WO1998007826A2

WO1998007826A2 - Bleaching agent compositions

Info

Publication number: WO1998007826A2
Application number: PCT/JP1997/002838
Authority: WO
Inventors: Tsuneo Kobayashi; Masahito Mikami; Rumi Takano; Yasuhisa Kuriyama; Jun Kokubu; Yasuo Hiro; Yoshiko Tsuji
Original assignee: Johnson Company, Ltd.
Priority date: 1996-08-20
Filing date: 1997-08-15
Publication date: 1998-02-26
Also published as: JPH1060489A; WO1998007826A3; JP3859778B2

Abstract

A bleaching agent composition is presented which comprises hydrogen peroxide or a peroxide which generates hydrogen peroxide, and a dicyandiamide derivative, wherein the pH of the aqueous solution of the mixture thereof becomes at least 7.5. The bleaching agent composition has an excellent bleaching effect on clothes and the like, and has excellent bleaching power to the mildew generated on the wall of a house or furniture, and does not have any odor.

Description

DESCRIPTION

BLEACHING AGENT COMPOSITIONS Technical Field The present invention relates to a hydrogen peroxide bleaching agent composition having excellent bleaching power. The bleaching agent composition of the present invention is used for the purpose of cleaning, bleaching, disinfecting/sterilizing, and deodorizing, in particular, it is favorably used for removing and bleaching mildew.

Background Art

Bleaching agents and fungicides can be divided into chlorine bleaching agents and peroxide bleaching agents . The chlorine bleaching agents containing sodium hypochlorite as their main component have been used for bleaching clothes, or bleaching mildew on the walls of a house or on furniture since they have high bleaching power. However, though the chlorine bleaching agents have excellent bleaching power, since they discolor the clothes, they are not appropriate for bleaching dyed or patterned cloths . They also have defects that they generate a peculiar odor due to the molecular chlorine, and give unpleasant feel to the users, and that they may cause chlorine gas poisoning if they are misused. On the other hand, peroxide bleaching agents have a broader range of use application as a bleaching agent than that of the chlorine bleaching agents, and have no unpleasant smell, thus the usage thereof, particularly that of the household bleaching agent has been increased. But, peroxides alone have poorer bleaching power in comparison with the chlorine bleaching agents, and the bleaching power thereof is not sufficient for bleaching the clothes at a low temperature, or for bleaching mildew and the like, which is attached on walls of a house or on furniture, in particular, on the bathroom walls, kitchen counter, ceiling or tile joints and the like.

Accordingly, peroxides such as hydrogen peroxide, sodium carbonate-hydrogen peroxide adduct, and sodium perborate have been conventionally used together with N-acyl compounds such as tetraacetylethylenediamine (TAED), tetraacetylglycoluryl (TAGU), and esters such as glucose pentaacetate and saccharose octaacetate, to improve the bleaching power. Various nitrile compounds have been also proposed as a bleach activating agent for improving the bleaching power of the peroxides . For example, various nitriles have been proposed as a useful bleach activating agent in United Kingdom Patent No. 802035, iminodiacetonitrile has been proposed as a useful bleach activating agent in USP No. 3,882,035, and p-chlorobenzoyl cyanamide has been proposed as a useful bleach activating agent in Japanese Patent Application Laid-Open No. 52-52880.

However, even though these activating agents are used together with the peroxides, the bleaching of clothes can not be carried out sufficiently at a low temperature, and the bleaching effect on the mildew in a house has been insufficient as well. Besides, acetylamide compounds such as TAED and acetyl esters such as glucose pentaacetate have a drawback that they react with hydrogen peroxide to generate peracetic acid and produce a peculiar odor.

Disclosure of Invention

An object of the present invention is to provide a bleaching agent composition which has an excellent effect in bleaching clothes and the like, exercises excellent bleaching power to the mildew generated on walls of a house or on furniture, and which does not have an odor. As a result of their intensive study on the above- mentioned problems, the present inventors found that a bleaching agent composition comprising (A) hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aqueous solution, and (B) at least one kind of dicyandiamide derivatives, wherein the pH value of the mixed aqueous solution of the component (A) and the component ( B ) becomes at least 7.5, has a very high activity in the bleaching of clothes and the bleaching of mildew grown on the walls of a house and the like, and has no irritating smell, and completed the present invention.

Preferred Embodiments of Invention

As hydrogen peroxide or a peroxide to generate hydrogen peroxide, a commercially available hydrogen peroxide aqueous solution, sodium carbonate-hydrogen peroxide adduct in which the sodium carbonate and hydrogen peroxide are added at the molar ratio of 2:3, sodium perborate hydrate, sodium perborate tetrahydrate and the like are used.

On the other hand, the dicyandiamide derivative is represented by the following structural formula (1). RR'N-C(=NH)NH-C≡N (1)

In the above-mentioned formula, R and R' represent H, or an alkyl or aryl group having 1 - 12 carbon atoms optionally having a substituent ( the substituent hereby means hydroxyl, sulfone, carboxyl , or sulfuric ester group ) , provided that R and R ' are not H at the same time. Examples thereof include N-ethyl dicyandiamide, N,N-dimethyl dicyandiamide, N-p-sulfophenyl dicyandiamide, N-p-hydroxyphenyl dicyandiamide, N-β- carboxyethyl dicyandiamide and the like. R and R' can be bonded together to form a five or six membered ring (such as N, N-cyclopentamethylene dicyandiamide). In such a case, the five or six membered ring may contain a hetero atom such as O and N (an example thereof includes N, N-cyclopenta-4 ' -oxa-methylene dicyandiamide). Further, R and R' can be an alkylene group linking two cyanoguanidyl groups across two dicyandiamide molecules (for example, N, N' -ethylene- bis-dicyandiamide ) . The production process for the above-mentioned dicyandiamide derivative is generally known, and an example thereof has been disclosed in USP No. 2,455,807 (1948).

The above-mentioned component (A) and the component ( B ) are used in the form of a mixed aqueous solution, the pH of which is at least 7.5, preferably 9 - 13. For producing a mixed aqueous solution having the pH of at least 7.5, generally a hydroxide of an alkali metal such as caustic soda and caustic potash, or an alkali agent such as sodium orthosilicate is used, however, an acid such as hydrochloric acid can be also used for controlling the pH depending on the situation. Examples of an alkali agent include, in addition to the above-mentioned alkali metal hydroxide, known alkali builders such as an aminocarboxylic acid type builder, oxycarboxylic acid type builder, phosphonic acid type builder, a polymeric type builder such as acrylate-vinylsulfonate, phosphate builder, silicate builder, borate builder, and carbonate builder, but among them, a silicate builder is preferable.

To use the bleaching agent composition of the present invention, the component (A): hydrogen peroxide or a peroxide which generates hydrogen peroxide, and the component (B): a dicyandiamide derivative, and if necessary, the third component (C): an alkali agent or an alkali builder are dusted on the object to be bleached or these are used together with a detergent during washing. However, the above-mentioned components (A), (B) and if necessary (C) are preferably made into a mixed aqueous solution previously in order to carry out the bleaching process easily. The content of hydrogen peroxide in such a case is 0.5 - 60 % by weight, preferably 0.5 - 10 % by weight, more preferably 1 - 6 % by weight. The content below this range results in weak bleaching power, and the content over this range makes the handling difficult. The content of the dicyandiamide derivative is 0.2 - 30 % by weight, preferably 0.5 - 10 % by weight, more preferably 0.5 - 5 % by weight. An alkali agent or an alkali builder is blended therewith if necessary so that the pH of the resulting mixed aqueous solution becomes at least 7.5, preferably in the range of from 9 to 13. Those components can be prepared separately or in combination, and dissolved in water immediately before the use to provide the aqueous solution or slurry. The bleaching agent composition of the present invention can be mixed with a known detergent or bleaching agent constituent such as a surfactant, an organic or inorganic builder, hydrotrope agent, solvent, perfume, abrasive agent, and a stabilizer for hydrogen peroxide, if necessary. It can also be used together with dicyandiamide, cyanourea, a dicyanoamine salt, a cyanamide salt and the like, if necessary. In order to increase the viscosity of the bleaching agent composition and reduce the dripping of the liquid when it is coated on a ceiling, or a vertical or inclined surface, a thickening agent including a synthesized or semisynthetic polymer such as an acrylic acid derivative polymer and a cellulose derivative, a natural polymer such as xanthan gum, guar gum and an inorganic type thickening agent such as alumina sol can be added as well.

To further illustrate the present invention, the following Examples and Comparative Examples are given, provided that the present invention is not limited by the following Examples.

The bleaching agent compositions obtained in the Examples and Comparative Examples were evaluated by the following test methods. 1. Bleaching test method and evaluation method 1 ) Standard soiled cloth For the bleaching test, EMPA #115 soiled cloth for bleaching test was used. The EMPA soiled cloth was cut into pieces of 10 cm x 10 cm and subjected to the bleaching test.

2 ) Bleaching test method 20 g of a bleaching agent composition was put into a beaker and one piece of EMPA soiled cloth was immersed therein and allowed to stand for 10 minutes. Then the soiled cloth was taken out and rinsed with tap water thoroughly and dried. 3 ) Evaluation method

The test cloth treated according to the above- mentioned process was classified into four levels according to the following criteria by visual examination. Bleaching degree IV: Almost completely bleached. Bleaching degree III: Bleached to some extent. Bleaching degree II: Scarcely bleached. Bleaching degree I: Not at all bleached. 2. Mildew stain removal test method and evaluation method

1 ) Mildew culturing process

An agar culture medium was sterilized by steam and put in a sterilized Petri dish, and black mildew ( Aureobasidium pullulans: IF06353, IAM F-24) was transplanted on the agar medium and cultured in an incubator at 28 "C for 30 days. 2 ) Mildew stain removal test method

A glass tube of a fixed length was inserted into the agar medium on which the black mildew was grown and bleaching agent composition was poured into the glass tube and allowed to stand for 30 minutes, then the degree of the mildew stain removed was evaluated.

3 ) Evaluation method

The mildew surface treated according to the above- mentioned process was classified into four levels according to the following criteria by visual examination.

Mildew stain removal degree IV: Almost completely removed .

Mildew stain removal degree III: Removed to some extent.

Mildew stain removal degree II: Scarcely removed.

Mildew stain removal degree I: Not at all removed. Examples 1 - 9 and Comparative Examples 1 - 3

Mixed aqueous solutions were prepared by dissolving materials in water such that the hydrogen peroxide concentration became 1.0 - 20.0 % by weight, and the dicyandiamide derivative concentration became 1.0 - 10.0 % by weight, then the pH of the mixed aqueous solutions was controlled to pH 7.0 - 10.5 by using sodium hydroxide or diluted hydrochloric acid to provide bleaching agent compositions. The obtained compositions were tested for their bleaching effect and mildew stain removal effect using EMPA #115 standard soiled cloth and the mildew stain. The results are shown in Table 1 and Table 2. The content of each component is given by per cent by weight in the following Tables.

Table 1

Examples 1 2 3 4 5 6

Hydrogen 6.0 6.0 6.0 4.0 6.0 10.0 peroxide

N-methyl 5.0 dicyandiamide

N-ethyl 4.0 10.0 3.0 dicyandiamide

N-propyl 5.0 dicyandiamide

N-ethyl, N-methyl 3.0 dicyandiamide

Caustic soda ( pH adjustment ) trace amount

Ion exchanged water remainder

Total 100 100 100 100 100 100 pH of the mixed aqueous 10.4 10.5 10.5 10.3 10.0 10.5 solution

Bleaching test IV IV IV III III III results

Mildew stain removal test III III IV III III III results

Table 2

Examples 7 8 9

Comparative 1 2 3 Examples

Hydrogen 6.0 6.0 6.0 6.0 6.0 peroxide

N-methyl dicyandiamide

N-ethyl 1.0 5.0 10.0 5.0 dicyandiamide

N-propyl 5.0 dicyandiamide

N-ethyl, N-methyl dicyandiamide

Caustic soda trace amount (pH adjustment)

Ion exchanged remainder water

Total 100 100 100 100 100 100 pH of the mixed aqueous 9.5 9.5 9.5 10.5 7.0 10.5 solution

Bleaching test III III III II II I

Mildew stain III III III II I I removal test

Examples 10 - 19 and Comparative Examples 4 - 6

Mixed aqueous solutions were prepared by dissolving materials in water such that the hydrogen peroxide concentration became 1.0 - 20.0 % by weight, and the dicyandiamide derivative concentration became 1.0 - 10.0 % by weight, then the pH of the mixed aqueous solutions was controlled to pH 7.0 - 10.5 by using sodium orthosilicate to provide bleaching agent compositions. The obtained compositions were tested for their bleaching effect and mildew stain removal effect using EMPA #115 standard soiled cloth and the mildew stain. The results are shown in Table 3 and Table 4.

Table 3

Examples 10 11 ₁₂ 13 14 15

Hydrogen 6.0 6.0 6.0 3.0 10.0 20.0 peroxide

N-β-sulfoethyl 2.0 dicyandiamide

N-p-sulfophenyl 6.0 dicyandiamide

N-β- carboxyethyl 6.0 dicyandiamide

N-p-oxyphenyl 5.0 dicyandiamide

N-ethyl, N-methyl 2.0 dicyandiamide

N, N-ethylene- bis- 3.0 dicyandiamide

Sodium orthosilicate trace amount ( pH adjustmen )

Ion exchanged remainder water

Total 100 100 100 100 100 100 pH of the mixed aqueous 10.4 10.5 10.5 10.3 10.0 9.5 solution

Bleaching test III IV IV III III III results

Mildew stain III IV IV III III III removal test Table 4

Examples 16 17 18 19

Comparative 4 5 6 Examples

Hydrogen 6.0 10.0 6.0 6.0 6.0 10.0 peroxide

N-β-sulfoethyl 5.0 dicyandiamide

N-p-sulfophenyl 5.0 10.0 5.0 dicyandiamide

N-β- carboxyethyl 5.0 dicyandiamide

N-p-oxyphenyl dicyandiamide

N-ethyl, N-methyl 2.0 dicyandiamide

N, N-ethylene- bis- dicyandia ide

N-methyl 4.0 dicyandiamide

Sodium trace amount orthosilicate

Ion exchanged water remainder

Total (%) 100 100 100 100 100 100 100 pH of the mixed aqueous 10.5 10.5 10.7 10.5 10.5 7.0 10.5 solution

Bleaching test IV IV IV IV II II I

Mildew stain IV IV IV IV II I I removal test Examples 20 - 23 and Comparative Examples 7 - 9

Bleaching compositions were prepared using sodium carbonate-hydrogen peroxide adduct or sodium perborate hydrate instead of hydrogen peroxide. The amount of the sodium carbonate-hydrogen peroxide adduct or sodium perborate hydrate used was represented by the amount of hydrogen peroxide contained. The obtained bleaching agent compositions were used for EMPA soiled cloth bleaching test and mildew stain removal test and the results are shown in Table 5.

Table 5

Examples 20 21 22 23

Comparative 7 8 9 Examples

Hydrogen 3.0 peroxide

SPC* 5.0 6.0 3.0 6.0

PB** 6.0 6.0

N-methyl 5.0 dicyandiamide

N-ethyl 5.0 dicyandiamide

N-β-sulfoethyl 6.0 dicyandiamide

N-p-sulfophenyl 10.0 5.0 dicyandiamide

N-β- carboxyethyl dicyandiamide

Sodium trace amount orthosilicate

Ion exchanged remainder water

Total 100 100 100 100 100 100 100 pH of the mixed aqueous 10.3 10.5 10.3 10.5 9.6 10.6 10.6 solution

Bleaching test IV IV IV IV II I II results

Mildew stain removal test IV IV IV IV II I II results

* : Sodium carbonate-hydrogen peroxide adduct ( the figure represents the concentration of hydrogen peroxide )

**: Sodium perborate hydrate (the figure represents the concentration of hydrogen peroxide ) Effect of Invention

The results of Table 1 to Table 5 show that all of the compositions containing both hydrogen peroxide, sodium carbonate-hydrogen peroxide adduct or sodium borate hydrate and a dicyandiamide derivative, which are so prepared that the pH of the mixed aqueous solution becomes at least 7.5, show an excellent bleaching effect and mildew stain removal effect, while all of the Comparative Examples which do not contain either hydrogen peroxide, sodium carbonate-hydrogen peroxide adduct, and sodium perborate hydrate, or a dicyandiamide derivative, or which contain both of them but the pH of the mixed aqueous solution is below 7.5, show no or little bleaching effect as well as mildew stain removal effect. Among the alkali agents used as a pH adjusting agent, alkali builders used in Table 3, Table 4 and Table 5 show better bleaching effect and mildew stain removal effect than that of the alkali metal hydroxide used in Table 1 and Table 2, accordingly, it is more preferable to use the alkali builder as an alkali agent.

Claims

CLAIMS 1. A bleaching agent composition comprising the following component (A), and the component (B); ( A ) : hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aqueous solution,

(B): at least one dicyandiamide derivative of the following general formula ( 1 )

RR'N-C(=NH)NH-C≡N (1) where R and R ' represent H or an alkyl or aryl group having 1 - 12 carbon atoms optionally having a substituent selected from hydroxyl group, sulfone group, carboxyl group and sulfuric ester group, provided that R and R' are not H at the same time, wherein the pH of the mixed aqueous solution of the component (A) and the component (B) becomes at least 7.5.

2. A bleaching agent composition comprising a mixed aqueous solution having pH of at least 7.5, containing the following component (A) and the component ( B ) ;

(A): hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aqueous solution,

RR'N-C( =NH)NH-C≡N (1) where R and R' represent H or an alkyl or aryl group having 1 - 12 carbon atoms optionally having a substituent selected from hydroxyl group, sulfone group, carboxyl group and sulfuric ester group, provided that R and R' are not H at the same time, wherein the content of the component (A) in terms of hydrogen peroxide is 0.5 - 60 % by weight and the content of the component (B) is 0.2 - 30 % by weight.

3. A bleaching agent composition comprising the following component (A), the component (B) and the component ( C ) ;

(B): at least one dicyandiamide derivative of the following general formula (1)

RR'N-C(=NH)NH-C≡N (1) where R and R ' represent H or an alkyl or aryl group having 1 - 12 carbon atoms optionally having a substituent selected from hydroxyl group, sulfone group, carboxyl group and sulfuric ester group, provided that R and R' are not H at the same time,

(C): an alkali agent or an alkali builder, wherein the pH of the mixed aqueous solution of the component ( A) , component ( B ) and component ( C ) becomes at least 7.5.