JPH0940999A - Mixed type oxygen-based bleaching agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching agent free from harmful gas evolution during use, excellent in bleaching power and free of an irritating odor by mixing an aq. H2 O2 soln. with a powder agent comprising an alkaline substance and a specific arom. compd., and adjusting the pH of the resultant mixture in a specific range. SOLUTION: (A) An aq. H2 O2 soln. of 0.5 to 10wt.% in H2 O2 concn. as a liq. agent is combined with (B) a powder mixture prepd. as a powder agent by blending an alkaline substance with an arom. compd. of formula I (wherein R<1> is an alkyl, alkenyl, aryl, or the like; R<2> is a lower alkyl or a group of formula II; X is an alkylene, arylene, or the like; A<-> is an anion; and (n) is a no. which makes the valence of the anion equal to that of the cation in the molecule) at a blending wt. ratio of 1:20 to 3:1, followed by pH adjustment in the range of 6 to 12 at an (A):(B) wt. ratio of 100:1 to 2:1 [e.g. use is made of the component (A) into which a small amt. of an org. sulfonic acid (salt) of formula III (wherein R<3> is H or a lower alkyl; R<4> is H, OH, or a lower alkyl; and M<1> to M<4> are each H or an alkali metal) is incorporated to a pH of 1.5 to 6], whereby the objective bleaching agent is obtd.

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 agent which does not generate harmful gas during use, has an excellent bleaching power and has no irritating odor, and is particularly suitable for removing mold on hard surfaces. It is a thing.

[0002]

2. Description of the Related Art Bathrooms, bathtubs, toilets,
Most of the stains on the sink, especially where water is used frequently, are often due to organic substances or insoluble inorganic substances caused by mold, etc., and it is difficult to remove them with ordinary detergents containing a surfactant as the main component. In order to remove these stains, conventionally, a method mainly containing a chlorine-based or oxygen-based bleaching agent as a main component and a method of removing it by its bleaching effect have been adopted.

However, although those having a chlorine-based bleaching agent such as sodium hypochlorite as a main component have an excellent dirt removing ability, they have a great risk of damaging the eyes and skin and have a strong chlorine odor. However, when using it, it is necessary to pay attention to sufficient ventilation, and when it is mistakenly used in combination with an acidic cleaning agent, it has a drawback that harmful chlorine gas is generated.

On the other hand, those containing an oxygen-based bleaching agent represented by hydrogen peroxide as a main component do not have the drawback of generating chlorine gas, but they cannot obtain a sufficient bleaching effect by themselves, and therefore various bleaching agents are used. An activator had to be used in combination (for example, JP-A-60-1299 and JP-A-62-162).
4794, JP-A-2-196896, JP-A-3-121200).

However, among these bleach activators, those which generate peracetic acid as a bleaching active species have a strong irritating odor and are unsuitable for use as residential use, and also generate an irritating odor. The fact is that bleach activators that are not used have hardly been put to practical use because of their low stain-removing power and high cost.

[0006]

Under the circumstances, the present invention provides a bleaching composition which exhibits excellent bleaching power, has no irritating odor, and is particularly suitable for use as a fungicide. It was made for the purpose of providing.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to develop a bleaching agent which exhibits a strong bleaching power and has no irritating odor. As a result, hydrogen peroxide and, in some cases, organic phosphonic acid have been obtained. Or, an aqueous solution containing a salt thereof and a powder comprising an alkaline substance and a divalent carboxylic acid ester having an aminium group in the molecule are combined so that the pH of the solution when they are mixed falls within a specific range. It was found that the above objects can be achieved by making adjustments, and the present invention has been completed based on this finding.

That is, according to the present invention, (A) the concentration is from 0.5 to
A liquid agent comprising a 10 wt% hydrogen peroxide aqueous solution, and (B)
(A) alkaline substance and (b) general formula

Embedded image (Wherein R ¹ is an alkyl group, an alkenyl group, an aryl group, an aminoalkyl group or a substituted aminoalkyl group, and each R
² is independently the same or different lower alkyl group, or -X-N ⁺ (R ¹ ) ₃ · nA ^- group, X is an alkylene group, alkenylene group, cycloalkylene group or arylene group, A
^- is an anion, n represents to 1:20 weight ratio of the aromatic compound represented by the number a is) to the monovalent number and cations and anions in the molecule 3: 1, preferably 1: 4 to 2:
1, more preferably in combination with a powder consisting of a powder mixture formulated in a ratio of 1: 3 to 1: 1,
P when component (A) and component (B) are mixed in a weight ratio of 100: 1 to 2: 1, preferably 50: 1 to 10: 1, more preferably 20: 1 to 4: 1.
The mixed use type oxygen bleaching agent is characterized in that H is adjusted to fall within the range of 6 to 12.

The bleaching agent of the present invention comprises a combination of the component (A) and the component (B). As the component (A), an aqueous hydrogen peroxide solution having a concentration of 0.5 to 10% by weight is used. To be The hydrogen peroxide content in this aqueous solution is 0.5% by weight
If it is less than 10% by weight, the bleaching power is insufficient, and if it exceeds 10% by weight, the effect of improving the bleaching power is not so much seen for the amount,
Rather, it is economically disadvantageous. From the viewpoint of bleaching power and economical efficiency, the preferable content of hydrogen peroxide is in the range of 1 to 8% by weight, particularly 3 to 6% by weight.

In the present invention, in order to improve the storage safety of the hydrogen peroxide aqueous solution and the bleaching sustainability, an aqueous hydrogen peroxide solution having a concentration of 0.5 to 10% by weight is added as the component (A). General formula

Embedded image (In the formula, R ³ is a hydrogen atom or a lower alkyl group, R ⁴ is a hydrogen atom, a hydroxyl group or a lower alkyl group, and M ¹ , M ² , M ³ and M ⁴ are each a hydrogen atom or an alkali metal). It is possible to use one containing at least one compound selected from organic phosphonic acids and salts thereof in a proportion of 0.001 to 1% by weight and having a pH in the range of 1.5 to 6.

It is necessary to select the content of the organic phosphonic acid or its salt in the range of 0.001 to 1% by weight, and if it is less than 0.001% by weight, the bleaching power sustaining effect is not sufficiently exhibited. If it exceeds 1% by weight, the bleaching persistence does not further improve, and it is rather economically disadvantageous. From the viewpoint of the effect of sustaining bleaching power and economy, the preferable content of the organic phosphonic acid or its salt is in the range of 0.01 to 1 wt%. Further, the pH of the aqueous solution of the component (A) needs to be adjusted in the range of 1.5 to 6 in order to effectively exhibit the bleaching power and the like, but the range of 2 to 4 is particularly advantageous. .

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The oxygen-based bleaching agent of the present invention comprises (A)
It is a so-called two-component mixed use type bleaching agent, which is a combination of a liquid agent as a component and a dusting agent as a component (B), which is used by mixing both when necessary. The component (A) is composed of an aqueous solution of hydrogen peroxide having a concentration of 0.5 to 10% by weight, and can further contain the organic phosphonic acid of the general formula (II) or a salt thereof, if desired.

R ³ in the general formula (II) is a hydrogen atom or a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group or tert-group. It is an alkyl group having 1 to 4 carbon atoms such as a butyl group, and is a hydrogen atom or a hydroxyl group, or a lower alkyl group, for example, an alkyl group having 1 to 4 carbon atoms as mentioned in the case of R ³ .

M ¹ , M ² , M ³ and M ⁴ are the same or different and each is a hydrogen atom or an alkali metal, and when all are hydrogen atoms, an organic phosphonic acid,
When part or all of the alkali metal is used, it becomes an organic phosphonate. Examples of the alkali metal include lithium,
Although sodium, potassium, etc. are mentioned, sodium or potassium is preferable from an economical point of view.

Typical examples of the organic phosphonic acid represented by the general formula (II) and salts thereof include 1-hydroxyethane-1,1-diphosphonic acid and 1-hydroxypropane-
1,1-diphosphonic acid, 1,1-ethanediphosphonic acid,
Mention may be made of 2,2-propanediphosphonic acid, 2,2-butanediphosphonic acid and their sodium or potassium salts. These organic phosphonic acids or salts thereof may be used alone or in combination of two or more.

Next, the alkaline substance used as the component (B) of the present invention may be any alkali metal or ammonium hydroxide, carbonate, hydrogen carbonate or the like which exhibits alkalinity when dissolved in water. Sodium carbonate or potassium carbonate is preferable because it is easy to handle and the pH can be easily adjusted. Particularly preferred is potassium carbonate. These are usually used as a powder having a particle size of 16 to 200 mesh.

In the component (B), the aromatic compound of the general formula (I) used together with the alkaline substance is a so-called bleach activator. R ¹ in this general formula (I) is
Alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, alkenyl group such as vinyl group and propenyl group, phenyl group, tolyl group, xylyl group, naphthyl group aryl groups such as, aminoethyl group, dimethylaminoethyl group, aminopropyl group, or an aminoalkyl or substituted aminoalkyl group such as dimethyl amino propyl group, or ^{-X-N + (R 2)} 3 · It is a group represented by nA ⁻ . Further, the three R ^{2 s} are each a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and the three R ^{2 s} may be the same or different. The above X is a saturated alkylene group such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, vinylene group, unsaturated alkylene group such as arylene group, cyclopentylene group, cyclohexene group. Cycloalkylene group such as silene group, phenylene group, tolylene group,
An arylene group such as a benzylene group.

Next, A ⁻ in the general formula (I) is an anion, for example, Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ SO ₄ ⁻ , CH ₃ C.
It is a monovalent anion such as OO ⁻ or a divalent anion such as SO ₄ ²⁻ , and n is a number that makes the valence of the cation and the valence of the anion in the molecule the same. The bonding position of the two oxycarbonyl groups bonded to the benzene ring is not particularly limited and may be any of the para position, meta position and ortho position.

Compounds represented by the above general formula (I), for example, monomethyl monocholine ester of terephthalic acid [2
-(4-methoxycarbonylbenzoyloxy) -N,
N, N-trimethylethaneaminium methosulfate] was prepared by reacting terephthalic acid monomethyl chloride with 2-dimethylaminoethanol to obtain methyl terephthalic acid 2-dimethylaminoethyl ester, and then reacting it with dimethyl sulfate. It can be produced by carrying out a quaternization reaction of an amine. In such a production method, an amine compound which is not quaternized may be contained, but there is no problem in bleaching performance.

Further, 2- [4- (2-dimethylaminoethoxy) carbonylbenzoyloxy] -N, N, N-trimethylethaneaminium methosulfate of the compound represented by the general formula (I) is, for example, terephthalate. It is prepared by reacting acid dichloride with 2-dimethylaminoethanol to obtain terephthalic acid di (2-dimethylaminoethyl) ester, and then reacting this with dimethyl sulfuric acid to carry out a quaternization reaction of amine. You can In such a production method, an amine compound which is not quaternized may be contained, but there is no problem in bleaching performance. Also, the quaternization rate varies depending on the reaction conditions,
Increasing the amount of dimethyl sulfate to act on results in the divalent quaternary salt benzene-1,4-bis (carbonyloxy-N,
N, N-trimethylethaneaminium) Dimethosulfate is produced as a by-product, which is included in the compound represented by the general formula (I) and has no problem in bleaching performance.

Further, in these production methods, methyl acetate is used in place of dimethyl sulfate, and a quaternization reaction is carried out under heating, whereby CH ₃ SO ₄ ^— is replaced with CH ₃ COO ⁻ as an anion in the compound. You will get what was done. The bleach activator comprising the compound represented by the general formula (I) may be used alone or in combination of two or more kinds. These are usually used as a powder having a particle size of 4 to 200 mesh.

As the powder of the component (B), the alkaline substance of the component (a) and the bleach activator of the component (b) are used.
It is necessary to mix and use in a weight ratio of 1:20 to 3: 1. If the ratio of both components deviates from this range, when the components (A) and (B) are mixed, the required p
It becomes difficult to maintain the H range, the bleach activator hydrolyzes, and the bleaching power decreases. In order to suppress the hydrolysis of the bleach activator and exert its bleaching power effectively, (a)
The mixing ratio of component (b) to component (b) is preferably in the range of 1: 4 to 2: 1 by weight, particularly preferably in the range of 1: 3 to 1: 1. In addition, the water content of the component (B) powder is preferably 15% by weight or less from the viewpoint of storage stability.
It is more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

In the bleaching composition of the present invention, the ratio of the components (A) and (B) used is 10 by weight.
It is necessary to select within the range of 0: 1 to 2: 1. If the ratio of both components deviates from this range, the bleaching performance will deteriorate. From the standpoint of bleaching performance, the preferred usage ratio of both components is (A)
The weight ratio of the component to the component (B) is in the range of 50: 1 to 10: 3, particularly preferably 20: 1 to 4: 1. Further, the pH of the solution when the component (A) and the component (B) are mixed needs to be in the range of 6 to 12. When the pH is out of the above range, the bleaching performance is deteriorated. From the viewpoint of bleaching performance, the preferred pH is in the range of 8-11.

The component (A) or the component (B) of the bleaching composition of the present invention may contain, if desired, a surfactant, a builder and a radical scavenger for the purpose of improving bleaching performance, storage stability, usability and the like. Agents, alcohols (ethanol, isopropanol, ethylene glycol, etc.), thickeners, fragrances, dyes, fluorescent dyes, enzymes and the like can be appropriately added. At this time, it is preferable that the liquid one is blended with the component (A) and the solid one is blended with the component (B), but it is necessary to select it in consideration of reactivity between substances and coexistence stability.

Since the surfactant has the function of promoting the penetration of the bleaching active species into the soil, it is desirable to incorporate it in the composition of the present invention. Examples of the surfactant include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, polyoxyalkyl sulfate ester salts, α-sulfo fatty acid alcohol ester salts, and sulfosuccinic acid monoester salts, polyoxyethylene alkyl salts. Nonionic surfactants such as ethers, sorbitan fatty acid esters, alkyl glycosides, alkyl glycoside fatty acid esters, polyoxyethylene fatty acid esters, fatty acid glycerides, oxyethyleneoxypropylene block copolymers, long-chain mono-, dialkyl quaternary ammonium salts, amine oxides And amphoteric surfactants such as carboxybetaine, sulfobetaine, and amino acid-based surfactants.

Examples of the builder include sodium sulfate, sodium silicate, sodium tripolyphosphate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, and other salts. Particularly, chelate builders such as phosphates and polyacrylates. Examples thereof include polycarboxylic acid salts and zeolite.

As the enzyme, for example, addition of water,
A hydrolase that promotes removal, a oxidoreductase that promotes redox, a group that transfers a group from one molecule to another, transforms dirt to promote removal, and breaks bonds between molecules A ligase or a lyase that promotes removal, an enzyme that isomerizes molecules to chemically change and remove stains, and the like can be used. Among these, hydrolases are preferable, and protease is particularly preferable.

The bleaching composition of the present invention contains (A) when necessary.
The component and the component (B) are used as a mixture, but from the viewpoint of storage stability, it is preferable to separately package both components and store them as a set. To bleach using the bleaching composition of the present invention, each component is taken from a set in which it is stored separately and mixed to form an aqueous solution, and this aqueous solution is applied to residential soil. It is convenient to apply this aqueous solution to dirt by a method of spraying using a spray container or the like. In addition, for application to stains, application using foam or the like, application by compounding with an adhesive or the like can also be used. Alternatively, each component may be separately applied to the soiled area and mixed there. in this case,
Since the component (B) is a solid, it can be applied in the form of an aqueous solution, slurry or paste by adding a necessary amount of water if desired.

[0029]

The oxygen-based bleaching composition of the present invention has a high bleaching power, has no irritating odor, and exhibits an excellent bleaching effect particularly on stains of organic substances such as mold and insoluble inorganic substances, It is particularly suitable as a mold remover for hard surfaces.

[0030]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The bleaching rate in each example was measured as follows. Bleaching rate: Black mold (Cladosporium clad)
osporioides) on the surface of the tile prepared by culturing and depositing each sample, and after leaving each sample for 5 minutes, wash the tile with water and measure the color difference with respect to the original tile.
The bleaching rate was calculated.

Examples 1 to 3, Comparative Examples 1 to 3 pH of aqueous hydrogen peroxide solution having a concentration of 5% by weight or 10% by weight
Was adjusted to pH 2 to 11 with hydrochloric acid to prepare the component (A), which was mixed with the component (B) having the composition shown in Table 1 and a bleaching test was conducted. Table 1 shows the results.

[0033]

[Table 1]

Examples 4 to 6 and Comparative Examples 4 to 6 Hydrogen peroxide aqueous solution to which 1-hydroxyethane-1,1-diphosphonic acid was added was used as the component (A), and the composition (B) shown in Table 2 was used. ) Component, and the bleaching test was performed. The results are shown in Table 2.

[0035]

[Table 2]

Examples 7 to 9 1-Hydroxypropane-1,1-
Using what added diphosphonic acid as (A) component,
A bleaching test was conducted by mixing with the component (B) having the composition shown in Table 3. Table 3 shows the results.

[0037]

[Table 3]

Examples 10 to 15 The components (A) and (B) having the compositions shown in Table 4 were mixed and a bleaching test was conducted. The results are shown in Table 4.

[0039]

[Table 4]

The symbols in each table have the following meanings. a: 1-hydroxyethane-1,1-diphosphonic acid b: 1-hydroxypropane-1,1-diphosphonic acid c: 2- (4-methoxycarbonylbenzoyloxy)
-N, N, N-trimethylethaneaminium methosulfate d: 2- (2-ethoxycarbonylbenzoyloxy)
-N, N, N-trimethylethaneaminium methosulfate e: 2- [4- (2-dimethylaminoethoxy) carbonylbenzoyloxy] -N, N, N-trimethylethaneaminium methosulfate f: 2- [3 -(2-Dimethylaminoethoxy) carbonylbenzoyloxy] -N, N, N-trimethylethaneaminium methosulfate g: benzene-1,4-bis (carbonyloxy-N,
N, N-trimethylethaneaminium) dimethosulfate

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 10, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image (In the formula, R ¹ is an alkyl group, an alkenyl group, an aryl group, an aminoalkyl group or a substituted aminoalkyl group or a —X—N ⁺ (R ² ) ₃ · nA ⁻ group, and each R ² is the same or different lower An alkyl group, X is an alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, A ⁻
Is an anion, and n is a number that makes a cation and an anion in a molecule have the same valency). From a powder mixture containing an aromatic compound represented by a weight ratio of 1:20 to 3: 1. Which is a combination of a powdery agent consisting of (A) component and (B)
A mixed use type oxygen-based bleaching agent, characterized in that the pH is adjusted to be within the range of 6 to 12 when mixed with the components in a weight ratio of 100: 1 to 2: 1.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

That is, according to the present invention, (A) the concentration is 0.5 to
A liquid agent comprising a 10 wt% hydrogen peroxide aqueous solution, and (B)
(A) alkaline substance and (b) general formula

Embedded image (In the formula, R ¹ is an alkyl group, an alkenyl group, an aryl group, an aminoalkyl group or a substituted aminoalkyl group or a —X—N ⁺ (R ² ) ₃ · nA ⁻ group, and each R ² is the same or different lower An alkyl group, X is an alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, A ⁻
Is an anion, and n is a number that makes the cation and anion in the molecule have the same valency). The weight ratio of the aromatic compound is 1:20 to 3: 1, preferably 1: 4 to 2:
1, more preferably in combination with a powder consisting of a powder mixture formulated in a ratio of 1: 3 to 1: 1,
P when component (A) and component (B) are mixed in a weight ratio of 100: 1 to 2: 1, preferably 50: 1 to 10: 1, more preferably 20: 1 to 4: 1.
The mixed use type oxygen bleaching agent is characterized in that H is adjusted to fall within the range of 6 to 12.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

In the present invention, in order to improve the storage stability of the hydrogen peroxide aqueous solution and the bleaching sustainability, an aqueous hydrogen peroxide solution having a concentration of 0.5 to 10 wt% is used as the component (A). General formula

Embedded image (In the formula, R ³ is a hydrogen atom or a lower alkyl group, R ⁴ is a hydrogen atom, a hydroxyl group or a lower alkyl group, and M ¹ , M ² , M ³ and M ⁴ are each a hydrogen atom or an alkali metal). It is possible to use one containing at least one compound selected from organic phosphonic acids and salts thereof in a proportion of 0.001 to 1% by weight and having a pH in the range of 1.5 to 6.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Further, 2- [4- (2-dimethylaminoethoxy) carbonylbenzoyloxy] -N, N, N-trimethylethaneaminium methosulfate of the compound represented by the general formula (I) is, for example, terephthalate. It is prepared by reacting acid dichloride with 2-dimethylaminoethanol to obtain terephthalic acid di (2-dimethylaminoethyl) ester, and then reacting this with dimethyl sulfuric acid to carry out a quaternization reaction of amine. You can In such a production method, an amine compound which is not quaternized may be contained, but there is no problem in bleaching performance. Also, the quaternization rate varies depending on the reaction conditions,
Increasing the amount of dimethyl sulfate to act on results in the divalent quaternary salt benzene-1,4-bis (carbonyloxy-N,
N, N-trimethylethaneaminium) dimethosulfate is produced, which is included in the compound represented by the general formula (I) and has no problem in bleaching performance.

Front Page Continuation (72) Inventor Shinichi Suzuki 1-3-7 Main Office, Sumida-ku, Tokyo Within Lion Co., Ltd.

Claims (1)

[Claims] 1. A liquid agent comprising (A) an aqueous hydrogen peroxide solution having a concentration of 0.5 to 10% by weight, (B) (a) an alkaline substance, and (b) a general formula: (Wherein R ¹ is an alkyl group, an alkenyl group, an aryl group, an aminoalkyl group or a substituted aminoalkyl group, and each R
² is independently the same or different lower alkyl group, or -X-N ⁺ (R ¹ ) ₃ · nA ^- group, X is an alkylene group, alkenylene group, cycloalkylene group or arylene group, A
^- is an anion, n represents to 1:20 weight ratio of the aromatic compound represented by the number a is) to the monovalent number and cations and anions in the molecule 3: Powder mixtures were blended at a ratio of 1 A mixture of a powdery agent consisting of (A) and a component (B) at a weight ratio of 100: 1 to 2: 1 and adjusted to have a pH in the range of 6 to 12. A mixed use type oxygen-based bleaching agent characterized in that