JPH07224300A - Bleaching agent composition for house - Google Patents

Abstract

PURPOSE:To obtain a breaching agent composition for house which emits no irritant odor and is highly effective in bleaching stains, in particular stains of an organic substance, e.g. a fungus, or of an insoluble inorganic substance. CONSTITUTION:This composition comprises as active components a peroxide bleaching agent (a) and a bleaching activator (b) comprising a compound represented by the formula [wherein X<1> is a group represented by (R)3 N<+>-Y-(where R's are the same or different lower alkyls and Y is an alkylene); X<2> is a hydrocarbon group, an (un)substituted aminoalkyl group, or the same as X<1>; A is an anion; and n is the number which makes the anion to have the same valency as the cation]. The component (a) is preferably hydrogen peroxide or a peroxide generating hydrogen peroxide in aqueous solution. The molar ratio of the component (a) to the component (b) is preferably 30:1 to 1:2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel residential bleaching composition, and more particularly to a residential bleaching composition free from irritating odor and having high bleaching power.

[0002]

2. Description of the Related Art Bathrooms, bathtubs, toilets,
Stain, etc., especially where water is frequently used, often has stains due to organic substances or insoluble inorganic substances caused by mold, etc., which cannot be easily removed with ordinary detergents containing a surfactant as a main component. Therefore, as a method for removing these stains, a method using a chlorine-based or oxygen-based bleaching agent as a main component and removing it by its bleaching effect has been conventionally adopted.

However, although those having a chlorine-based bleaching agent such as sodium hypochlorite as a main component are excellent in stain removal performance, they are very dangerous to eyes and skin and have a peculiar chlorine odor. It has strong drawbacks that it requires ventilation when used, and when it is mistakenly used together with an acidic detergent, it produces harmful chlorine gas.

On the other hand, those containing an oxygen-based bleaching agent represented by hydrogen peroxide as a main component do not have a problem such as chlorine gas generation, but when they are used alone, a sufficient bleaching effect is not obtained and therefore bleaching activation is performed. Various combinations of agents have been proposed (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 produce peracetic acid as a bleaching active species have a strong irritating odor, and it is difficult to put them into practical use for residential use, and irritating odors are also present. A bleach activator that does not generate, because of low stain removal power, high cost, etc.
The reality is that it has hardly been put to practical use.

[0006]

Under these circumstances, the present invention has been made for the purpose of providing a residential bleaching composition free from irritating odor and having high bleaching power. is there.

[0007]

Means for Solving the Problems As a result of intensive studies to develop a residential bleaching composition having no pungent odor and high bleaching power, the present inventors have found that a peroxide bleaching agent and By using a bleach activator consisting of an aromatic divalent carboxylic acid ester having an aminium group in the molecule,
It has been found that the object can be achieved, and the present invention has been completed based on this finding.

That is, the present invention comprises (A) a peroxide bleach and (B) a general formula

[Chemical 2] [Wherein X ¹ is a (R) ₃ N ⁺ —Y-group (wherein each R is the same or different lower alkyl group, Y is an alkylene group), X ²
Is a hydrocarbon group, a substituted or unsubstituted aminoalkyl group or X
¹ is the same group as ¹ and A is an anion, and n is a number that makes the cation and anion in the molecule have the same valency]. The present invention provides a residential bleaching composition.

The peroxide bleach used as the component (A) in the composition of the present invention includes, for example, hydrogen peroxide and peroxides that generate hydrogen peroxide in an aqueous solution. As the oxide, sodium percarbonate,
Percarbonates such as potassium percarbonate, sodium perborate monohydrate, perborates such as sodium perborate tetrahydrate, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / hydrogen peroxide Examples include perphosphate salts such as adducts, and hydrogen peroxide adducts such as urea, sodium sulfate, and sodium silicate. Of these, hydrogen peroxide, sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferable. These peroxide bleaching agents may be used alone or in combination of two or more kinds.

In the composition of the present invention, the compound represented by the general formula (I) is used as the bleaching activator of the component (B).

X ^{1 in} this general formula (I) is (R) ₃ N ⁺ −
Each of the three R's represented by Y- is a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, which may be the same or different. Examples of the alkylene group of Y include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group and an octylene group.

Next, examples of the hydrocarbon group of X ² include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a vinyl group, an alkenyl group such as an allyl group, and a phenyl group. An aryl group, an aralkyl group such as a benzyl group, a tolyl group, an alkaryl group such as a xylyl group, and examples of the substituted or unsubstituted aminoalkyl group include an aminomethyl group, a dimethylaminoethyl group, and a diethylaminoethyl group. , A dimethylaminopropyl group, a dimethylaminobutyl group, and the like. A in the general formula (I) is an anion, for example, Cl ⁻ ,
Br ⁻ , I ⁻ , CH ₃ SO ₄ ⁻ , CH ₃ COO ⁻ , a monovalent anion, a monovalent equivalent of SO ₄ ²⁻ , a divalent anion, etc., and n is a cation in the molecule. Is the same as the valence of the anion. Further, the bonding positions of the two oxycarbonyl groups bonded to the benzene ring are not particularly limited and may be any of the para position, meta position, or ortho position.

The method for producing the compound represented by the general formula (I) is described in the following: terephthalic acid monomethyl monocholine ester [2- (4-methoxycarbonylbenzoyloxy)]
-N, N, N-trimethylethaneaminium methosulfate], for example, terephthalic acid monomethyl chloride is reacted with 2-dimethylaminoethanol to obtain terephthalic acid methyl 2-dimethylaminoethyl ester, The desired compound can be obtained by reacting this with dimethylsulfate to carry out the quaternization reaction of the amine. In such a production method, an amine compound which is not quaternized may be contained, but there is no problem in bleaching performance.

As the compound represented by the general formula (I), 2- [4- (2-dimethylaminoethoxy)]
Carbonylbenzoyloxy] -N, N, N-trimethylethaneaminium methosulfate is taken as an example to explain its production method. For example, terephthalic acid dichloride is reacted with 2-dimethylaminoethanol to prepare terephthalic acid di (2-dimethylamino). After obtaining the ethyl) ester, dimethyl sulfate is allowed to act on the ethyl) ester to carry out the quaternization reaction of the amine, whereby the desired compound is obtained. In such a production method, an amine compound which is not quaternized may be contained, but there is no problem in bleaching performance. The quaternization rate varies depending on the reaction conditions, and when the amount of dimethylsulfate to act on is increased, benzene-1,4-bis (carbonyloxy-N, N, N-) is a divalent quaternary salt.
Trimethylethaneaminium) dimethyl sulfate is also formed, but this is included in the compound represented by the general formula (I), and there is no problem in bleaching performance.

Further, in these production methods, using methyl acetate instead of dimethyl sulfate, by performing the quaternization reaction under heating, CH ₃ SO ₄ as the anion in the compound ^- substituted ^- is CH ₃ COO 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.

In the bleaching composition of the present invention, the mixing ratio of the peroxide-based bleaching agent (A) and the bleaching activator (B) is in the range of 30: 1 to 1: 2. Is preferable, and a range of 20: 1 to 1: 1 is particularly preferable. When this molar ratio deviates from the above range, it becomes difficult to obtain a sufficient bleaching power.

In addition to the above-mentioned essential components, the bleaching composition of the present invention may contain, if necessary, various conventionally used additive components within a range not impairing the object of the present invention. .

Examples of the additive components include pH adjusters, various surfactants, water-soluble solvents, solubilizers, various inorganic or organic builders, enzymes, abrasives, fragrances, pigments,
Examples include fluorescent agents.

The pH adjusting agent is preferably used as a blending component, since it is desirable to adjust the pH to 6 to 13, particularly 8 to 12 so that the composition of the present invention can sufficiently exert its effects. Advantageously, it is incorporated into the composition when used.

Examples of the pH adjusting agent include alkalis or buffers, commercially available alkaline detergents and the like. Examples of the alkali or buffer include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, mono-, di- or triethanolamine, and substituted or unsubstituted ammonium compounds such as ammonium hydroxide,
Examples thereof include carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate, silicates such as sodium silicate and potassium silicate, and phosphates such as sodium tripolyphosphate and sodium pyrophosphate.

Further, the composition of the present invention lowers the pH of the system with the generation of bleaching active species. Therefore, in order to maximize the effect, the pH after washing is 6 to 13, especially 8 It is desirable to incorporate an amount of alkali or buffer that can be maintained at -12.

Since the surfactant has a function of promoting the penetrating power 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 polymers, long-chain mono-, dialkyl quaternary ammonium salts, amine oxides Cationic surfactants, such as
Examples include amphoteric surfactants such as carboxybetaine, sulfobetaine, and amino acid surfactants.

Examples of the builder include sodium sulfate, sodium silicate, sodium tripolyphosphate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, 1-hydroxyethane-1,1-disulfonic acid and other salts, and particularly chelate. Builders such as phosphates, polyacrylates, polycarboxylic acids and zeolites are preferred.

As the water-soluble solvent, for example, methanol,
Ethanol, monopropanol such as 2-propanol, 1-propanol, dihydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, glycerin, etc. And the mono- or diethers of the above divalent and trivalent alcohols with lower monohydric alcohols. In addition, examples of the solubilizer include urea and p-toluenesulfonic acid.

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 and chemically alters stains, and the like can be used. Among these, hydrolases are preferable, and protease is particularly preferable.

The bleaching composition of the present invention can be used in the form of a solution in which the component (A) and the component (B) are allowed to coexist, preferably in the form of an aqueous solution. In this case, the pH of the solution is 6
Since storage stability will fall if it becomes more than the above, it is important to adjust pH to less than 6. In order to prevent this storage stability problem, it is preferable to use a set product form in which the component (A) and the component (B) are stored separately. In this case, it is advantageous to use a solution form for each component because it is easy to use.

Examples of such an aqueous solution include (A)
Hydrogen peroxide as component and benzene-1,4- as component (B)
An aqueous solution coexisting with bis (carbonyloxy-N, N, N-trimethylethaneaminium) dimethosulfate can be mentioned. The hydrogen peroxide content in this aqueous solution is preferably 0.1 to 30% by weight, more preferably 1 to 20%.
The content of the bleaching activator in the component (B) is preferably 0.1 to 30% by weight, more preferably 0.5 to 30% by weight.
It is 25% by weight.

Further, the bleaching agent composition of the present invention can be used in the form of solid, powder or the like, not in the form of solution. In this case, it is preferable that one or more bleach activators are prepared in a granular form and blended, and a pH adjusting agent such as sodium carbonate or potassium carbonate can also be blended, which is optimal when dissolved in water. It can be pH. As such a form, for example, the component (A) is sodium percarbonate and the component (B) is a bleach activator 2- (4-
Methoxycarbonylbenzoyloxy) -N, N, N-
There may be mentioned a composition which is trimethylethaneaminium methosulfate, the content of sodium percarbonate in this composition being preferably 0.1 to 80% by weight, more preferably 1%.
-60% by weight, and the bleach activator content is preferably 0.1-60% by weight, more preferably 1-50% by weight.
Is.

For bleaching using the bleaching composition of the present invention, for example, in the case of a set in which each component is a solution or an aqueous solution and each component is stored separately, p is added to a solution obtained by mixing each component solution.
After adjusting the pH to a predetermined level by adding an H-adjusting agent, it is preferable to apply this solution to soil around the house. Further, each component solution may be separately applied to the stain so that the stains are mixed on the stain. The application of this solution to dirt is preferably carried out by a method of spraying using a spray container or the like. In addition, application to stains may be performed by using foam or the like, or by using a mixture of an adhesive and the like. When either component is a solid, it is applied as a solution, slurry, paste, etc. by adding the required amount of water.

[0030]

Industrial Applicability The residential bleaching composition of the present invention has no irritating odor and has a high bleaching power, and exhibits an excellent bleaching effect particularly to stains of organic substances such as mold and insoluble inorganic substances. .

[0031]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

The bleaching effect of each sample was evaluated by the stain removing effect and the mold removing effect as follows. (1) Bleaching effect: After using the toilet bowl for men for 2 weeks without flushing water, 10 ml of the sample was sprayed on the toilet bowl, and after 15 minutes, the toilet bowl was washed with water, and the bleaching effect was measured by 10 people according to the following criteria. The panel was visually judged and the average value was calculated. 5 points: The stain was completely removed. 4 points: Almost all dirt was removed. 3 points: Dirt was removed about half. 2 points: A little dirt was removed. 1 point: No stain is removed.

(2) Mold-removing effect; mold (C
ladosporium cladosporioid
es) is soaked in a test cloth prepared by culturing a cotton cloth,
The test cloth was taken out from the test cloth after being placed in a constant temperature bath of 25 ° C. and left for 15 minutes, and the treated cloth was subjected to color difference measurement with respect to the original test cloth, and the bleaching rate was shown.

Examples 1 to 12 and Comparative Example A bleaching agent composition sample comprising an aqueous solution containing 3% by weight of hydrogen peroxide, 2% by weight of sodium carbonate and 2% by weight of each of the bleaching activators shown in Table 1. A sample for comparison consisting of an aqueous solution containing 3% by weight of hydrogen oxide and 2% by weight of sodium carbonate was prepared. All the bleaching agent composition samples of the examples did not generate an irritating odor upon use. Table 1 shows the stain removal effect and mold removal effect of each of these samples.

[0035]

[Table 1]

A solution composition (each component is used in parts by weight) having the respective formulation shown in Examples 13 to 17 below is prepared,
Immediately before use, the pH was adjusted to 10 and used in a tiled bathtub and bathroom where mold was generated. As a result, stains such as tile joints were removed very well, and no irritating odor was generated during use.

Example 13 H ₂ O ₂ 2.5 benzene-1,4-bis (carbonyloxy-N, N, N-trimethylethaneaminium) dimethyl sulphate 10 diethylene glycol 10 water 77.5

[0038] Example 14 _H 2 _O 2 5-1,4-bis (carbonyloxy -N, N, N-trimethyl-butane aminium) dimethylsulfate 10 polypropylene glycol 10 1-hydroxyethane-1,1-disulfonic acid 0.5 Dodecylbenzenesulfonic acid Na 5 water 69.5

Example 15 H ₂ O ₂ 2.5 2- (4-methoxycarbonylbenzoyloxy) -N, N, N-trimethylethaneaminium methosulfate 2.5 Na 5 polypolyphosphate Polyoxyethylene (12) lauryl Ether 15 water 75

Example 16 H ₂ O ₂ 15 Benzene-1,3-bis (carbonyloxy-N, N, N-trimethylbutanaminium) dimethyl sulphate 20 Polyoxyethylene (10) lauryl ether 10 Nitrilotriacetic acid Na 1 α -Sulfomyristic acid methyl ester Na 8 water 46

Example 17 H ₂ O ₂ 7 benzene-1,4-bis (carbonyloxy-N, N, N-trimethylethaneaminium) dimethylsulfate 15 glycerin 10 1-hydroxyethane-1,1-disulfonic acid 0 .5 Cetyltrimethylammonium chloride 4 Lauryldimethylamine oxide 10 Water 53.5

A powder composition (each component is used in parts by weight) having the respective compounding recipes of Examples 18 to 22 below is prepared,
Immediately before use, it was dissolved in water to a concentration of 15% by weight and used in a mold-molded tiled bath and bathroom. As a result, stains such as tile joints were removed very well, and no irritating odor was generated during use.

Example 18 Sodium Percarbonate 60 Benzene-1,4-bis (carbonyloxy-N, N, N-trimethylethaneaminium) Dimethyl Sulfate 30 Sodium Carbonate 10

Example 19 Sodium Percarbonate 40 Benzene-1,4-bis (carbonyloxy-N, N, N-trimethylbutanaminium) Dimethyl Sulfate 25 Natripolyphosphate 10 Sodium Carbonate 20 Sodium Sulfate 5

Example 20 Sodium percarbonate 25 2- (4-Methoxycarbonylbenzoyloxy) -N, N, N-trimethylethaneaminium methosulfate 45 Nitrilotriacetic acid Na 10 Sodium carbonate 20

Example 21 Sodium perborate monohydrate 25 Benzene-1,3-bis (carbonyloxy-N, N, N-trimethylbutaneaminium) dimethyl sulphate 25 Zeolite 10 Polypropylene glycol 10 α-sulfomyristin Acid methyl ester Na 10 Potassium carbonate 20

Example 22 Sodium perborate tetrahydrate 50 Benzene-1,4-bis (carbonyloxy-N, N, N-trimethylethaneaminium) dimethyl sulphate 30 Polyoxyethylene (20) lauryl ether 10 Sodium carbonate 10

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takao Oosugi 1-3-7, Sumida-ku, Tokyo Lion Corporation (72) Inventor Naoki Mizushima 1-3-7, Sumida-ku, Tokyo No. Lion Co., Ltd. (72) Inventor Shinichi Suzuki 1-3-7, Honjo, Sumida-ku, Tokyo Within Lion Co., Ltd.

Claims (3)

[Claims] 1. A peroxide bleaching agent (A) and a general formula (B): [Wherein X ¹ is a (R) ₃ N ⁺ —Y-group (wherein each R is the same or different lower alkyl group, Y is an alkylene group), X ²
Is a hydrocarbon group, a substituted or unsubstituted aminoalkyl group or X
¹ is the same group as ¹ and A is an anion, and n is a number that makes the cation and anion in the molecule have the same valency]. A residential bleaching composition, characterized in that 2. The residential bleaching composition according to claim 1, wherein the peroxide bleaching agent is at least one selected from hydrogen peroxide and peroxides that generate hydrogen peroxide in an aqueous solution. . 3. The residential bleaching composition according to claim 1, wherein the mixing ratio of the peroxide bleaching agent and the bleaching activator is 30: 1 to 1: 2 in a molar ratio.