Bleaching Composition Technical Field

This invention relates to a bleaching composition which has high bleaching power and is safe to colored fabrics and to a bleaching detergent composition containing the same. Background Art

Prevalent bleaching agents or beaching detergents for clothes mostly contain sodium percarbonate or sodium perborate as a bleaching base. Since these bases alone have insufficient bleaching properties, they are usually combined with an organic peracid precursor, such as tetraacetylethylenediamine (TAED), pentaacetylglucose (PAG) or sodium octanoyloxybenzenesulfonate (OOBS). The organic peracid precursor reacts with a peroxyhydrate, such as sodium percarbonate, to generate an organic peracid of higher bleaching performance which is effective to remove stains of foods, sweat, etc. However, the organic peracid thus generated has a disadvantage of weakening fiber. In particular, when such a bleaching component is scattered over color clothes together with a detergent component and the clothes are given a thorough soak for a while, the dyes of the fiber are also decolorized.

In order to overcome these problems, use of an amino acid (see JP-B-57-30183, the term "JP-B" as used herein means an "examined published Japanese patent application" ) or an

acylated amino acid (see JP-B-60-40544) has been proposed. These techniques are effective when applied to a bleaching component solely comprising an oxygen type peroxide but insufficient when applied to the oxygen type peroxide combined with an organic peracid or a precursor thereof. Disclosure of Invention

As a result of extensive investigations, the present inventors have found that excellent effects on prevention of decoloration can be obtained by compounding an oxygen type bleaching agent with integral granules of at least one of an amine, an amine salt and an ammonium salt and an organic peracid or a precursor thereof.

That is, the bleaching composition according to the present invention comprises (a) an oxygen type peroxide, (b) an organic peracid or a precursor thereof, and (c) at least one of an amine, an amine salt and a quaternary ammonium salt, the components (b) and (c) being integrally granulated with a binder or impregnated.

Component (c) , i.e., one or more of an amine, an amine salt and a quaternary ammonium salt (hereinafter sometimes referred to simply as an amine salt, etc.), prevents an organic peracid from decomposing and providing a highly concentrated decomposition product locally on color fiber thereby to prevent decoloration. The effect of the- amine salt, etc. is manifested by integrally granulating or impregnating the amine salt, etc. with an organic peracid or

a precursor thereof by means of a nonionic surface active agent and a binder, such as polyethylene glycol or a fatty acid.

The bleaching detergent composition according to the present invention contains the above-mentioned bleaching composition.

Component (a) which can be used in the present invention includes hydrogen peroxide, a peroxyhydrate, e.g., an alkali metal salt of percarbonate or persulfate, and inorganic peroxides, e.g., an alkali metal salt of perborate or persulfate. Sodium and potassium are preferable for the alkali metal salt. Component (a) is used in an amount of from 2 to 90% by weight, preferably from 5 to 70% by weight, and more preferably from 20 to 70% by weight, based on the whole bleaching composition.

Component (b), an organic peracid or a precursor thereof, includes perdodecanedicarboxylic acid, perbenzoic acid, monomagnesium perphthalate; an imide, e.g., tetraacetylethylenediamine, tetraacetylglycoluril or diacetylglycine anhydride; acetyl sugars, e.g., pentaacetylglucose and tetraacetylmethylglucoside; and sulfonates or carboxylates of fatty acid phenol esters, e.g., alkanoyloxybenzenesulfonates and alkanoyloxybenzenecarboxylates. Preferred example of component (b) is a straight chain organic peracid or a precursor thereof. More preferred example of component (b)

is a sulfonate or carboxylate of straight chain organic peracid precursor.

Component (b) is used in an amount of from 5 to 80% by weight, and preferably from 10 to 60% by weight, based on the amount of the component (a) in the bleaching composition or bleaching detergent composition of the present invention.

If the amount of component (b) is less than 0.3% by weight, desired bleaching effects are not manifested in some cases.

No further bleaching effect is obtained even with more than 60% by weight of component (b) .

Amines of component (c) include alkanolamines, e.g., monoethanolamine, diethanolamine, triethanolamine, N- methyldiethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine; ethylenediamine and derivatives thereof, e.g., diethylenetriamine, diethylenetetramine, hydroxypropylethylenediamine, hydroxyethylethylenediamine, and N,N-dimethylethylenediamine; polymethylenediamines or derivatives thereof, e.g., trimethylenediamine and tetramethylenediamine; alkylamines, e.g., methylamine, octylamine, dodecylamine, dodecyldimethylamine, and dioctadecylmethylamine; ethylene oxide adducts of these alkylamines; and aromatic amines, e.g., aniline and N-methylaniline. Among them, monoethanolamine, diethanolamine, triethanolamine, N- methylethanolamine and hydroxypropylethylenediamine are preferable. Secondary amines such as diethanolamine, N-

methylethanolamine and hydroxypropylethylenediamine are more preferable.

The above-enumerated amines may be used in the form of a salt with an acid. The salt-forming acid includes inorganic acids, e.g., sulfuric acid, hydrochloric acid, or hydrobromic acid; and organic acids, e.g., acetic acid, octanoic acid, lauric acid, myristic acid, dodecylsulfuric acid, an -olefinsulfonic acid, an alkylbenzensulfonic acid, benzoic acid, hydroxybenzoic acid, hydroxysulfonic acid, hydroxybenzenesufonic acid, citric acid, succinic acid, glutaric acid, adipic acid, and azelaic acid. Among them, benzoic acid, hydroxybenzoic acid, hydroxybenzensulfonic acid, glutaric acid, adipic acid and citric acid are preferable. Organic acids having a benzene group such as benzoic acid, hydroxybenzoic acid and hydroxybenzenesulfonic acid are more preferable. The quaternary ammonium salt of component (c) includes dodecyltrimethylammonium chloride, and dioctadecyldimethylammonium chloride. Preferred example of component (c) is an amine salt such as an alkanolamine salt. More preferred example of component (c) is a fatty acid salt or sulfate of secondary alkanolamine. Most preferred example of component (c) is an aromatic fatty acid salt or aromatic sulfate of secondary alkanolamine.

Component (c) is used in an amount usually of from 0.3 to 3 times, and preferably of from 0.4 to 2 times, the weight of component (b) in the bleaching composition or

bleaching detergent composition of the present invention. If the amount of component (c) is less than 0.3 times the weight of component (b), sufficient effects on prevention of decoloration cannot be produced. If it exceeds 3 times, granulation would be difficult.

It is essential that components (b) and (c) should be used as integrally granulated by using a binder. Binders to be used are those capable of solidifying at 40°C or higher to exhibit binding properties. Such binders include nonionic surface active agents, e.g., an ethylene oxide and/or propylene. oxide adduct of an alcohol or fatty acid containing from 8 to 18 carbon atoms; polyethylene glycol having an average molecular weight of 2000 to 30000; saturated or unsaturated fatty acids containing from 8 to 18 carbon atoms; and dibasic acids, e.g., succinic acid and glutaric acid. These binders may be used either individually or in combination thereof.

The binder is used in an amount usually of from 0.1 to 4 times, and preferably of from 0.2 to 2 times, the weight of component (b).

Granulation of components (b) and (c) may be carried out by using an inorganic salt, e.g., salt cake, as an additive for improving granulating properties.

The bleaching composition of the present invention is prepared by mixing component (a) and granules obtained by granulating components (b) and (c) (hereinafter referred to

as a granular organic peracid precursor). If desired, the bleaching composition may contain other optional components, such as enzymes, inorganic salts (e.g., sodium carbonate), surface active agents, and fluorescent whitening agents. Components (a) and the above-mentioned granular organic peracid precursor can be compounded with a detergent composition for clothes, etc. to provide a bleaching detergent composition.

The detergent composition may contain surface active agents commonly added to detergents and other known components, such as inorganic salts, chelate builders, soil redeposition inhibitors, enzymes, fluorescent whitening agents, and perf mes.

Examples of suitable surface active agents include anionic surface active agents, such as alkylbenzenesulfonates, α-olefinsulfonates, alkylsulfates, α- sulfo-fatty acid lower alkyl ester salts, higher fatty acid salts, alkanesulfonates, and polyoxyethylene alkylsulfate ester salts; nonionic surface active agents, such as polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene fatty acid esters, sugar fatty acid esters, and alkylamine oxides; cationic surface active agents, such as tetraalkylammonium chlorides; and amphoteric surface active agents, such as alkylsulfobetains. The content of surface active agent in the bleaching detergent composition ranges

from 3 to 40% by weight, and preferably from 5 to 30% by weight.

Examples of suitable inorganic salts include carbonates, sulfates, and silicates. The content of inorganic salts in the bleaching detergent composition ranges from 5 to 40% by weight, and preferably from 10 to 35% by weight.

Examples of suitable chelate builders include phosphates, polyacrylates, polycarboxylates, and zeolite. The content of chelete builders in the bleaching detergent composition ranges from 5 to 30% by weight, and preferably from 10 to 25% by weight.

Examples of suitable soil redeposition inhibitors include polyvinyl alcohol and enzymes such as amylase, cellulase, alkali lipase and alkali protease. The content of soil redeposition inhibitors in the bleaching detergent composition ranges from 0.3 to 5% by weight, and preferably from 0.5 to 3% by weight. The content of enzymes in the bleaching detergent composition ranges from 0.1 to 5% by weight, and preferably from 0.2 to 3% by weight.

The content of component (a) in the bleaching detergent composition ranges from 2 to 90% by weight, preferably from 2 to 40% by weight, and more preferably from

2 to 20% by weight. Best Mode for Carrying Out the Invention

The present invention will now be illustrated in greater detail with reference to Examples, but the present invention should not be construed as being limited thereof. The property of the compositions prepared in prevention of decoloration was evaluated according to the following test method.

In a cylindrical container having a diameter of 15 cm and a depth of 5 cm was put cloth (11 cm x 11 cm) dyed with Reactive Red-21, and 10 m of tap water at 40°C was poured thereon to give a thorough wet. Then, 5 g of a bleaching composition or 10 g of a bleaching detergent composition was uniformly scattered thereon. After standing for 30 minutes, the cloth was thoroughly washed with water and dried in air, and the degree of decoloration of the cloth was observed with the naked eye and evaluated according to the following rating system.

Rating system for Degree of Decoloration: 5 ... Serious decoloration

4 Considerable decoloration 3 Obvious decoloration 2 Slight decoloration 1 Very slight decoloration 0 No decoloration

Examples 1 to 23 and Comparative Examples 1 and 2 (1) Preparation of Granular Organic Peracid Precursor:

Two grams of an amine salt, etc. shown in Table 1 below, 5 g of tetraacetylethylenediamine (TAED), and 3 g of polyethylene glycol (molecular weight: 20000) were dry- blended at room temperature, melt-kneaded at 80° to 120°C, extruded, and pelletized. The pellets were classified to obtain granules which pass through 12 mesh and did not pass through 60 mesh.

TABLE 1

TABLE 1 (cont'd)

-H -H -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ SO, <_-

H

-H -H -CH ₃ cr -H -CH ₃ -CH ₂ CH ₂ OH ι/2so ₄ - -H -H -CH ₂ CH ₂ N(CH ₃ ) so ₄ ² -

H

-H -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH C ₁₃ H ₂₇ COO- -H -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH CnH^CONCfyCOO- CH ₃ n -H -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH l/2C _u H ₂₃ CONHCHCOO-

CH ₂ CH ₂ COO-

I P -H -H •CH ₂ CH ₂ OH -CH ₂ CH ₂ OH C ₆ H ₅ COO- q ^■C 11 ^H 23 -CH ₃ -CH ₃ -CH ₃ cr r ^■C 17 35 ^-C 17 ^H 35 -CH ₃ -CH ₃ Cl ^" s -H -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH

-H -H -CH ₂ CH ₂ OH ■CH ₂ CH ₂ OH w -H -H -CH ₂ CH ₂ OH -CH ₂ CH ₂ OH HOOC(CH ₂ ) ₄ COO ^"

For comparison, 5 g of tetraacetylethylenediamine and 5 g of polyethylene glycol (molecular weight: 20000) were granulated in the same manner as described above to prepare granular organic peracid precursor containing no amine salt, etc. (Comparative Example 1). Further, 5 g of tetraacetylethylenediamine and 2 g of polyethylene glycol (molecular weight: 20000) were granulated in the same manner as described above, and compound a of Table 1 was dry-blended with the granules (Comparative Example 2) . (2) Preparation of Bleaching Composition and Bleaching Detergent Composition and Evaluation Thereof:

A composition having the formulation shown in Tables 2 to 4 below was prepared using the granular organic peracid precursor prepared in (1) above, and decoloring properties of the composition was evaluated. The results obtained are shown in Table 5 below.

The bleaching compositions were prepared by dry blending the components. The bleaching detergent compositions were prepared by once preparing detergent particles by dry blending the components other than an enzyme, sodium percarbonate and the granular organic peracid precursor and then dry blending the above components.

-T m o

Tl in __ α ω an υi

^__ m I m- m m

-\ c m co

Note: Compounding ratio of each components was referred to as % by weight.

1) Sodium salt of straight or branched alkylbenzenesulfonate (alkyl average: 10 to 14 carbon atoms)

2) Polyoxyethylene (p = 9) secondary alkyl ether (alkyl average: 12 to 13 carbon atoms)

3) Protease (Alkalase 6.OT manufactured by NOVO INDUSTRI A/S) 4) Tinopal CBS-X manufactured by CIBA-Geigy A.G.)

o

TABLE 3

Formulation of Former Bleaching Detergent Composition (bulk density: 0.33)

Component

A0S-Na

LAS-Na ²⁾

AS-Na ³⁾

AES-Na*> ( p = 3 )

Soap ^5j

PEG#6000 ⁶⁾

Zeolite (4A type)

Sodium silicate

Sodium carbonate

Sodium percarbonate

Organic peracid precursor

Fluorescent 0.2 0.2 whitening agent ⁷⁾

Water

Sodium sulfate balance balance

Note: Compounding ratio of each components was referred to as % by weight.

1) Sodium α-olefinsulfonate having 14 to 18 carbon atoms

2) Sodium salt of straight chain alkylbenzenesulfonate having 10 to 14 carbon atoms in the alkyl moiety thereof

3) Sodium alkylsulfate having 12 to 15 carbon atoms

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RECTIFIED SHEET (RULE 91) ISA/EP

4 ) Sodium polyoxyethylene alkyl ether sulfonate having 12 to 15 carbon atoms in the alkyl moiety thereof

5) Sodium salt of saturated fatty acid having 14 to 18 carbon atoms

6) Polyethylene glycol (molecular weight: 6000)

7) Tinopal CBS-X manufactured by CIBA-Geigy A.G.

TABLE 4

19 -

RECTIFIED SHEET (RULE 91) ISA/EP

Note: Compounding-ratio of each components was referred to as % by weight.

1) Sodium salt of saturated fatty acid methyl ester sulfonate having 12 to 16 carbon atoms in the fatty acid moiety thereof

2) Potassium α-olefinsulfonate having 14 to 18 carbon atoms 3) Sodium salt of straight chain alkylbenzenesulfonate having 10 to 14 carbon atoms in the alkyl moiety thereof

4) Potassium salt of straight chain alkylbenzenesulfonate having 10 to 14 carbon atoms in alkyl moiety thereof

5) Sodium alkylsulfate having 12 to 15 carbon atoms 6) Sodium polyoxyethylene alkyl ether sulfate having

12 to 15 carbon atoms in the alkyl moiety thereof

7) Sodiu salt of saturated fatty acid having 14 to 18 carbon atoms

8) alkyl ether ethoxylate (average ethyleneoxide addition mole number: 15)

9) Polyethylene glycol (molecular weight: 6000)

10) Tinopal CBS-X manufactured by CIBA-Geigy A.G.

TABLE 5

Degree of Decoloration

Bleaching Bleaching Detergent Composition Composition

B B D E

to tO

Examples 24 to 28 TAED, amine salt o (see Table 1) and PEG 20,000 were dry-blended in the amounts as shown in the following Table 6 at room temperature, melt-kneaded at 80 to 120°C, extruded, and pelletized. The pellets were classified to obtain granules which pass through 12 mesh and did not pass through 60 mesh. The bleaching composition A (see Table 2) was prepared using the thus-obtained glanular organic peracid precursor, and decoloring properties of the composition was evaluated. The results obtained are shown in Table 6 below.

TABLE 6

Examples 29 to 34 and Comparative Examples 3 to 8

Five grams of each of organic peracid precursors represented by formulae (I) to (VI) shown below, 2 g of polyethylene glycol (molecular weight: 20000), and 3 g of amine salt a (see Table 1) were granulated in the same manner as in Example 1 to prepare granular organic peracid precursor.

O 0 C _a H _l7 COCH ₂ CO —ζ_ χ-S0 ₃ N a (ID

O C _. H ₁₅ CO- _VcθONa ( or -COOH) (III)

wherein Ac: acetyl group; Me: methyl group For comparison, 5 g of the organic peracid precursor and 5 g of polyethylene glycol (molecular weight: 20000) were granulated (Comparative Examples 3 to 8).

A bleaching composition and a bleaching detergent composition were prepared by using each of the resulting granules in the same manner as in Example 1. The property of the composition in prevention of decoloration was evaluated. The results obtained are shown in Table 7 below.

TABLE 7

Degree of Decoloration

Bleaching Bleaching Detergent Composition A Composition D

1 0 1 0 1 0 2 1 2 1 2 1 4 3

3

4 3

5 4

5

5

Industrial Applicability

The bleaching composition or bleaching detergent composition according to the present invention comprising granular organic peracid precursor prepared by integrally granulating an organic peracid or a precursor thereof and an amine salt, etc. with a binder and an oxygen type peroxide

- 25 -

RECTIFIED SHEET (RULE 91) ISA/EP

carries out bleaching while preventing decoloration of color fibers or clothes-