JPH0196298A - Bleaching agent composition - Google Patents

Abstract

PURPOSE:To obtain a stable reducing type bleaching agent composition, containing respective specific powdery thiourea dioxide, sodium carbonate, sodium hydrogencarbonate and aminocarboxylic acid in a specific proportion and capable of preventing emission of offensive smell by preservation for a long period. CONSTITUTION:The aimed composition obtained by containing (A) thiourea dioxide having preferably 50-500mum particle diameter, (B) sodium carbonate having 50-150mum average particle diameter, (C) sodium hydrogencarbonate having preferably 50-500mum average particle diameter and (D) one or more powdery aminopolycarboxylic acids selected from the group consisting of ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid and diethylenetriaminepentaacetic acid at weight ratio [(B)/(C)] of the components (B) to (C) within the range of 6/1-1/1 and a weight ratio [(B+C)/(D)] of the total of the components (B) and (C) to the component (D) within the range of 20:1-4:1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bleach composition, and more particularly, to a stable reduced bleach composition that is prevented from generating off-flavors during long-term storage.

Bleach is widely used for bleaching and preventing yellowing of clothing made from roasted rice, and for removing rust from gold products. Bleaching agents are broadly classified into reducing bleaching agents and oxidizing bleaching agents, and oxidizing bleaching agents are widely used because of their superior bleaching effect. However, oxidizing bleach has a low bleaching effect on mud stains and iron rust stains.
It's not always satisfying.

Therefore, attempts have been made to use reducing bleaching agents for stains that cannot be bleached with oxidizing bleaching agents, and many proposals have been made and have been put into practical use. Reducing bleaches include 1. Reducing agents that exhibit a direct or indirect reducing action, such as hydrosulfide, sulfite, thiourea dioxide, Rongalite (formaldehyde sulfinic acid), ascorbic acid, hydroquinone, oxalic acid, and thioglycolic acid. is used.

As household reductive bleaching agents, those containing thiourea dioxide as a main agent are widely used in terms of bleaching effect, usability, storage stability, safety, cost, etc. Thiourea dioxide does not exhibit reducing properties by itself, but is often used in combination with an alkaline agent to exhibit reducing properties.

However, when thiourea dioxide coexists with an alkaline agent, it deteriorates due to the influence of moisture in the air, tends to discolor and develop a strange odor, and its long-term storage stability decreases. Therefore, a technique has been proposed to stabilize the coexistence system of thiourea dioxide and an alkaline agent. In particular, JP-A No. 57-128767 discloses a reducing agent composition consisting of thiourea dioxide, anhydrous alkali metal salt of carbonate or trialkali metal salt of intermediate phosphate, and anhydrous alkali metal salt of bicarbonate. It is also described that sodium ethylenediaminetetraacetate and the like can be added as optional ingredients. However, the carbonate and bicarbonate used here must be anhydrous, and only by using anhydride can the composition be stabilized, that is, suppress the generation of off-flavors over time. be.

However, these anhydrous salts, especially alkali metal salts, tend to absorb moisture from the air, and care must be taken when storing them in the form of anhydrous salts. In particular, when bleach compositions are used at home, they often absorb moisture during repeated opening and sealing, making it difficult to maintain stability until the bleach composition is used up. There was a problem.

Purpose of the Invention The present invention further improves the stability of a bleach composition consisting of a coexisting system of thiourea dioxide and an alkaline agent, prevents deterioration due to storage at high temperatures and high humidity, and suppresses the occurrence of abnormal odors and discoloration. The purpose is to

Structure of the Invention The bleach composition of the present invention comprises the following (A), (B), and (C).
) and (D) components, and the blending ratio of components (B) and (C) used as alkaline agents is (B)/
(C) = 6/1 to 1/1, and alkaline agent [
(B) + (C)] and (D) aminopolycarboxylic acid at a weight ratio of 1' [(B) + (C)]/(D) = 20
/1 to 4/1 (7) range.

(A) Powdered thiourea dioxide.

(B) Powdered sodium carbonate with an average particle size of 50 to 150 μm.

(C) Powdered sodium bicarbonate.

(D) One or a mixture of two or more powdered aminopolycarboxylic acids selected from the group consisting of ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, and diethylenelutriaminepentaacetic acid.

The present invention will be explained in more detail below.

Powdered thiourea dioxide, component (A), can be produced using thiourea and hydrogen peroxide as raw materials by a known method;
It is commercially available as (manufactured by Tokai Denka Kogyo ■) and can be easily obtained.

(A) The particle size of the powdered thiourea dioxide is not particularly limited, but is preferably in the range of 50 to 500 μm from the viewpoint of dissolution rate in water and balance with the particle size of other powdered components.

The appropriate amount of thiourea dioxide (A) in the bleach composition of the present invention is 3 to 30% by weight, preferably 5 to 2% by weight.
It is 0% by weight.

(A) Thiourea dioxide has a strong ring element action in an alkaline aqueous solution. Various alkaline agents can be considered, but in the present invention, it is important to use (B) powdered sodium carbonate and (C) powdered sodium bicarbonate together.

(B) As powdered sodium carbonate, the average particle size is 50
A material in the range of ~150 μm is used.

When the average particle size exceeds 150 μm and the particle size becomes large, the bleach composition cannot be maintained sufficiently stable and an unpleasant odor is generated during storage. Further, when the average particle size is less than 50 μm, stability cannot be similarly improved.

The particle size of the powdered sodium bicarbonate component (C) is not particularly limited, but is preferably in the range of 50 to 500 μm from the viewpoint of balance with other powdered components.

The above-mentioned components (B) and (C) are both alkaline agents, and even if they are added alone to thiourea dioxide, they can bring out the reducing power of thiourea dioxide. In order to maintain stability that can withstand long-term storage, it is necessary to use components (B) and (C) together as an alkaline agent. Furthermore, even in this case,
It is not enough to simply use both alkali agents together, but the blending ratio of component (B) and component (C) in terms of weight ratio (B)
It is important to set the range of /(C) = 6/1 to 1/1. If it is outside this range, the storage stability of the bleached blade will deteriorate.

The amount of alkaline agent added to the bleach composition of the present invention, that is, (
The total blending amount of component B) and component (C) is desirably such that when the bleach composition is dissolved in water, it exhibits weak alkalinity with a pH value in the range of 8 to 11. (A
), component (D), and optional components (especially acidic components).

In order to obtain a highly bleached blade, it is desirable that the total amount of component (B-) and component (C) be 50 to 90% by weight in the bleach composition.

The powdered aminopolycarboxylic acids of component (D) include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (
NTA), iminodiacetic acid (IDA).

One or a mixture of two or more acidic aminopolycarboxylic acids selected from the group consisting of hydroxyethyliminodiacetic acid (HEIDA) and diethylenetriaminepentaacetic acid (DTPA) is used.

These compounds have cleavage ability and are usually used as alkali metal salts, but in the present invention, it is important to use them not in the salt form but in the acid form. In the salt form, even when blended into a bleach composition, the stabilizing effect of suppressing the generation of off-odor is low.

The amount of powdered aminopolycarboxylic acid (D) blended into the bleach composition is also influenced by the amount of alkaline agent blended, but in order to maintain stability, it is necessary to add [(B) + (C)
]/(D) = 20/1 to 4/I.

The bleach composition of the present invention is obtained by powder-mixing components (A), (B), (C), and (D).

The reduced bleach composition of the present invention includes the above (A), (8),
Although components (C) and (D) are contained as essential components, other components can be blended within a range that does not impair the effects of the present invention. Examples of such optional ingredients include surfactants, fluorescent bleaches, enzymes, fragrances, colorants, carriers, and fillers.

Surfactants not only make it easier to wet the object to be treated and promote contact between bleaching active species and dirt, but also have the added cleaning effect of the surfactant itself, which is expected to further improve the bleaching effect. component, which is preferably incorporated into the bleach composition of the present invention.

Examples of such surfactants include alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfate salts, anionic surfactants such as soap; polyoxyethylene adducts of higher alcohols, and polyoxyethylene adducts of alkylphenols. and nonionic surfactants such as sorbitan fatty acid esters. The amount of surfactant blended is not particularly limited, but
It is sufficient to incorporate 0.1 to 1 O by weight into the bleach composition.

As an optical brightener, 4,4-bis-2-sulfostyryl biphenyl disodium salt (Chino□ Pearl CBS-
X (manufactured by Ciba Geigy), examples of enzymes include alkaline protease and alkaline cellulase, and examples of carriers include water-soluble inorganic substances such as sodium sulfate and magnesium sulfate.

The method of using the bleach composition of the present invention is the same as that of ordinary oxygen bleaches. Normally.

It is used as an aqueous solution with a concentration of 5 to Log/Q.

According to the reducing bleach composition of the present invention, (A) thiourea dioxide and (B) granular sodium carbonate and (C) granular sodium bicarbonate are added as the alkaline agent to be used together with (A) thiourea dioxide.
B)/(C) = 6/1 to 1/l (weight ratio), and (B) powdered sodium carbonate has an average particle diameter of 50 to 150 μm, and further contains EDTA, N
(D) aminopolycarboxylic acid in a specific acid form selected from TA, IDA, HE IDA, DTPA [(B) + (
By blending in the range of C)]/(D) = 20/1 to 4/1 (weight ratio), 1 achieves high storage stability even under high temperature and high humidity conditions such as normal home usage environments. can.

The bleach composition of the present invention can be used not only as a bleaching agent for ordinary clothes, etc., but also as a rust remover for metal products, as a detergent additive to improve cleaning power when added to detergents, and as a detergent for preventing yellowing of washed items. It can also be used as a remover.

The present invention will be described below with reference to five examples.

Prior to this, the storage stability test method used in the Examples will be explained.

200g of the test bleach composition in a 300m Q capacity container.
After filling and storing under the following storage conditions, evaluate the occurrence of off-odor.

(1) Storage conditions Container: Plastic bottle with pinholes sufficient to alleviate the upper limit of internal pressure Storage conditions: Temperature 45°C Temperature 35°C, 85% R11 Period: 30 days (2) Off-odor generation evaluation method Odor A sensory test was conducted by an expert, and the odor of the bleach composition was compared with that immediately after blending, and evaluation was made using the following criteria.

++: A strong off-odor is felt +: An off-odor is felt ±: A very slight off-odor is felt -: No off-odor is felt at all Examples include thiourea oxide [component (A) 310% by weight, shown in Table 1] A bleach composition consisting of a mixed alkaline agent of 85 weight parts of sodium carbonate [component (B)] and sodium hydrogen carbonate [component (C)] and 5 parts by weight of EDTA (component (D)) was prepared by powder blending. Each was prepared. Then,
A storage stability test was conducted on these bleach compositions,
The results are shown in Table 1.

From the results in Table 1, it can be seen that the off-odor of the bleach composition over time depends on the blending ratio of (B) sodium carbonate and (C) sodium bicarbonate used as alkaline agents, and on the particle size of (B) sodium carbonate powder. In all of the six products of the present invention, which show that the degree of odor generation varies greatly, the generation of off-flavors is suppressed. On the other hand, in the comparative example, the occurrence of off-odor cannot be suppressed. That is, CB)/(C)=1/2. (
B) average particle size = 50μ (experiment Nα9) or 100μ
In the case of (Experiment-10), after 30 days at 45°C, a distinct odor was felt;
When stored at 85% RH, a distinct odor will develop after 30 days. (B)/(C) = 1/2, CB)
When the average particle size of = 150μ (experiment Nα11), the temperature was 45°C.
A product stored at 35° C. and 85% RH has an unpleasant odor after 30 days. A product with a value of CB)/(C) of 10/l (experiment Nα16.17) also fails to suppress the generation of off-odor regardless of the average particle size of component (B). (B) component with an average particle size of 20μ (experiment Nα12.14),
In both cases of 200μ (experiment N (113, 15)), a strange odor was generated.

(The following is a blank space) Table 1 Example 2 Various bleach compositions were prepared by powder heating based on the compositions shown in Table 2 below.

The plan is gone ± 4 times 1! fu Thiourea dioxide 10wt% sodium carbonate (average particle size 100μm) 41h
t% sodium bicarbonate 12wt
% aminopolycarboxylic acid 111o to 20 wt% sodium sulfate parts *1) The types and amounts of the aminocarboxylic acids used are as shown in Table 3.

A storage stability test was conducted on these bleach compositions, and the results are shown in Table 3.

(Left below) From the results in Table 3, (D) type of aminopolycarboxylic acid, blending ratio of alkali agent/aminopolycarboxylic acid [(B)
+(C)]/(D) indicates that the degree of off-odor generation when the bleach composition is administered orally varies. The product of the present invention contains EDTA, NTA, and I as aminopolycarboxylic acids.
DA, HEIDA.

A compound selected from DTPA is used, and the blending ratio of alkali agent/aminopolycarboxylic acid is 20/1 to 4/
1, none of which produce any off-odor.

In contrast, those that do not contain aminopolycarboxylic acid (
Experiment &12) had no effect of suppressing the generation of off-odor at all, and the effect of suppressing the generation of off-odor was also low when the sodium salt of the aminopolycarboxylic acid of the present invention was used (Experiment NQ17.18.19). Furthermore, although included in the aminopolycarboxylic acid salts, iminoniprobionic acid (Experiment Nα20), nitrilotripropionic acid (Experiment & 21), ethylenediaminetetrapropionic acid (Experiment & 22), etc. have almost no effect on suppressing the generation of off-odor. It is understood that the present invention has an excellent effect of suppressing the generation of off-flavors.

Claims (1)

[Claims] 1. The following components (A), (B), (C) and (D) in a weight ratio of (B)/(C) = 6/1 to 1/1, and [(
B)+(C)]/(D)=20/1 to 4/1. (A) Powdered thiourea dioxide, (B) Powdered sodium carbonate with an average particle size of 50 to 150 μm, (C) Powdered sodium bicarbonate, (D) Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxy One or a mixture of two or more powdered aminopolycarboxylic acids selected from the group consisting of ethyliminodiacetic acid and diethylenelutriaminepentaacetic acid.