Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – Specific organic component
Reexamination Certificate
2000-01-06
2001-07-24
Kopec, Mark (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
Specific organic component
C510S509000, C510S485000, C510S531000, C510S532000, C510S533000, C510S534000, C510S276000, C510S289000, C510S300000, C510S315000, C510S334000, C510S367000, C510S377000, C510S443000, C510S444000, C510S507000
Reexamination Certificate
active
06265371
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a powdery detergent composition. More specifically, it relates to a powdery detergent composition having a high detergency and an excellent storage stability (caking resistance).
PRIOR ART
A detergent for clothes contained before a phosphorus compound such as sodium tripolyphosphate as a sequestering agent. At present, a zeolite, crystalline sodium aluminosilicate is mainly used.
Nevertheless, since the zeolite sometimes cannot exhibit a satisfactory performance by the washing for a short period of time at a low temperature, it contains a polymeric dispersant such as a polycarboxylic acid type polymer or the like. This polymer has a function of sequestering at a low water temperature, but it involves a problem that a biodegradability is insufficient.
In recent years, studies on builders having an excellent biodegradability and an excellent sequestering performance have been made. For example, there are JP-A 50-3979, JP-A 55-157695, JP-A 55-160099, JP-A 56-81399, WO-9612784, WO-9630479, U.S. Pat. No. 3,637,511 and the like. However, when a detergent is blended with these specific organic builders, there is a problem in the storage stability (caking resistance) of the detergent.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to provide a granular detergent composition which contains high-performance water-soluble builders and which is excellent in the storage stability (caking resistance) while having a high detergency.
The present inventors have found that a detergent composition containing a water-soluble polycarboxylic acid chelating agent having a specific average degree of neutralization and an alkali agent in specific amounts respectively can solve the above-mentioned problems.
The present invention is to provide a granular detergent composition comprising
(a) 1 to 50% by weight of a chelating agent composed of a compound having an average degree of neutralization in a molecule of 20 to 70%, a molecular weight of 600 or less, the number of carboxyl groups contained in one molecule of 3 to 5, and a constant of a chelating stability with Ca
2+
of 6 to 13,
(b) 5 to 60% by weight of an alkali agent composed of a compound a 0.1% by weight aqueous solution or dispersion of which has the maximum pH of 10 or more at 20° C., at least 5 ml of a 0.1 N HCl aqueous solution being required to adjust 1 liter of the aqueous solution or the dispersion to pH 9, and
(c) 5 to 50% by weight of a surfactant.
The components used in the present invention are described below.
The average degree of neutralization of the chelating agent as component (a) is 20 to 70%, preferably 30 to 60%. When the average degree of neutralization is less than 20%, the solubility of the powders is decreased, and no satisfactory washing ability is obtained. Meanwhile, when it is more than 70%, a hygroscopic property is increased, and properties of powders such as a caking resistance and the like are deteriorated to make difficult the handling. The “average degree of neutralization” here is an average of a degree of neutralization of an acid-type chelating agent with an alkali, and it is represented by the following equation:
Average degree of
neutralization (%)
=
Number of salt-type carboxyl
groups in overall component (a)
Number of all carboxyl groups
in overall component (a)
×
100
Further, the molecular weight of the chelating agent as component (a) is 600 or less, and the number of carboxyl groups contained in one molecule is 3 to 5. When the molecular weight of the chelating agent is more than 600 and the number of carboxyl groups contained in one molecule is 6 or more, an amount of metallic ions sequestered per unit gram of the chelating agent is decreased. Meanwhile, when the number of carboxyl groups in one molecule is 2 or less, no satisfactory chelating power is obtained.
Further, this chelating agent is one in which the constant of chelating stability with Ca
2+
is 6 to 13 from viewpoints of the detergency and the hygroscopic property. The “constant of chelating stability” is an index of a chelating power.
The constant of Ca chelating stability is determined by the following method.
A solution containing 0.1 mol/l of NH
4
Cl—NH
4
OH (pH 10.0) is prepared as a buffer. All of sample solutions were prepared by using this buffer. In the measurement of the Ca
2+
concentration, an ion meter (920A manufactured by Orion Research Incorporated, U.S.A.) and a Ca
2+
ion electrode were used. First, a relation of a calcium chloride concentration and a potential of the electrode is found, and a calibration curve is formed. A solution (5.36×10
−2
mol/l) of calcium chloride, and a solution (5.36×10
−4
mol/l) of a chelating agent sample are prepared. 1 ml of the calcium chloride solution is added to 100 ml of the chelating agent sample solution, and the solution is stirred for 5 min. The residual Ca
2+
concentration is measured by using the Ca
2+
ion electrode. Assuming the chelating agent forms a chelate complex with Ca
2+
at a ratio of 1:1, the constant of Ca chelating stability is determined by the following equation:
The constant of
chelating stability
=
log
10
[
[
Ca
]
Total
-
[
Ca
]
[
Ca
]
{
[
L
]
Total
-
(
[
Ca
]
Total
-
[
Ca
]
)
}
]
[Ca]: residual concentration of metallic ions (mol/l)
[L]
total
: initial concentration of a chelating agent (mol/l)
[ca]
total
: initial concentration of metallic ions (mol/l)
An aminopolycarboxylic acid represented by the following structure is preferable as the above-mentioned chelating agent.
wherein R is —(CH
2
)
n
—A, A is H, OH or COOM, M is H, Na, K or NH
4
and n is 0 to 3.
Particularly, from a viewpoint of the biodegradability, partially neutralized substances such as N,N-bis(carboxymethyl)-2-aminopentandioic acid, N,N-bis(carboxymethyl)-2-aminobutandioic acid, N,N-bis(carboxymethyl)-2-aminopropanoic acid, N,N-bis (carboxymethyl)-2-amino-3-hydroxypropanoic acid and the like are preferable. The partially neutralized substance such as N,N-bis(carboxymethyl)-2-aminopentanoic acid or N,N-bis(carboxymethyl)-2-amino-3-hydroxypropanoic acid is particularly preferable.
The content of these chelating agents is 1 to 50% by weight, preferably 2 to 40% by weight, further preferably 2.5 to 30% by weight in the composition. When it is less than 1% by weight, no satisfactory effect is provided. Further, when it is more than 50% by weight, amounts of an activator and other builders are relatively reduced, and no sufficient detergency is obtained.
The alkali agent as component (b) is, in the present invention, composed of a compound in which a maximum pH of an aqueous solution or a dispersion having a concentration of 0.1% by weight (hereinafter referred to also as “maximum pH”) is 10 or more (20° C.), and 5 ml or more of a 0.1 N HCl aqueous solution (hereinafter referred to also as an “amount of an HCl aqueous solution”) are required to adjust 1 l of the aqueous solution or the dispersion to pH 9. When the maximum pH of the alkali agent is less than 10 or the amount of the HCl aqueous solution is less than 5 ml, no satisfactory detergency is provided.
Concrete examples of the alkali agent include crystalline silicates, amorphous silicates, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium sesquicarbonate, sodium hydrogencarbonate and the like, and amorphous alkali metal silicates such as JIS No. 1, No. 2 and No. 3 and the like, and phosphates such as tripolyphosphates. These alkali agents of inorganic salts are not only used as a neutralizer of a chelating agent but also effective for forming a structure of grains in drying a detergent, making it possible to obtain a relatively hard detergent having an excellent fluidity.
Further, the alkali agent as component (b) is blended in the composition in an amount of 5 to 60% by weight, preferably 10 to 50% by weight. When it is less than 5% by weight, the washing ability is poor, an
Hagino Genjiro
Noguchi Sachiko
Tagata Shuji
Birch & Stewart Kolasch & Birch, LLP
Boyer Charles
Kao Corporation
Kopec Mark
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