulator, manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 liters, equipped with a jacket) and stirring was started. Warm water of 40 ° C. was flowed through the jacket. A material obtained by heating a polyoxyalkylene alkyl ether equivalent to the blending amount in advance to 70 ° C. was added thereto and granulated. Further, after adding a 1/3 amount of the crystalline aluminosilicate and granulating (surface modification step), the obtained particles were added with 1% of the amount.
The powdery detergent containing water shown in Table 1 was obtained by dry-mixing the crystalline aluminosilicate in an amount of / 6 and the enzyme in an amount equivalent to the compounding amount. The bulk density and the average particle size were as shown in Table 1.

Test Example 1 Using the detergent compositions obtained in the above Examples and Comparative Examples, a cleaning test was performed under the following conditions. (Preparation of artificially stained cloth) An artificially stained cloth having the following composition was adhered to a cloth (cotton gold cloth 2003, manufactured by Tanika Shoten) to prepare an artificially stained 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 attaching the artificially contaminated liquid to the cloth includes a gravure roll cell capacity of 58 cm ³ / cm ² ,
The coating speed was 1.0 m / min, the drying temperature was 100 ° C., and the drying time was 1 minute. [Composition of artificial contaminated liquid] Lauric acid 0.44% by weight Myristic acid 3.09% by weight 2.31% by weight pentadecanoic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57% by weight Olein 7.75% by weight of acid 13.06% by weight of triolein 2.18% by weight of n-hexadecyl palmitate 6.53% by weight of squalene 1.94% by weight of egg white lecithin liquid crystal material 8.11% by weight of Kanuma red soil 8.11% by weight of carbon black 0.01 Weight% tap water balance

(Washing conditions) Using a tergotometer, rotation speed 100 rpm, washing time 10 minutes, temperature 20
° C, water used 4 ° DH (Ca / Mg = 3/1), two different standard usages (detergent concentration), ie 0.67 g /
Washing was performed at liter and 0.50 g / liter. Usually, the hardness component of the washing water is represented by Ca ²⁺ and Mg ²⁺ , and the weight ratio is Ca / Mg = (60-85) /
(40 to 15), but here, Ca / Mg = 3/1 was used as model water. “° DH” means Mg
This is the hardness when equivalent moles of ions are replaced with Ca.

(Calculation of cleaning rate) 55% of original cloth and before and after cleaning
The reflectance at 0 nm 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 shown in Table 1. 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 Table 1 are as follows. AS-Na: Sodium alkyl sulfate, 12 carbon atoms Fatty acid Na: sodium tallow fatty acid, 14 to 18 carbon atoms Polyoxyethylene alkyl ether: 12 to 14 carbon atoms in alkyl, average of ethylene oxide in Dovanol 23 (manufactured by Mitsubishi Yuka) AA / MA copolymer with 8 mole addition: "Sokalan CP5"
(Manufactured by BASF Actchenge Shellshaft, a copolymer of acrylic acid-maleic acid as a monomer, average molecular weight of 70,000, sodium polyacrylate: a polymer of sodium acrylate,
Average molecular weight 10000 Crystalline aluminosilicate: 4A type zeolite, average particle size 3 μm (manufactured by Zeobuilder Co., Ltd.) Enzyme: Cellulase K (described in JP-A-63-264699) 0.5% by weight, API-21 (Showa) Denko Corporation)
1.0% by weight, 0.5% by weight of Lipolase 100T (Novo)

[0073]

[Table 1]

In the results of Table 1, the cleaning rates of the detergent compositions using crystalline sodium silicate having the same composition but different composition ratios of the crystalline phases are compared. The powder detergent compositions for clothing of the present invention have different detergent concentrations. In both cases, the cleaning rate is improved by about 4%, and this value is considered to correspond to a remarkable effect in the art.

[0075]

Industrial Applicability The powder detergent composition of the present invention exhibits a high ion exchange rate because the crystalline phase of crystalline sodium silicate is adjusted so as to have a specific composition ratio, and is excellent in clothing. This has the effect of imparting improved cleaning properties.
Furthermore, in addition to the crystalline sodium silicate adjusted to have a specific composition ratio, the powder detergent composition of the present invention uses other sequestering agents and surfactants in a specific ratio in combination. Therefore, there is an effect that the standard usage amount can be reduced.

[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 the relationship between the amount of CaCl ₂ aqueous solution added and the calcium ion concentration.

[Explanation of symbols]

 A Intersection between the extension of line Q and the horizontal axis of the graph in FIG. 2 P Data when only buffer is used (blank) Q Data when buffer containing sample is used

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ichiro Sakamoto 1334 Minato, Wakayama City Kao Corporation Research Laboratory (72) Inventor Shigeru Tamura 1334 Minato Wakayama City Research Center Kao Corporation Research Laboratory (72) Inventor Masaki Tsumori Wakayama City No. 1334 Minato In-house of Kao Corporation (56) References JP-A-4-160013 (JP, A) JP-A-4-202009 (JP, A) JP-A-7-187655 (JP, A) JP-A-2 178398 (JP, A) Table 7-509527 (JP, A) WO 97/19156 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-17 / 08

Claims (9)

(57) [Claims] 1. A crystalline sodium silicate of the following formula (1) having an average particle diameter in the range of 1 to 100 μm: Na ₂ O.xSiO ₂ .yH ₂ O (1) (where x and y are Represents the number of moles, x = 1.5-2.
2, y = 0-5. ), The crystalline phase of the crystalline sodium silicate is δ phase and α phase, or further β phase and / or NS
And the constituent weight ratio of the α, β and δ crystal phases is 0.05 ≦ α / (α + β + δ) ≦ 0.2
0, 0 ≦ β / (α + β + δ) ≦ 0.12 and 0.78
A powder detergent composition for clothing having a bulk density of 0.50 g / mL or more, wherein ≦ δ / (α + β + δ) ≦ 0.95. 2. The composition weight ratio of the crystalline phase of the crystalline sodium silicate represented by the formula (1) is 0.085 ≦ α / (α +
β + δ) ≦ 0.15, 0.01 ≦ β / (α + β + δ) ≦
0.10 and 0.80 ≦ δ / (α + β + δ) ≦ 0.9
The powder detergent composition for clothing according to claim 1, which is 0. Wherein a) a surfactant, b) crystalline sodium silicate having an average particle diameter of below formula in the range of 1 to 100 [mu] m (1) wherein _{Na 2 O · xSiO 2 · yH} 2 O (1) (Where x and y represent moles, x = 1.5-2.
2, y = 0-5. The crystalline phase of the crystalline sodium silicate may be a δ phase and an α phase, or a β phase and / or N phase.
It is composed of a crystalline phase of S phase, and a constituent weight ratio of crystalline phases of α phase, β phase and δ phase is 0.05 ≦ α / (α + β + δ) ≦ 0.2.
0, 0 ≦ β / (α + β + δ) ≦ 0.12 and 0.78
≦ δ / (α + β + δ) ≦ 0.95. ), And c) a sequestering agent other than the component b, wherein the total amount of the components a, b, and c is 70 to 1 of the total detergent composition.
And the ratio of the component b to the component a is b / a = 9/1 to 9/11 by weight, and the ratio of the component b to the component c is b / c = 4/1 by weight. ~ 1/15
The powder detergent composition for clothing according to claim 1 or 2, wherein 4. The ratio of the b component to the a component is b / a = 9/1 to 1/1 in weight ratio, and the ratio of the b component to the c component is b / c = 3/1 to 1 in weight ratio. The powder detergent composition for clothing according to claim 3, wherein the ratio is / 15. 5. The powder detergent composition for clothing according to claim 3, wherein 50% by weight or more of the component a is a polyoxyethylene alkyl ether. 6. When the hardness of the washing liquid is 2 to 6 ° DH, the ratio of the component b to the component c is b / c = 3/1 to 1.
The standard usage amount at 3/7 is 0.33-0.67
The powder detergent composition for clothing according to any one of claims 1 to 5, which is g / L. 7. When the hardness of the washing liquid is 6 to 10 ° DH, the ratio of the component b to the component c is b / c = 4/3.
When the standard usage amount is up to 1/6, 0.50 to 1.2
The powder detergent composition for clothing according to any one of claims 1 to 5, which is 0 g / L. 8. When the hardness of the washing liquid is 10 to 20 ° DH, the ratio of the component b to the component c is b / c = 1 / b.
When the standard usage amount is 1 to 1/15, 0.80
The powder detergent composition for clothing according to any one of claims 1 to 5, which is 2.50 g / L. 9. The detergent composition having a bulk density of 0.65 to 1.
The powder detergent composition for clothing according to any one of claims 1 to 8, which is 20 g / mL.