JP2003089800A - Bleaching composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oxygen-based bleaching composition which highly stably produces hydrogen peroxide in washing liquid and has an excellent bleaching power, even when soaked for a long time. SOLUTION: This bleaching composition is characterized by comprising (a) hydrogen peroxide or a peroxide which is dissolved in water to produce the hydrogen peroxide, (b) a phenolic radical-trapping agent, (c) a phosphate- based metal catching agent, and (d) a bleach-activating catalyst comprising a ligand represented by formula (I) [(l) is an integer of 0 to 2; X is R, when (l) is 0, is R', when (l) is 1, or is N, P or C (R), when (l) is 2; (n) and (m) are each 0 to 2; A and B are each a group represented by formula (II):-NR<3> R<4> or (III):-N=R<5> ] and a transition metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen-based bleaching composition which has a high stability of hydrogen peroxide in a washing liquid even when immersed for a long time and has an excellent bleaching power.

[0002]

2. Description of the Related Art Oxygen-based bleaching agents have become the mainstream of bleaching agents for clothing because they have the characteristic that they can be used for colored patterns, but on the other hand, they are inferior to chlorine-based bleaching agents in terms of their bleaching power. There is a problem that it is, and the improvement is the first issue.

Many studies have been conducted so far in order to improve the bleaching power of oxygen-based bleaching agents, a method using an organic peracid precursor and a method using a complex containing a metal atom such as manganese. and so on.

It is known that an organic peracid produced by reacting an organic peracid precursor with hydrogen peroxide brings a high bleaching power to stain stains. A precursor is required, and an agent that can effectively improve the bleaching performance with a very small amount economically and environmentally has been desired.

On the other hand, a method utilizing a complex containing a metal atom is described in Nature, VOL. 369 (1994) 6
Pages 37-639 and J. Am. Chem. Soc. , VO
L. 115 (1993) 1772-1773. While organic peracids act on the soil in a stoichiometric amount, a mechanism has been proposed for the metal complex, in which the complex catalytically activates hydrogen peroxide in the washing liquid to bring about a high bleaching effect on the stain stain. Therefore, high bleaching power can be obtained with a small amount of complex.

That is, the method of utilizing a complex containing a metal atom having a characteristic of being able to activate hydrogen peroxide more efficiently shows an effect at a low concentration, and is therefore economically and environmentally preferable.

Since the bleaching effect of a metal complex differs depending on the combination of the central metal and the ligand, various combinations of the ligand and the transition metal have been studied. For example, U.S. Pat. No. 3,156,654, U.S. Pat. No. 3,532,634 and British Patent No. 984,45.
No. 9 discloses a combination of a commonly used chelating agent such as EDTA, NTA or pyridinecarboxylic acid and a transition metal such as Co or Cu. However, this combination catalyzes the decomposition of peroxy compounds, but does not contribute significantly to the activation of bleaching. JP-B-6-33431 and JP-B-6-70240 disclose a manganese complex having a hydroxycarboxylic acid as a ligand, and JP-B-6-99719 discloses a manganese complex having a polyhydroxy compound as a ligand. The complex is disclosed in JP-A-52-1.
No. 55279, JP-A-1-97267, JP-A-2-261547, JP-A-8-503247 and JP-A-8-503248 disclose iron or porphyrin or phthalocyanine as a ligand. Manganese complexes are disclosed in Japanese Patent Publication Nos. 7-12437 and 7-65074.
No. 7-68543 and No. 7-122076.
JP-A-5-263098 and JP-A-6-12.
1933 discloses a manganese complex having a cyclic polyamine as a ligand, and JP-A-10-140193 discloses a complex of a ligand having three or more coordinating nitrogen atoms with a transition metal. 2000-54256 discloses a manganese complex having a condensation compound of an amine and salicylaldehyde as a ligand, and US Pat. No. 5,021,187 discloses a copper complex having a substituted diamine as a ligand. Has been done,
It has been confirmed that these have improved bleaching performance.

[0008] However, there are various consumer bleaching methods, especially dipping bleaching is commonly used as a method of removing stubborn stains. Bleaching soaked,
It is an important subject to maintain the activity of the bleaching solution for a long time by a method of immersing the article to be washed in the bleaching agent solution for several tens of minutes to several hours. That is, it becomes necessary to suppress the decomposition of hydrogen peroxide. The cause of decomposition of hydrogen peroxide is not only caused by the complex itself, but also transition metals carried as impurities in the complex and trace amounts of iron, manganese, copper, zinc, etc. in tap water, which are often present at a level of several ppm. These metals must also be carefully considered as the cause of abnormal decomposition of hydrogen peroxide.

In order to suppress the decomposition of hydrogen peroxide by such trace metals, it is generally known to use a metal scavenger. However, Japanese Patent No. 3009471
As described in Japanese Patent Publication, in the conventional technology,
Addition of a metal scavenger improves the stability of hydrogen peroxide, but there is a problem that the bleaching activity of the complex is lost.
Therefore, it is difficult to use the conventional technique together with a metal scavenger having a high metal scavenging ability, and the bleaching power in bleaching while soaking for a long time is not satisfactory.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a bleaching composition having a high bleaching power with less decomposition of hydrogen peroxide even when immersed for a long time. With the goal.

[0011]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above-mentioned objects, the present inventors have found that a bleaching activation catalyst having a specific structure, a phenolic radical trapping agent, and a phosphon By combining with an acid-based metal scavenger, a bleaching activation catalyst having a specific structure,
It has been found that the metal scavenger and the radical trapping agent have a synergistic effect in stabilizing hydrogen peroxide and improving the bleaching power, and have a stable high bleaching power even with respect to stubborn stains. Completed

That is, the present invention relates to (a) hydrogen peroxide or a peroxide which is dissolved in water to generate hydrogen peroxide, (b) a phenol-based radical trapping agent, (c) a phosphonic acid-based metal scavenger, and (D) A bleaching composition comprising a bleaching activation catalyst containing a ligand represented by the following general formula (I) and a transition metal.

[0013]

[Chemical 2] (However, in the above formula (I), l is directly bonded to X-
It is an integer of 0 to 2 showing the number of [(CH) _m (R ² ) -A]. X is represented by R when l is 0, represented by R ′ when 1 is 1, and is represented by nitrogen atom, phosphorus atom or C (R) when l is 2. Is. R, R ¹ and R
² may be the same or different, each is a hydrogen atom, an optionally substituted alkyl group,
It is a cycloalkyl group or an aryl group, and R ′ is an optionally substituted alkylene group or cycloalkylene group. n and m may be the same or different and each is a number from 0 to 2. A and B may be the same or different and each is a group represented by the following formula (II) or (III). ^{) -NR 3 R 4 ... (II} ) -N = R 5 ... (III) ( where the formula (II) in, (III), R ³ and R ⁴ may be the same or different, R ^3, R ⁴ is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, respectively. In the alkyl group, the cycloalkyl group, the aryl group and the benzyl group, some or all of the hydrogen atoms are a hydroxyl group, a halogen atom or a halogen atom. It may be substituted with an atom, a sulfonic acid group, a carboxylic acid group, an alkyl group or an aryl group having a carbon chain length of 1 to 3. R ⁵ is an alkylidene group, a cycloalkylidene group or a benzylidene group, and these groups are Part or all of the hydrogen atoms are a hydroxyl group, a halogen atom, a sulfonic acid group, a carboxylic acid group, an alkoxyl group having a carbon chain length of 1 to 3, and an alkyl group respectively having a carbon chain length of 1 to 3.
May be substituted with a dialkylamino group, an alkyl group having a carbon chain length of 1 to 3, or an aryl group. )

The present invention will be described in more detail below. The bleaching composition of the present invention comprises (a) hydrogen peroxide or a peroxide that dissolves in water to generate hydrogen peroxide, (b) a phenolic radical trapping agent, (c) a phosphonic acid metal scavenger, and (D) It contains a bleaching activation catalyst having a specific structure and may be a liquid bleaching composition or a solid bleaching composition such as powder, granules, tablets, briquettes, sheets or bars. Well, if it is a solid bleaching composition,
Ions of all inorganic ions (inorganic ions resulting from dissociation of all compounds in the composition including the above-mentioned component (a)) when the composition is diluted to 1% by mass in deionized water In order for the total intensity to fall within the specified range,
By adding an inorganic compound other than the above-mentioned components as the component (e), higher effects can be obtained.

The component (a) of the bleaching composition of the present invention is hydrogen peroxide or a peroxide which dissolves in water to generate hydrogen peroxide, and the bleaching composition of the present invention is a liquid. In the case of a bleaching composition, hydrogen peroxide is used as the component (a), and the bleaching composition of the present invention may be a solid bleaching composition such as powder, granules, tablets, briquettes, sheets or bars. For example, a peroxide that dissolves in water to generate hydrogen peroxide is used as the component (a). Specific examples of peroxides that dissolve in water to generate hydrogen peroxide include sodium percarbonate, sodium perborate, and sodium perborate trihydrate. Consider the solubility during use. Then, it is preferable to use sodium percarbonate. These may be used alone or in combination of two or more.

The above (a) in the bleaching composition of the present invention
The content of the components is not particularly limited and can be appropriately selected depending on the form of the composition. For example, when the composition of the present invention is a liquid bleaching composition, it is 2
Mass% or more is preferable, more preferably 2 to 5 mass%,
More preferably, it is 4 to 5 mass%. If it is less than 2% by mass, a sufficient bleaching effect may not be obtained. Further, when the composition of the present invention is a solid bleaching composition, it is preferably 2% by mass or more, more preferably 10% by mass, based on the total amount of the composition.
90% by mass, more preferably 20 to 90% by mass. If it is less than 2% by mass, a sufficient bleaching effect may not be obtained.

The component (b) of the present invention is a phenolic radical trapping agent. Examples of the phenolic radical trapping agent include a compound having a phenolic hydroxyl group, an ester derivative of a phenolic hydroxyl group, an ether derivative and the like. As such compounds, more specifically, cresol, thymol, chlorophenol, bromophenol, methoxyphenol, nitrophenol,
Hydroxybenzoic acid, salicylic acid, hydroxybenzenesulfonic acid, di-t-butyl-hydroxytoluene, naphthol, hydroquinone, catechol, pyrogallol,
Examples include phenoxyethanol and phenol.

Among these, preferred compounds are G. E.
Penketh, J .; Appl. Chem, 7, 512
(1957), the redox potential (O.
P. ) ₀ (25 ° C.) is a compound of 1.25 V or less,
A compound of 0.75 V or less is more preferable. In addition,
The lower limit of the oxidation potential (OP) ₀ (25 ° C.) is not particularly limited, but in consideration of the influence on the bleaching effect, the oxidation potential (OP) ₀ (25 ° C.) is usually set. The lower limit of () is preferably about 0.60V. If the redox potential exceeds the above range, the stabilizing effect of hydrogen peroxide may not be sufficient. If the redox potential is too low, the bleaching power may decrease.

Further, if the composition of the present invention is a liquid bleaching composition, it is easy to mix. On the other hand, if the composition of the present invention is a solid bleaching composition, it is bleached by immersion. In order to dissolve quickly even with a small mechanical force such as when treating, using a highly soluble radical trapping agent among the phenolic radical trapping agents,
It is more effective, and specifically, one having a logP value of 3 or less, which is a hydrophobic parameter indicating solubility, is preferable. Here, the above-mentioned hydrophobicity parameter is generally used as a parameter indicating the property of the target compound. The P (partition coefficient) in the logP value is expressed as P = Co / Cw as the ratio of the activity of the substance at equilibrium between water and octanol (where Co is the concentration in octanol, and Cw is It is the concentration in water). For more information on the hydrophobicity parameter,
For example, the special issue of science, No. 122 (1979), No. 7
It is described on page 3. As a method of measuring the distribution coefficient,
The Flask Shaking method, the thin layer chromatographic method, and the measuring method by HPLC are known, but Ghos
It can also be calculated by calculation using the parameters of e, Prichchet, Crippen and others.
(J. Comp. Chem., 9, 80 (1998)).

Considering the influence on the bleaching power and the solubility as mentioned above, 4-methoxyphenol, 4-hydroxybenzoic acid, hydroquinone and catechol are more preferable among the above compounds, and when coexisting with a peroxide. Considering the stability of the radical trapping agent, the 4-methoxyphenol and 4-hydroxybenzoic acid are particularly preferable among them.

Regarding the component (b), these may be used alone or in combination of two or more kinds.

The above (b) in the bleaching composition of the present invention
The content of the components is not particularly limited, but the preferred content is 0.001 to 4 mass% in the bleaching composition,
It is more preferably in the range of 0.05 to 2% by mass, further preferably 0.1 to 0.5% by mass, and 0.001% by mass.
If it is less than 4%, the stabilization of hydrogen peroxide may be insufficient, and if it exceeds 4% by mass, there may occur a problem that the radical trap agent that has reacted with radicals is discolored or the object to be washed is stained. Moreover, it may not be economically preferable.

When the bleaching composition of the present invention is a solid bleaching composition, the component (b) contains a surfactant, citric acid, etc. in order to improve the solubility and the storage stability. The composition is preferably contained in the composition as a mixed particle with one or more granulating bases containing organic acid, and is used by granulating with an aluminosilicate, polyethylene glycol, an inorganic compound of component (e) described later, or the like. Is preferred. As an example of the granulation method, the component (b) is dissolved in a melted granulation base material,
Examples include a method of pulverizing and granulating and a method of spraying a granulating base material while stirring the component (b), and coating.
A suitable granulation method can be selected depending on the granulation base material used. As the granulating base material used here, if it is a polymer compound, polyethylene glycol or polycarboxylic acid or its salt, and if it is a surfactant, either an ionic surfactant or a nonionic surfactant is used. However, preferred surfactants include sodium alkylbenzene sulfonate having 10 to 15 carbon atoms, potassium alkylbenzene sulfonate having 10 to 15 carbon atoms, and α-having 14 carbon atoms.
Sodium olefin sulfonate, potassium α-olefin sulfonate having 14 carbon atoms, polyoxyethylene alkyl ether having 12 to 15 carbon atoms and 5 to 20 ethylene oxide average addition moles, among others, α-olefin sulfone having 14 carbon atoms. Sodium acid is particularly preferred.
Further, as the inorganic compound, carbonate or aluminosilicate,
An inorganic salt such as sulfate. When the component (b) is used as mixed particles, it is preferable that the granulation base material is mixed in the same mass or more with respect to the component (b). If the amount is less than the same, the effect of granulation may not be sufficiently obtained.

The component (c) of the present invention is a phosphonic acid type metal scavenger. Examples of the phosphonic acid-based metal scavenger used in the present invention include 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and ethane-1,1-diphosphonic acid,
Ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid) ), Nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and other organic phosphonic acid derivatives and salts thereof, When the composition of the present invention is a liquid bleaching composition, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is preferable among them in view of influence on bleaching power and blending suitability. If the composition is a solid bleaching composition, 1-hydroxyethane-1, -Diphosphonic acid (HEDP) trisodium, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) tetrasodium and ethylenediaminetetra (methylenephosphonate) sodium are preferable, and considering the effect on bleaching power and storage stability. , 1-Hydroxyethane-1,1-diphosphonic acid (HEDP) tetrasodium is more preferred.

The above (c) in the bleaching composition of the present invention
The content of the component is not particularly limited and can be appropriately selected depending on the type thereof, and for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) 4
In the case of sodium, it is preferably in the range of 0.05 to 4% by mass, more preferably in the range of 0.1 to 2% by mass, and in the case of sodium ethylenediaminetetra (methylenephosphonate), 0.05 to 2% by mass. The range is preferable, and the range is more preferably 0.1 to 2% by mass. If it is less than the above range, a sufficient stabilizing effect of hydrogen peroxide may not be obtained, and if it exceeds the range, the bleaching power may be lowered.

The component (d) of the present invention has the following general formula (I):
A bleaching activation catalyst containing a ligand represented by and a transition metal.

[0027]

[Chemical 3] (However, in the above formula (I), l is directly bonded to X-
It is an integer of 0 to 2 showing the number of [(CH) _m (R ² ) -A]. X is represented by R when l is 0, represented by R ′ when 1 is 1, and is represented by nitrogen atom, phosphorus atom or C (R) when l is 2. Is. R, R ¹ and R
² may be the same or different, each is a hydrogen atom, an optionally substituted alkyl group,
It is a cycloalkyl group or an aryl group, and R ′ is an optionally substituted alkylene group or cycloalkylene group. n and m may be the same or different and each is a number from 0 to 2. A and B may be the same or different and each is a group represented by the following formula (II) or (III). ^{) -NR 3 R 4 ... (II} ) -N = R 5 ... (III) ( where the formula (II) in, (III), R ³ and R ⁴ may be the same or different, R ^3, R ⁴ is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, respectively. In the alkyl group, the cycloalkyl group, the aryl group and the benzyl group, some or all of the hydrogen atoms are a hydroxyl group, a halogen atom or a halogen atom. It may be substituted with an atom, a sulfonic acid group, a carboxylic acid group, an alkyl group or an aryl group having a carbon chain length of 1 to 3. R ⁵ is an alkylidene group, a cycloalkylidene group or a benzylidene group, and these groups are Part or all of the hydrogen atoms are a hydroxyl group, a halogen atom, a sulfonic acid group, a carboxylic acid group, an alkoxyl group having a carbon chain length of 1 to 3, and an alkyl group respectively having a carbon chain length of 1 to 3.
May be substituted with a dialkylamino group, an alkyl group having a carbon chain length of 1 to 3, or an aryl group such as a phenyl group. )

Here, in the above general formula (I), R, R ¹ ,
The alkyl group, cycloalkyl group and aryl group in R ² , R ³ and R ⁴ respectively have an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alkyl group having 6 to 24 carbon atoms. An aryl group is preferable, and an alkylene group and a cycloalkylene group in R ′ are preferably an alkylene group having 1 to 20 carbon atoms and a cycloalkylene group having 3 to 8 carbon atoms, respectively, and have bleaching power and hydrogen peroxide stability. Considering the above, R, R ¹ and R ² have 1 to 3 carbon atoms.
As the alkyl group and R'of, an alkylene group having 1 to 4 carbon atoms is more preferable. Further, as these substituents,
Halogen atom, hydroxyl group, alkoxyl group, cyano group, amino group, quaternary ammonium group, sulfonic acid group,
Examples thereof include thienyl group and carboxylic acid group. In the above general formula (I), n is 0 or 2, m is 0 or 2, and l is 1 to 2
Is preferred, and when 1 is 2, X is a nitrogen atom or C
A group represented by (R) is preferable, and from the viewpoint of bleaching power and stability of hydrogen peroxide, R is particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹ and R ² are hydrogen. Particularly preferred is an atom. For the same reason, when l is 1, R ′ is particularly preferably an alkylene group having 1 to 4 carbon atoms. When there are two A's in the molecule, these A's may be the same or different, but the same case is preferable. A and B
With respect to, it is preferable that both A and B are groups represented by the above formula (III), and it is more preferable that A and B are the same. R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group or aryl group having 1 to 4 carbon atoms, and R ^3
5 is preferably an alkylidene group having 1 to 3 carbon atoms, a salicylidene group, or a hydroxysalicylidene group, and more preferably a salicylidene group or a hydroxysalicylidene group.

More specific examples of the ligand represented by the above general formula (I) of the present invention include the following compounds.

[0030]

[Chemical 4]

[0031]

[Chemical 5]

[0032]

[Chemical 6]

The transition metal contained in the bleaching activation catalyst which is the component (d) of the present invention includes water, a hydroxyl group, a phenolic hydroxyl group and an amino group in addition to the ligand represented by the general formula (I). A carboxylic acid group, a thiol group, a halogen atom and the like may be coordinated.

The transition metal of the component (d) is copper,
Examples thereof include iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten and molybdenum. Among these, cobalt and manganese are preferable, and manganese is particularly preferable.

These ligands of component (d) may be used alone or in combination of two or more. More specifically, the preferred (d) bleaching activation catalyst in the present invention is (tris (salicylideneiminoethyl) amine)-
Manganese complex, (N, N′-ethylenebis (4-hydroxysalicylideneiminate))-manganese complex, (tris (2,4-dihydroxybenzylideneiminoethyl) amine) -manganese complex and the like can be mentioned. Among these, Considering the stability of hydrogen peroxide, (tris (salicylideneiminoethyl) amine) -manganese complex is more preferable.

The above (d) in the bleaching composition of the present invention
The content of the component is not particularly limited and can be appropriately selected depending on the form of the composition, for example, when the composition of the present invention is a liquid bleaching composition, the preferred content is the composition. 0.0001 to 0.01% by mass, more preferably 0.0005 to 0.005% by mass,
More preferably, it is 0.0005 to 0.002 mass%. On the other hand, if the composition of the present invention is a solid bleaching composition, the preferred content is 0.001 to 1% by mass, more preferably 0.05 to 1% by mass in the composition,
More preferably, it is 0.1 to 1 mass%. If it is less than this range, the improvement of the bleaching effect may be insufficient, and if it exceeds this range, the effect may not be further enhanced.

Here, when the bleaching composition of the present invention is a solid composition, (d) in the solid bleaching composition
In order to more effectively suppress the decomposition of hydrogen peroxide by the component and the decomposition of peroxide during storage, the component (d) is
Component (b) above and surfactant and / or melting point 37-65
C., preferably 50 to 65.degree. C., and used as composite particles granulated with a binder compound. In order to improve the solubility of the component (b), it is preferable to use both a surfactant and the binder compound. More preferable.

As the binder compound, polyethylene glycol # 1500 to # 20000 (weight average molecular weight 500 to 19000) or weight average molecular weight 1000 to
100,000 polyacrylic acid and its salts are mentioned, and especially polyethylene glycol # with a melting point of 50 to 65 ° C.
4000- # 6000 (weight average molecular weight 2600-10
000) is preferred.

When used as composite particles, the mass ratio of component (b) and component (d) is preferably 10/1 to 1/1.
0, more preferably 5/1 to 1/5, and the content of the component (d) in the composite particles is preferably 2 to 30% by mass,
More preferably, it is 5 to 20 mass%. Further, the mass ratio of the sum of the contents of the components (b) and (d) and the sum of the contents of the surfactant and / or the binder compound having a melting point of 37 to 65 ° C. in the composite particles is 7: 3 to 1: 1. 25 is preferable, and 1: 1 to 1:10 is more preferable. Mass ratio is 7: 3
If the ratio of the sum of the contents of the component (b) and the component (d) is too high, the solubility of the radical trapping agent or the effect of suppressing decomposition of peroxide during storage may be insufficiently improved, which is low. If it is too much, it will take time for the components (b) and (d) to dissolve out, and rapid effects may not be expected.

Further, in order to further improve the effect of suppressing decomposition of hydrogen peroxide, it is preferable that the above-mentioned component (c) is also contained in the above-mentioned granulated product. As another method for improving the solubility of the granulated product, it is also preferable to granulate with an organic acid such as citric acid or adipic acid. The particle size of the composite particles (granulated product) is not particularly limited, but in consideration of solubility and the like, the average particle size is 200 to 1000 μm, particularly 300.
It is suitable that it is ˜700 μm. Here, the average particle diameter can be confirmed by a method such as obtaining a particle size distribution using a sieve and calculating from the particle size distribution.

When the composition of the present invention is a solid bleaching composition, in addition to the above components (a) to (d), an inorganic salt other than the above components such as an inorganic salt is usually used as the component (e). In the case of the present invention, the stability of hydrogen peroxide is further improved by adjusting the ionic strength of the inorganic ion in the bleaching solution to be within a predetermined range in the case of the present invention. Therefore, the content of the inorganic compound of the component (e) in the solid bleaching composition of the present invention was diluted so that the composition was 1% by mass in deionized water. The total ionic strength of all the inorganic ions present in the diluted solution is 0.15 to 0.2
It is desirable to adjust to 7, preferably 0.19 to 0.23. If the ionic strength is outside this range, the effect of adjusting the ionic strength to improve the stability of hydrogen peroxide is not sufficient, and if it exceeds 0.27, the bleaching effect may be reduced. The cause of such a stabilizing phenomenon is not clear, but is presumed to be due to the salting out effect and the buffering effect of the inorganic ions.

The ionic strength (μ) in the present invention is given by the following formula.

[0043]

[Equation 1]

Here, in the above formula, Ci is the molar concentration of the i-th ion, Zi is its charge, and the total is a dilution of the solid bleaching composition diluted to 1% by mass in deionized water. Perform for all inorganic ions in solution.

The ionic strength of the diluted solution is variously adjusted according to the contents and types of the inorganic compounds other than the component (a) and the component (e) other than the component (a) and the counterion of the surfactant. can do. As the inorganic compound of the component (e) of the present invention, those having a sufficiently high solubility in water at about 5 ° C. are preferable because they can be rapidly dissolved even when subjected to bleaching treatment in winter. Further, in terms of having a high ionic strength with a smaller content, an inorganic salt having a high valence or a small molecular weight is effective, and specifically, an alkali metal carbonate such as sodium carbonate or potassium carbonate, an amorphous salt. Examples thereof include alkali metal silicates, alkali metal borates, and alkali metal phosphates, and also neutral salts such as sodium sulfate, sodium sulfite, sodium chloride, and potassium chloride. Further, in order to increase the ionic strength and adjust the pH at the same time, it is more effective to use an inorganic salt which dissolves in water and exhibits alkalinity and weak alkalinity. Specifically, sodium carbonate, potassium carbonate, carbonate Sodium hydrogen, sodium metasilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate 3
Issue etc. Sodium silicate and sodium carbonate, water 55/29 from the viewpoint of solubility in water and alkalinity
It is preferable to use NABION (manufactured by Rhodia) which is a mixture having a ratio of / 16. The total ionic strength of the inorganic ions in the diluted solution, as described above,
Not only the inorganic compound of component (e), but also inorganic ions resulting from the dissociation of hydrogen peroxide and peroxide of component (a), and sodium and potassium ions used as counterions for surfactants and metal scavengers. Ionic strength is also included. Here, when obtaining the ionic strength of a compound that does not completely dissociate even with an inorganic compound such as hydrogen peroxide, the dissociation constant at 25 ° C. and 25 ° C. when diluted to 1% by mass in deionized water are used. Ionic strength is determined by pH. Further, as described below, the bleaching composition of the present invention may further contain a bleach activator, a boron compound, etc., if necessary, in order to enhance the bleaching effect. Sodium and the like used for ions are included in the total ionic strength, and when the boron compound is an inorganic salt, it is used as the inorganic compound which is the component (e) of the present invention.

In the solid bleaching composition of the present invention, the above (e) is added.
When the component is contained, its preferable content is an amount such that the sum of the ionic strengths in the diluent is within the above-mentioned specific range, and specifically, the content is appropriately determined depending on the contents of other components as described above. It is selected, but usually 5 to 60 mass% is preferable in the solid bleaching composition, more preferably 10 to
It is in the range of 50% by mass, more preferably 20 to 50% by mass. Outside the above range, it may be difficult to adjust to a desired ionic strength.

The bleaching composition of the present invention, whether it is a liquid bleaching composition or a solid bleaching composition, is within a range that does not impair the effects of the present invention. Bleach activator, if necessary, to further increase
A boron compound and a pH adjusting agent can also be contained.

As the bleach activator, tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate. , Sodium dodecanoyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyl Oxybenzene, undecanoyloxybenzene, dodecanoyloxybenzene and the like can be added. Among these, preferred bleach activators include decanoyloxybenzoic acid, sodium dodecanoyloxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate, and the like, and 4-decanoyloxybenzoic acid is more preferred.

When the bleaching composition of the present invention contains the above bleaching activator, the content of the bleaching activator in the composition is preferably 1 to 10% by mass, more preferably 1 to 5% by mass. If it is less than 1% by mass, the bleaching effect may not be sufficient, and if it exceeds 10% by mass, the bleaching effect may not be further enhanced. These bleach activators may be used alone or in combination of two or more. In addition, it is known that the bleach activator is hydrolyzed by the presence of an alkaline component and water in the bleach to lose its function. Therefore, in order to prevent such decomposition, when the bleaching activator is added to the solid bleaching composition, a nonionic surfactant or a weight average molecular weight of 1500 to 20000 is used.
Polyethylene glycol, anionic surfactant, film-forming polymer, fatty acid and the like are preferably mixed and blended as a granulated product.

When a boron compound is added to the bleaching composition of the present invention, the boron compound acts on hydrogen peroxide and free metal to further enhance the stability of hydrogen peroxide in the bleaching solution. Examples of the boron compound that can be added to the bleaching composition of the present invention include boric acid, sodium borate, potassium borate, ammonium borate, and sodium borate.
Compounds containing boron in the molecule such as potassium tetraborate and ammonium tetraborate are preferable, and among these, sodium tetraborate is particularly preferable.

The pH of the bleaching composition of the present invention is not particularly limited and can be appropriately selected depending on the form of the composition. For example, for a solid bleaching composition, 1 mass of deionized water is used. PH at 25 ℃ at the time of dilution
Is preferably 9 to 11, and more preferably 10 to 11. On the other hand, in the liquid bleaching composition, the pH of the composition at 25 ° C is preferably 2-8. Outside of the above range, it may be difficult to obtain the bleaching performance and stability aimed at by the present invention. As a means for controlling the pH, the pH is usually adjusted with an alkaline agent. In the solid bleaching composition, sodium carbonate, which is generally called dense ash or light ash, is used as the alkaline agent, and potassium carbonate is also used. , Alkali metal carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, etc., amorphous metal silicates such as sodium metasilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, disodium hydrogen phosphate, etc. Inorganic salts contained in the inorganic compound of the above-mentioned component (e) such as alkali metal phosphate can be used, and in the liquid bleaching composition, sodium hydroxide, potassium hydroxide, monoethanolamine, Diethanolamine, triethanolamine and the like can be used. These may be used alone or in combination of two or more. Further, in order to prevent the pH from becoming too high, it is possible to adjust the pH within the above range using an acid or the like. Examples of the acid include sulfuric acid and hydrochloric acid, and the metal scavenger contained in the component (c) of the present invention can also be used. In addition, alkali metal dihydrogen phosphate such as potassium dihydrogen phosphate and fatty acids, lactic acid, citric acid, succinic acid, malic acid, gluconic acid, oleic acid, decanoic acid,
Alternatively, those polycarboxylic acids or the like can be used. When the alkaline agent or acid used to control the pH is an inorganic compound, the above (e)
Included in the ingredients. In addition, it is also possible to use a buffering agent for preventing the pH from being lowered by an acid component derived from stains on clothes during washing.

Further, the bleaching composition of the present invention may contain various components usually added to the bleaching composition, in addition to the above components, as long as the effects of the present invention are not impaired.
For example, the following auxiliary components can be contained.

(1) Surfactant The surfactant is a surfactant having at least one linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, or an alkyl group having 8 to 24 carbon atoms. A surfactant having at least one aryl group substituted with
Examples of the anionic surfactant include alkylbenzene sulfonate, soap, alkyl sulfate, polyoxyethylene alkyl sulfate, fatty acid α-sulfomethyl ester, α-olefin sulfonate and the like. Examples of nonionic surfactants include alkyl glycosides, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid ester oxyethylene propylene block polymers, fatty acid monoglycerides, and amine oxides. Examples of the amphoteric surfactant include carbobetaine, sulfobetaine, hydroxysulfobetaine, etc. These may be used alone or in combination of two or more kinds.

Among the above-mentioned surfactants, sodium α-olefinsulfonate and nonionic surfactants are preferable, and among the nonionic surfactants, Japanese Patent Publication No. 6-15038.
The nonionic surfactant obtained by the method described in JP-A No. 2004-96, that is, the distribution of the number of moles of ethylene oxide added to the average number of moles of ethylene oxide added is within a range of n ± 2.
% Or more is preferable. Further, in particular, 1 of the phenolic radical trapping agent of the component (b) in the present invention
When the ogP value is 2 or more, in order to quickly dissolve the radical trap agent in water, α- having 14 carbon atoms is used.
Among the sodium olefin sulfonates and the above nonionic surfactants, it is more preferable to use one having an alkyl chain length of 12 to 14 and an average addition mole number of ethylene oxide of 3 to 7. The content (total amount) of the surfactant in the present invention is, in the bleach composition, 0.1 to 15% by mass from the viewpoint of bleaching power and solubilization of a poorly water-soluble substance (fragrance, etc.).
Is preferable, and more preferably 0.3 to 12 mass%. Further, in the whitening detergent composition, from the viewpoint of bleaching power and detergency, 15 to 50 mass% is preferable, and 20 to 40 mass% is more preferable.

(2) Fragrances A list of fragrance raw materials used as fragrances can be found in various literatures such as "Perfume and Flavor".
Chemicals ", Vol. I and II, S
teffen Arctander, Allured
Pub. Co. (1994) and "Synthetic fragrance science and product knowledge", Genichi Indo, Kagaku Kogyo Nipposha (1996) and "Perfume and Flavor Mate".
rials of Natural Origin ", S
teffen Arctander, Allured
Pub. Co. (1994) and "Aroma Encyclopedia", edited by The Japan Fragrance Association, Asakura Shoten (1989) and "Flower".
oils and Floral Compound
s In Perfumery ", DanuteLaj
au Anis Anonis, Allured Pub.
Co. (1993), each of which is incorporated by reference. Typical fragrances include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, aliphatic ethers and aromatic ethers. Ethers, aliphatic oxides, oxides such as oxides of terpenes, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes, aldehydes such as aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogen Ketones such as derivatized aromatic ketones, aliphatic cyclic ketones, non-benzene type aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carvone acid,
Acids such as aromatic carboxylic acids, acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenated aromatic lactones, lactones such as aromatic lactones, aliphatic esters, furan carboxylic acid esters, fats Aromatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, aromatic carboxylic acid esters and other esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indole and other nitrogen-containing compounds, etc. One or more of the synthetic flavors and natural flavors from animals and plants, and mixed flavors including natural flavors and / or synthetic flavors can be mixed and used.

More specifically, the aldehydes C _{6 to} C ₁₂ ,
Anisaldehyde, acetal R, acetophenone, acetylcedrene, adxal, allyl amyl glycolate, allyl cyclohexane propionate, alpha damascon, beta damascon, delta damascon, ambrette lid, ambroxane, amylcinnamic aldehyde, amyl Cinnamic aldehyde dimethyl acetal, amyl valerianate, amyl salicylate, isoamyl acetate, isoamyl salicylate,
Auranium thiol, acetyl yugenol, vacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, paratertiary butyl cyclohexanol, paratertiary butyl cyclohexyl acetate, ortho tertiary butyl cyclohexanol , Benzaldehyde, Benzylformate, Caryophyllene, Kashmeran, Carvone, Cedro Amber, Cedryl acetate, Cedrol, Celestrid, Cynamic alcohol, Cynamic aldehyde, Cisjasmon, Citral, Citral dimethyl acetal, Citrasal, Citronellal, Citronellol, Citro Neryl Acetate, Citronellyl Formate, Citronelli Nitrile, Shikurasetto, cyclamen aldehyde, Shikurapuroppu, Caron, coumarin, cinnamyl acetate, delta C ₆ -C ₁₃ lactones, dimethyl benzyl carbinol, dihydrojasmonate, dihydro linalool, dihydromyrcenol, Jimetoru, Jimirusetoru, diphenyl oxide, Echiruwanirin, Yugenoru, Furuiteto, Fen steel alcohol, phenylethyl phenylacetate, Garakisoriddo, gamma C ₆ -C _{1 3-lactone,} alpha-pinene, beta-pinene, limonene, myrcene, beta-caryophyllene, geraniol, geranyl acetate, geranyl formate , Geranyl nitrile, hedion, helion, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexene Se Neil salicylate, hexyl cinnamic aldehyde, hexyl salicylate, hyacinth dimethyl acetal,
Hydrotropic alcohol, hydroxycitronellal, indole, ionone, isobornyl acetate, isocyclocitral, isoE super, isougenol, isononyl acetate, isobutylquinoline,
Jasmar, Jasmolactone, Jasmofilan,
Coabon, Ligtral, Liliar, Lime Oxide, Linalool, Linalool Oxide, Linalyl Acetate, Linal, Manzanate, Mayol, Mensanyl Acetate, Mensonate, Methylanthranilate, Methyljugenol, Menthol, Alpha Methylionone, Betamethylionone, Gamma methyl ionone, methyl isougenol, methyl lavender ketone, methyl salicylate, mugelaldehyde, mugol, musk TM-II, musk 781, musk C ₁₄ , muscone, civetone, cyclopentadecanone, cyclohexadecenone, cyclopentadeca Nolide, ambrettolide, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, Ethylene brassate, ethylene dodecanedioate, oxahexadecen-2-one, 1
4-methyl-hexadecenolide, 14-methyl-hexadecanolide, muskketone, musktivetine, nopyr alcohol, nopyracetate, nerylacetate, nerol, methylphenylacetate, miracaldehyde, neobergamate, oakmos No. 1, Oligobon, oxyphenylone, paracrezier methyl ether, pentalide, phenylethyl alcohol, phenylethyl acetate, alphapinene, luvafran, rosephenone, rose oxide, sandaroa, sandera, santalex, styralyl acetate, styralyl Propionate, terpineol, terpinyl acetate, tetrahydrolinalool, tetrahydrolinaryl acetate, tetrahydrogeraniol,
Tetrahydrogeranyl acetate, tonalid, traseolide, tripral, thymol, crocodile, belldox, yarayala, anise oil, bay oil, boad rose oil, cananga oil, cardamom oil, cassia oil, cedarwood oil, orange oil, mandarin oil, tangerine oil ,
Basil oil, nutmeg oil, citronella oil, clove oil, coriander oil, elemi oil, eucalyptus oil, fennel oil,
Galvanum oil, geranium oil, hiba oil, cypress oil, jasmine oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okochia oil, patchouli oil, peppermint oil, perilla oil, petitgrain Oil, pine oil, rose oil, rosemary oil, soy sauce oil, savory oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine oil, vanilla bean tincture , Vetiver oil, ylang-ylang oil, grapefruit oil, yuzu oil, benzoin, Peruvian balsam, true balsam, tuberose oil, musschinki, castor tincture, civet tincture, ambergris tincture and the like.

Further, as a solvent or a suspending agent for the fragrance, ethanol, acetin (triacetin), MMB acetate (3-methoxy-3-methylbutylacetate), ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, deltil is used. Extra (isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG
(Triethylene glycol), benzyl benzoate, propylene glycol, diethyl phthalate, tripropylene glycol, aborin (dimethyl phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol DPG-FC (dipropylene glycol), farnesene, Dioctyl adipate, tributyrin (glyceryl tributanoate), hydrolite-
5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abietate, avalin (methyl abiate), citroflex A-2 (acetyltriethyl citrate), citroflex A- 4 (tributylacetyl citrate), Citroflex No. Two
(Triethyl citrate), Citroflex No. Four
(Tributyl citrate), Durafix (methyldihydroabietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), propylene glycol, 1,3-butylene glycol and the like. The bleaching composition contains 0.1 to 99% by mass of the solvent or the holding agent in the fragrance composition, and preferably 1 to 50% by mass.

Examples of the perfume stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and its derivatives, catechin compounds, flavonoid compounds, polyphenol compounds, etc., and 0.0001 to 10% by mass in the perfume composition. It is blended, but preferably 0.001 to 5 mass% is blended. Among these,
A preferred stabilizer is dibutyl hydroxytoluene. The perfume composition is a mixture of the above-mentioned perfume ingredients, solvent, perfume stabilizer and the like. The bleaching composition contains a fragrance composition in an amount of 0.001 to 20% by mass, preferably 0.01 to 10% by mass.

(3) Various dyes can be used to improve the appearance of the dye composition. Examples of the dye used in the bleaching composition include dyes and pigments. Among them, pigments are preferable, and those having oxidation resistance such as oxides are particularly preferable. Preferred compounds include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, navy blue, cyanine blue,
Examples include cyanine green. Further, it is preferable to granulate these dyes together with the complex, and in this case, it is preferable to use one in which the dye is dissolved or dispersed in a binder component such as polyethylene glycol (PEG). Furthermore, as a bluing agent, a blue pigment such as ultramarine is used in the above (e).
It can also be used by spraying it onto the sodium sulphate, sodium carbonate, granular bleaching agent composition, etc. contained in the components and granulating.

(4) Fluorescent agent As a fluorescent dye, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-)
3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis (triazol-2-yl) stilbene derivative, bis (triazinylamino) stilbenzylsulfonic acid derivative, Whitex SA (manufactured by Sumitomo Chemical Co., Ltd.), Chinopearl CBS (manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like can be contained. Among these, Chino Pearl CB
S and Whitex SA are preferable, and as the compounding amount,
0.1-1 mass% is preferable. These may be used alone or in combination of two or more.

(5) Enzymes Enzymes (which are enzymes that inherently perform an enzyme action during the washing step) are classified according to the reactivity of the enzyme, such as hydrolases, oxidoreductases, lyases, transferases and isomerases. Although the above can be mentioned, any of them can be applied to the present invention. Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases. Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain,
Promelin, carboxypeptidase A and B, aminopeptidase, and aspergillopeptidase A and B, which are commercially available products such as sabinase, alcalase (Novo Industry Co., Ltd.), API21 (Showa Denko KK), Maxacar (Gistprocay). (Death), JP-A-5-254
Protease K-14 or K-1 described in Japanese Patent No. 92
6 etc. can be mentioned. Specific examples of esterases include gastric lipases, bankreatic lipases, plant lipases, phospholipases, cholinesterases, and phosphotases.
Specific examples of lipases include commercially available lipases such as lipolase (Novo Industry Co., Ltd.) and liposam (Showa Denko KK). Further, as cellulase, commercially available cellzyme (Novo Industry Co., Ltd.),
The cellulase and the like described in claim 4 of JP-A-63-264699 can be mentioned, and the amylase can be, for example, commercially available Termamyl (Novo Industry Co., Ltd.) and the like. Among these, Termamyl and Alcalase are more preferable, and the compounding amount is preferably 0.1 to 2% by mass. These may be used alone or in combination of two or more. When the composition of the present invention is a solid bleaching composition, it is desirable that the enzyme is separately granulated as stable particles and used in a dry blended state with detergent dough (particles).

(6) Enzyme stabilizer As an enzyme stabilizer, in order to remove chlorine in tap water,
A reducing agent such as sodium sulfite and sodium hydrogen sulfite, a calcium salt, a magnesium salt, a polyol, a boron compound and the like can be added. 4 of these
Sodium borate is preferred, and the compounding amount is 0.05
2 mass% is preferable. These may be used alone or in combination of two or more. In addition, when the composition of the present invention is a solid bleaching composition, sodium sulfite, sodium hydrogen sulfite, and sodium 4-borate are the same as those in the above (e).
Included in the ingredients.

(7) Other polymers As a binder or a powder physical property agent when densifying the polymer, and in order to impart an anti-redeposition effect to the hydrophobic fine particles, the weight average molecular weight is 200 to 200,00.
0 polyethylene glycol and weight average molecular weight 1000
˜100,000 polymers of acrylic acid and / or maleic acid, polyvinyl alcohol and the like can be added. Further, polyvinylpyrrolidone can be added to the bleaching composition of the present invention in order to impart a color transfer preventing effect. Among them, the weight average molecular weight is 1500 to 7
000 polyethylene glycol is preferable, and the blending amount is preferably 0.05 to 5 mass%. These may be used alone or in combination of two or more.

(8) Anti-caking agent As an anti-caking agent, paratoluene sulfonate,
Xylene sulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be added.

(9) Defoaming Agent As the defoaming agent, there can be mentioned conventionally known ones such as silicone / silica type defoaming agents. This defoaming agent is described in JP-A-3-186307 described below. A defoaming agent granulated product produced by the method described in the lower left column of page 4 of the publication may be used. First, 20 g of Dow Corning silicone (compound type, PS antifoam) as an antifoaming component is added to 100 g of Nitto Chemical Co., Ltd. maltodextrin (enzyme-modified dextrin) and mixed to obtain a homogeneous mixture. Next, 50% by mass of the obtained homogeneous mixture, 25% by mass of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% by mass of anhydrous anhydrous Glauber's salt were mixed at 70-80 ° C., and then extruded by Fuji Paudal Co., Ltd. Granulator (Model EXK
Granulate according to S-1) to obtain a granulated product.

Further, if it is a component generally added to a detergent for clothes and a bleaching agent, it can be added if necessary.

In the composition of the present invention, the compound produced by the oxidation reaction of the phenol derivative is 0.000.
It may enter from 1 to 1% by mass. Examples of these compounds include formic acid, acetic acid, glycolic acid, propionic acid, malonic acid, malic acid, oxalic acid and the like.

The form of the bleaching composition of the present invention is a liquid or a solid such as a powder, granules, tablets, briquettes, sheets or bars, and more preferably a powder, as described above. The method for preparing the bleaching composition of the present invention is not particularly limited and, for example, as described above, except that the above components are appropriately granulated or compounded as necessary, according to the conventional method of each form. It can be prepared. Further, when commercializing, containers are used in consideration of their respective operability and stability, and it is particularly preferable to select a container that has little influence on decomposition of peroxide by humidity and light.

The bleaching composition of the present invention is a product to be bleached,
The use method is not particularly limited, for example, clothing,
Fabric products such as cloths, sheets and curtains, paper products such as wood pulp, tableware and glass, hard surfaces such as washing tubs can be treated in the same manner as ordinary bleaching compositions, so that they can be used as organic products. Dirt, yellowing substances, stains, molds and the like can be bleached, especially in the case of the bleaching composition of the present invention, considering that it is excellent in the stability of hydrogen peroxide in a diluent, the composition If the product is a liquid bleaching composition, for example, after the stock solution is applied to the bleached product, it is immersed in water having a volume of 50 to 1500 times the volume of the composition, or diluted to a volume of 50 to 1500 times the volume of the composition. If the object to be bleached is immersed in the liquid, or if it is a solid bleaching composition, 0.0
A method such as immersing the bleached substance in a 5 to 2 mass% solution is suitable, and particularly, the immersing time is about 30 minutes to 24 hours,
Preferably, it can be suitably used for a long-time immersion of about 2 to 24 hours.

[0070]

EFFECTS OF THE INVENTION According to the present invention, an oxygen-based bleaching composition is obtained which has a high stability of hydrogen peroxide in a washing solution even after being immersed for a long time and has an excellent bleaching power.

[0071]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise specified,% in each example is% by mass, the concentrations of the components shown in Table 9 were converted to pure components, and the components used in Tables 10 and 11 were blended as they were.

Examples 1 to 21 and Comparative Examples 1 to 12 Liquid bleaching compositions according to the compositions of Tables 9 to 11, respectively.
The liquid bleaching compositions of Examples 1 to 7 and Comparative Examples 1 to 6 and the powder bleaching compositions of Examples 8 to 21 and Comparative Examples 7 to 12 were prepared according to the conventional method of powder bleaching composition. The bleaching power (bleaching rate) and hydrogen peroxide residual rate of each composition were evaluated by the following methods. The results are also shown in Tables 9 to 11. The abbreviation components in the table have the following meanings.

Hydrogen peroxide: Mitsubishi Gas Chemical Co., Ltd. (Purity: 35%, food additive standard) Sodium percarbonate: Mitsubishi Chemical Co., Ltd. (effective oxygen: 1
0.9, trade name: SPC-Z) 4-methoxyphenol: manufactured by Kawaguchi Chemical Industry Co., Ltd. (product name: MQ-F) 4-hydroxybenzoic acid: p-hydroxybenzoic acid manufactured by Kanto Chemical Co., Inc. Reagent Di-t-butyl-hydroxytoluene: JGC Universal Co., Ltd. (Brand name: BHT-C) Phenol: Kanto Chemical Co., Inc. Special grade reagent HEDP-H: 1-hydroxyethane-1,1-diphosphonic acid ALBRIGHT & WILSON Company name (BRIQUEST ADPA) HEDP-4Na: 1-Hydroxyethane-1,1-diphosphonic acid tetrasodium Solusia Japan KK
(Product name: Dequest 2016D) Ethylenediaminetetra (methylenephosphonic acid) -N
a: ALBRIGHT & WILSON (Product name:
BRIQUEST 422) EDTA-4Na: manufactured by Lion Chemical Co., Ltd. (trade name:
Disorbin NA-T) Tris ((2-pyridyl) methyl) amine-manganese complex (comparative product): The synthetic method is shown below. TACN (Comparative): Tris-μ-oxo-bis [(1,4,7-trimethyl-1,4,7triazacyclononane) manganese (IV)] pentafluorophosphate (Journal of the American)
Chemical Society 1998 11
0, pages 7398-7411). d-18: (N, N'-ethylenebis (4-hydroxysalicylidene iminate))-manganese complex. The synthetic method is shown below. d-5: (Tris (salicylideneiminoethyl) amine) -manganese complex. The synthetic method is shown below. Sodium carbonate: manufactured by Tokuyama Corporation (trade name: soda ash dense) Sodium hydrogen carbonate: anhydrous sodium hydrogen carbonate Kanto Chemical Co., Inc. special grade reagent sodium sulfate: manufactured by Nippon Kagaku Co., Ltd. (trade name: neutral anhydrous sodium sulfate) Phosphoric acid Potassium dihydrogen: Kanto Chemical Co., Ltd. special grade reagent bleach activator-1: Mitsui Chemicals, Inc. (4-decanoyloxybenzoic acid) Bleach activator-2: Mitsui Chemicals, Inc. (dodecanoyloxybenzene) Sodium sulfonate) POE-AE: manufactured by Lion Chemical Co., Ltd. (Nonionic surfactant, alkyl chain length 12 to 14, average number of moles of ethylene oxide added is 5, ethylene oxide 3 to 7)
90% of total molar adduct. (Pure content: 90%)) LAS-Na: manufactured by Lion Corporation (straight chain alkyl (C
10-C14) Sodium benzenesulfonate) LAS-K: manufactured by Lion Corporation (straight chain alkyl (C1
0 to C14) Potassium benzenesulfonate) α-SF-Na: manufactured by Lion Corporation (carbon chain length 14 to
16 α-sulfofatty acid methyl ester sodium) AOS-Na: manufactured by Lion Corporation (carbon chain length 14 α
-Sodium olefin sulfonate) AOS-K: manufactured by Lion Corporation (carbon chain length 14-18)
α-Olefin sulfonate potassium) NaOH: Kaneka Fuchi Chemical Industry Co., Ltd. (trade name: liquid caustic soda) Enzyme: Novozyme (trade name: Durazyme 8.0
T) Fragrance composition: As the fragrance compositions A to D, the mixtures obtained by the formulations shown in Tables 1 to 7 were used.

Tris ((2-pyridyl) methyl) amine
-As a synthetic material of a manganese complex , 2- (chloromethyl) pyridine hydrochloride (a reagent manufactured by Sigma-Aldrich Co., Ltd.), 2,2'-dipicolylamine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), manganese chloride-4 Hydrate (Kanto Chemical Co., Inc. reagent), 5.4N
Sodium hydroxide (sodium hydroxide (Kanto Chemical Co., Inc.
Reagent), diethyl ether (Kanto Chemical Co., Inc. reagent), ethanol (Kanka Chemical Industry Co., Ltd.)
Reagent (manufacturing reagent) was used to synthesize a ligand (tris ((2-pyridyl) methyl) amine) according to the example of JP-A-10-140193. Crystal of the obtained ligand 1.0
g (0.003 mol) was dissolved in 100 ml of ethanol, and 0.68 g of manganese chloride tetrahydrate was added to this solution.
(0.003 mol) was added at room temperature. Concentrate ethanol under reduced pressure to about 50 ml, and then add 2 at 5 ℃.
It was left for 4 hours. The precipitated crystals were filtered off (Tris ((2
-Pyridyl) methyl) amine-manganese complex (comparative product)
1.1 g of crystals were obtained.

D-18: (N, N′-ethylenebis (4
-Hydroxysalicylidene iminate))-manganese complex
As a synthetic material for the body , ethylenediamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 2,4-dihydroxybenzaldehyde (reagent manufactured by Kanto Chemical Co., Ltd.), manganese chloride tetrahydrate (reagent manufactured by Kanto Chemical Co., Ltd.) , Methanol (Kanto Chemical Co., Inc.)
Reagent) and ethanol (Reagent manufactured by Kanka Chemical Industry Co., Ltd.) were used to synthesize by the following method. 30.1 g (0.501 mol) of ethylenediamine was placed in a reaction vessel, dissolved with 300 ml of methanol, and cooled to 0 ° C. 134.1 g of 2,4-dihydroxybenzaldehyde
A solution of (1.000 mol) in 100 ml of methanol was added dropwise over 1 hour. 0 ° C after dropping
It was stirred for 1 hour. After stirring, leave at 0 ° C for 3 hours,
The precipitated yellow crystals were filtered using a Kiriyama funnel. The obtained crystals were recrystallized with 500 ml of ethanol and purified to obtain 135 g of N, N'-ethylenebis (4-hydroxysalicylidene iminate) crystals. 1.0 g (0.003 mol) of crystals of N, N'-ethylenebis (4-hydroxysalicylidene iminate) obtained above
Was dissolved in 100 ml of ethanol, and to this solution was added 0.66 g (0.003 mol) of manganese chloride tetrahydrate at room temperature. After concentrating ethanol under reduced pressure to about 50 ml, the mixture was allowed to stand at 5 ° C. for 24 hours. The precipitated brown crystals were filtered off (N, N'-ethylenebis (4-hydroxysalicylidene iminate))-manganese complex (d
-18) crystals of 1.0 g were obtained.

D-5: (Tris (salicylidene iminoe
(Cyl) amine) -manganese complex synthesis material tris (2-aminoethyl) amine (Tokyo Kasei Kogyo Co., Ltd. reagent), salicylaldehyde (Tokyo Kasei Kogyo Co., Ltd. reagent), manganese chloride tetrahydrate ( Kanto Chemical Co., Ltd. Reagent), Methanol (Kanto Chemical Co., Ltd. Reagent), Ethanol (Kanka Chemical Industry Co., Ltd. Reagent)
Was used in the following method. 48.7 g (0.333 mol) of tris (2-aminoethyl) amine was placed in a reaction vessel, dissolved with 300 ml of methanol, and cooled to 0 ° C. 121.9 g of salicylaldehyde (0.
A solution of 998 mol) dissolved in 100 ml of methanol was added dropwise over 1 hour. After the dropping was completed, the mixture was further stirred at 0 ° C. for 1 hour. After completion of stirring, the mixture was allowed to stand at 0 ° C. for 3 hours, and then the precipitated yellow crystals were filtered using a Kiriyama funnel. The crystals obtained were recrystallized from 500 ml of ethanol and purified to give crystals of tris (salicylideneiminoethyl) amine 14
3 g was obtained. 1.0 g (0.002 mol) of crystals of tris (salicylideneiminoethyl) amine obtained above
Was dissolved in 100 ml of ethanol, and 0.43 g (0.002 mol) of manganese chloride tetrahydrate was added to this solution at room temperature. After concentrating ethanol under reduced pressure to about 50 ml, the mixture was allowed to stand at 5 ° C. for 24 hours. The precipitated dark green crystals were filtered off, and crystals of (tris (salicylideneiminoethyl) amine) -manganese complex (d-5) 1.1 g
Got

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

[Table 6]

[0083]

[Table 7]

Table 8 shows the redox potential and the hydrophobicity parameter logP value of each radical trapping agent used.

[0085]

[Table 8]

(I) Preparation of black tea-contaminated cloth 84 g of Nitto black tea (yellow package) was boiled in 4 L of tap water for 15 minutes, then rubbed with desalted cotton, and a 35 × 35 cm plain-woven cotton cloth ( # 100) 12
Soak 0 g and boil for 15 minutes. Remove from heat, let stand for 2 hours, let it air dry, wash with tap water until the washings are no longer colored, dehydrate and press, then 5 x 5
The test piece of cm was used for the experiment.

(II) Preparation of artificial iron water 4 kg of iron nails (JIS A5508 N75) were thoroughly washed with a commercial kitchen detergent (Lion's product name: Mama Lemon) until the surface oil was removed, and rinsed until the bubbles disappeared. After that, it was put into 18 L of tap water and left for 120 hours, then the nail was removed, and the iron concentration was measured by the orthophenanthroline method, and the iron was used in the experiment. (Iron concentration: 88.3 pp
m)

(III) Bleaching Rate The following bleaching rate test was conducted using 5 pieces of the soiled cloth obtained above. The liquid bleaching compositions shown in Table 9 were tested for bleaching rate by application, and the powder bleaching compositions shown in Tables 10 and 11 were tested for bleaching rate.

The bleaching rate for application and application was as follows: 1 ml of the liquid bleaching composition shown in Table 9 was applied to each contaminated cloth, left for 5 minutes, and then 500 ml of a commercial detergent solution (0.3% by mass, deionized water was used). And using artificial iron water, use calcium chloride to adjust to 3 ° DH hard water), and leave it for 6 hours, then rinse with tap water for 2 minutes and dehydrate for 1 minute.
It was air dried at 5 ° C for 12 hours. (Commercial detergent: New top,
Made by Lion Corporation

The bleaching rate for soaking was 0.5% by mass of the powder bleaching composition shown in Tables 10 and 11 (deionized water and artificial iron water were used, and calcium chloride was used to adjust to 3 ° DH hard water. 200 ml of the test solution prepared in 1) is prepared and placed 6
After aging, tap water rinsing was performed for 2 minutes and dehydration was performed for 1 minute, followed by air drying at 25 ° C. for 12 hours.

The treatment conditions of application and application are as follows. Soaking temperature: 25 ° C, iron concentration: 2ppm

The original cloth and the reflectance before and after washing were measured with NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd. using a filter of 460 nm, and the washing bleaching rate was calculated by the following formula:
The bleaching performance was evaluated. As for the bleaching rate, the average value of the bleaching rate for five contaminated cloths was calculated and evaluated according to the following criteria. The results are shown in Tables 9-11.

Standard composition (25 ° C., 3 ° DH, no iron content,
6 hours of application) In case of application: hydrogen peroxide 5% (pH = 6) (bleaching rate 55%) In case of application: sodium percarbonate 50%, (bleaching rate 4
5%)

[0094]

[Equation 2]

X: The bleaching rate is lower than that of the standard composition. Δ: The bleaching rate is equal to or higher than that of the standard composition, 0% or more +5.
Less than%: bleaching rate is higher than the standard composition, + 5% or more and 10%
Less than ◎: bleaching rate is significantly higher than the standard composition, + 10% or more

(IV) Measurement of residual rate of hydrogen peroxide For the liquid bleaching composition shown in Table 9, 2 ml of 20
It was dissolved in 0 ml of a commercially available detergent solution (0.3% by mass, deionized water and artificial iron water were used and adjusted to 3 ° DH hard water with calcium chloride), and the residual rate of hydrogen peroxide was measured. . (Commercial detergent: New top, manufactured by Lion Corporation)

The powder bleaching composition shown in Tables 10 and 11 had a concentration of 0.5% by mass (using deionized water and artificial iron water,
200 ml of a test solution of 3 ° DH hard water was prepared using calcium chloride, and the residual rate of hydrogen peroxide was measured.

The processing conditions for the liquid bleaching composition and the powder bleaching composition are as follows. Treatment temperature: 25 ° C, iron concentration: 2ppm

The residual amount of hydrogen peroxide after 4 hours was measured by the iodometry method, the residual ratio of hydrogen peroxide was calculated by the following formula, and the results evaluated by the following criteria are shown in Tables 9 to 11.

[0100]

[Equation 3]

X: The residual ratio of hydrogen peroxide is less than 50% △: Hydrogen peroxide residual rate is 50% or more and less than 70% ○: Hydrogen peroxide residual rate is 70% or more and less than 90% ⊚: Hydrogen peroxide residual rate is 90% or more

[0102]

[Table 9]

[0103]

[Table 10]

[0104]

[Table 11]

[Experimental Example] (I) Preparation of bleaching activation catalyst / granulation containing radical trapping agent Radical trapping agent and bleaching activation catalyst ((tris (salicylideneiminoethyl) amine) used in the above Examples
-Manganese complex) was granulated using polyethylene glycol (weight average molecular weight 6000, melting point 58 ° C). That is, the radical trapping agent and the bleaching activation catalyst were dissolved and uniformly dispersed in polyethylene glycol melted at 60 ° C. to have the composition shown in Table 12, and an anionic surfactant (alkyl chain length 14, alkyl chain length 14, After mixing with AOS-Na), pulverization and granulation were performed according to a conventional method.

Radical trapping agent and granules used in the experiment (bleach activating catalyst / granule containing radical trapping agent)
Table 12 shows the abbreviations and the mixing ratios. The average particle size is
The particle size distribution was calculated using a sieve and calculated.

[0107]

[Table 12]

(II) Stability of sodium percarbonate after storage Sodium percarbonate 1.25 in a screw cap bottle with a capacity of 20 ml.
g, bleach activating catalyst / radical trapping agent-containing granule 0.10 g (for b-1, b-2 and b-3, radical trapping agent 0.02 g, bleaching activation catalyst ((tris (salicylideneimino 0.01 g of ethyl) amine) -manganese complex) and 0.025 g of HEDP-4Na were added, and sodium carbonate was added to make the whole amount 2.50 g. Then, the cap was put on, and the whole was shaken to homogenize at 25 ° C. After being stored for 2 weeks, the amount of residual hydrogen peroxide was measured by the iodometry method, and the stability of sodium percarbonate was calculated by the following formula.

[0109]

[Equation 4]

(III) Solubility of Granules Containing Bleaching Activation Catalyst / Radical Trap Agent 500 g of tap water at 25 ° C. was placed in a 500 ml beaker, and 1.25 g each of sodium percarbonate and sodium carbonate.
After the dissolution, 0.10 g of the bleaching activation catalyst / radical trapping agent-containing granulated product was added, and the time until the granulated product was dissolved and uniformly dispersed was measured visually, and evaluated according to the following criteria. The results are shown in Table 13.

◯: Time until dissolution and uniform dispersion is less than 3 minutes Δ: Time until dissolution and uniform dispersion is 3 minutes or more and less than 7 minutes X: Time until dissolution and uniform dispersion is 7 minutes that's all

[0112]

[Table 13]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H003 AB15 AB19 AB21 AC08 DA01                       EA11 EA12 EA16 EA21 EB04                       EB07 EB24 EB26 ED02 EE04                       EE05 FA26 FA43 FA44

Claims (4)

[Claims] 1. A hydrogen peroxide or a peroxide which is dissolved in water to generate hydrogen peroxide, (b) a phenolic radical trapping agent, (c) a phosphonic acid metal scavenger, and (d) A bleaching composition comprising a bleaching activation catalyst containing a ligand represented by the general formula (I) and a transition metal. [Chemical 1] (However, in the above formula (I), l is directly bonded to X-
It is an integer of 0 to 2 showing the number of [(CH) _m (R ² ) -A]. X is represented by R when l is 0, represented by R ′ when 1 is 1, and is represented by nitrogen atom, phosphorus atom or C (R) when l is 2. Is. R, R ¹ and R
² may be the same or different, each is a hydrogen atom, an optionally substituted alkyl group,
It is a cycloalkyl group or an aryl group, and R ′ is an optionally substituted alkylene group or cycloalkylene group. n and m may be the same or different and each is a number from 0 to 2. A and B may be the same or different and each is a group represented by the following formula (II) or (III). ^{) -NR 3 R 4 ... (II} ) -N = R 5 ... (III) ( where the formula (II) in, (III), R ³ and R ⁴ may be the same or different, R ^3, R ⁴ is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, respectively. In the alkyl group, the cycloalkyl group, the aryl group and the benzyl group, some or all of the hydrogen atoms are a hydroxyl group, a halogen atom or a halogen atom. Optionally substituted with an atom, a sulfonic acid group, a carboxylic acid group, an alkyl group or an aryl group having a carbon chain length of 1 to 3. R ⁵ is an alkylidene group, a cycloalkylidene group or a benzylidene group, and these groups are Part or all of the hydrogen atoms are a hydroxyl group, a halogen atom, a sulfonic acid group, a carboxylic acid group, an alkoxyl group having a carbon chain length of 1 to 3, and an alkyl group respectively having a carbon chain length of 1 to 3.
May be substituted with a dialkylamino group, an alkyl group having a carbon chain length of 1 to 3, or an aryl group. ) 2. The bleaching composition is a solid bleaching composition such as powder, granules, tablets, briquettes, sheets or bars, and the bleaching composition is 1% by mass in deionized water. The total ionic strength of the inorganic ions when diluted to 0.15 to 0.27,
The bleaching composition according to claim 1, which comprises an inorganic compound. 3. The component (d) is (tris (salicylideneiminoethyl) amine) -manganese complex or (N,
The bleaching composition according to claim 1 or 2, which is an N'-ethylenebis (4-hydroxysalicylidene iminate))-manganese complex. 4. The bleaching composition is a solid bleaching composition such as powder, granules, tablets, briquettes, sheets or bars, which comprises the component (b) and the component (d).
The bleaching composition according to claim 1, 2 or 3, which comprises composite particles containing a surfactant and / or a binder compound having a melting point of 37 to 65 ° C.