JPH0762395A - Bleaching agent composition for house - Google Patents

Abstract

PURPOSE:To obtain a bleaching agent compsn. which does not emit an irritant odor and is excellent in bleaching effects esp. in bleaching org. stains such as mildew or insol. inorg. stains by compounding a peroxide bleaching agent with a bleaching assistant. CONSTITUTION:This compsn. is obtd. by compounding a peroxide bleaching agent (e.g. hydrogen peroxide or a peroxide generating hydrogen peroxide in an aq. soln.) with at least one bleaching assistant selected from compds. of formulas I, II, and III (wherein X1 to X6 and Y1 to Y6 are each an alkylene, alkenylene, cycloalkylene, or arylene group optionally interrupted by a carbon ring; R<1> to R<6> are each a lower alkyl; and Z<->1 to Z<->3 are each a counter ion) (e.g. a methosulfate salt of succinic acid monocholine ester) in a molar ratio of the former to the latter of (20:1)-(1:2). If necessary, the compsn. is further compunded with conventionally used additives: esp. a pH-adjusting agent is useful for sufficiently realizing the effects of the compsn., the pH being adjusted pref. to 6-13, still pref. to 8-12.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a residential bleaching composition which has no pungent odor and has high bleaching power.

[0002]

2. Description of the Related Art Bathrooms, bathtubs, toilets,
Dirt on the sink, especially where water is used frequently,
A large amount of organic substances or insoluble inorganic substances caused by mold and the like cannot be easily removed by an ordinary detergent containing a surfactant as a main component. As a method for removing these stains, a chlorine-based or oxygen-based bleaching agent is used as a main component, and removal by a bleaching effect is used.

However, when a chlorine-based bleaching agent such as sodium hypochlorite is used as a main component, it has excellent stain removal performance, but it is highly dangerous to eyes and skin and has a strong chlorine odor. In use, it is necessary to take measures such as ventilation, and further, generation of toxic chlorine gas is regarded as a problem due to misuse such as combined use with an acidic detergent.

On the other hand, when an oxygen-based bleaching agent typified by hydrogen peroxide is used as a main component, there is no problem such as generation of chlorine gas, but when it is used alone, a sufficient bleaching effect cannot be obtained,
Therefore, various combinations of bleach activators have been proposed (for example, JP-A-60-1299 and JP-A-6-62).
No. 2-4794, Japanese Patent Application Laid-Open No. 2-196896,
JP-A-3-121200).

However, among these bleaching activators, those which generate peracetic acid as a bleaching active species have a strong irritating odor, so that it is difficult to put them into practical use for residential use, and irritating odors are also difficult. The bleach activator that does not generate is hardly practically used because of its low stain removing power and high cost.

[0006]

SUMMARY OF THE INVENTION Under these circumstances, the present invention has been made for the purpose of providing a residential bleaching composition free from irritating odor and excellent in bleaching power.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies to develop a residential bleaching composition having the above-mentioned preferable properties, the present inventors have found that a bleach activator together with a peroxide bleaching agent is obtained. As a result, it was found that the object can be achieved by using an ester of an organic acid having at least two carboxyl groups and an alcohol having a quaternary ammonium group, and the present invention has been completed based on this finding.

That is, the present invention comprises (A) a peroxide bleach, (B) and (b-1) the general formula (I).

[Chemical 4] (In the formula, X ¹ and Y ¹ are an alkylene group which may be interrupted by a carbon ring, an alkenylene group, a cycloalkylene group, or an arylene group, which may have a substituent and are the same as each other. Or different, R
¹ , R ² and R ³ are the same or different lower alkyl groups,
Z ¹ represents a counter ion), (b-2) general formula (II)

[Chemical 5] (In the formula, X ² , X ³ , Y ² and Y ³ are an alkylene group which may be interrupted by a carbocycle or an alkenylene group, a cycloalkylene group or an arylene group, which have a substituent. R ⁴ and R ⁵ are the same or different, R ⁴ and R ⁵ are the same or different lower alkyl groups, Z ² represents a counter ion), and (b-3) the general formula (III)

[Chemical 6] (In the formula, X ⁴ , X ⁵ , X ⁶ , Y ⁴ , Y ⁵ and ⁶ are an alkylene group which may be interrupted by a carbocycle or an alkenylene group, a cycloalkylene group or an arylene group, which are substituted. At least one bleaching activator selected from the compounds represented by the formula (I), which may have the same or different groups, R ⁶ is a lower alkyl group, and Z ³ is a counter ion. And a residential bleaching composition comprising:

In the present invention, the general formula (I), the general formula (II) and the general formula (III) are used as the bleach activator.
At least one selected from the compounds represented by is used. In these general formulas, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ are lower alkyl groups, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group.
These may be the same or different from each other. X ¹ ,
X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵
And Y ⁶ is an alkylene group which may be interrupted by a carbon ring such as an aromatic ring or an alicyclic ring, an alkenylene group, a cycloalkylene group, or an arylene group, which may have a substituent, and These may be the same or different from each other. Examples of the alkylene group in these include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and the like, an alkenylene group includes a vinylene group, and the like, and a cycloalkylene group includes a cyclohexylene group and cyclobutylene. And the like. Examples of the arylene group include a phenylene group and a naphthylene group. The carboxyl group bound to these may be in either acid or salt state, and examples of the salt include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and substituted or unsubstituted ammonium salts. Can be mentioned. Z ₁ ⁻ , Z ₂ ^−, and Z ₃ ⁻ are counter ions, and for example, Cl ⁻ , Br ⁻ , I
_{^{-, CH 3 SO 4 -,}} CH 3 COO - , etc. monovalent anion equivalent to a monovalent, such as divalent anion SO ₄ ^2-like.

(B-1) represented by the above general formula (I)
The method for producing the compound of the component is a methosulfate salt of succinic acid monocholine ester (N, N, N-trimethyl-
[2-{(3-carboxy-1-oxopropyl) oxy} ethane] aminium methosulfate) will be described as an example. 2-dimethylaminoethanol is reacted with succinic anhydride to give 2-dimethylaminoethyl ester of succinic acid. Then, the desired compound is obtained by carrying out a quaternization reaction of the amine with dimethylsulfate or by reacting choline with succinic anhydride. The former production method may include an amine compound which is not quaternized, but there is no problem in bleaching performance.

(B-represented by the above general formula (II)
The method for producing the compound as the component 2) will be described by taking N, N, dimethyl-bis [2-{(3-carboxy-1-oxopropyl) oxy} ethane] aminium methosulfate as an example. The desired compound is obtained by reacting succinic acid to generate a disuccinic acid ester and then performing a quaternization reaction of the amine with dimethylsulfate.

(B-represented by the general formula (III)
The method for producing the compound as the component 3) will be described by taking N-methyl-tris [2-{(3-carboxy-1-oxopropyl) oxy} ethane] aminium methosulfate as an example, and triethanolamine containing succinic anhydride. After reacting to generate a trisuccinic acid ester, a desired compound is obtained by performing a quaternization reaction of an amine with dimethylsulfate.

Examples of the peroxide bleach used in the bleach composition of the present invention together with the bleach activator include hydrogen peroxide, percarbonates such as sodium percarbonate and potassium percarbonate, and sodium perborate. , Sodium perborate monohydrate, sodium perborate tetrahydrate, etc. perborate, perphosphate, other tripolyphosphate, pyrophosphate, citrate, sodium sulfate, urea, sodium silicate, etc. In particular, hydrogen peroxide or peroxides that generate hydrogen peroxide in an aqueous solution, especially sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate Is preferred. These may be used alone or in combination of two or more.

In the bleaching composition of the present invention, the mixing ratio of the peroxide bleaching agent and the bleaching activator is 2 in molar ratio.
It is preferably from 0: 1 to 1: 2, especially from 10: 1 to 1: 1. If it deviates from this range, it becomes difficult to obtain sufficient bleaching power.

In the bleaching composition of the present invention, in addition to the above-mentioned essential components, if necessary, various conventionally used additive components are appropriately blended in accordance with the use within a range not impairing the object of the present invention. can do.

Examples of the additive component include a pH adjusting agent, various anionic or nonionic surfactants,
Examples include water-soluble solvents, solubilizing agents, various inorganic or organic builders, enzymes, perfumes, pigments, fluorescent agents and the like.

The pH adjuster has a pH of 6 to 13 and particularly 8 to 12 in order to exert a sufficient effect on the bleaching composition of the present invention.
Since it is desirable to adjust the amount to 1, it is preferable to use it as a blending component, and it is particularly desirable to blend it for the first time when using it. Examples of the pH adjusting agent include alkalis or buffers, commercially available alkaline detergents, and the like. Examples of the alkali or buffer include sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide, mono-,
Di- or triethanolamine, substituted or unsubstituted ammonium compounds such as ammonium hydroxide, carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate,
Examples thereof include silicates such as sodium silicate and potassium silicate, and phosphates such as sodium tripolyphosphate and sodium pyrophosphate.

Further, the bleaching composition of the present invention lowers the pH of the system to be used with generation of bleaching active species. Therefore, in order to maximize the effect, the pH after washing is also 6 to. 13 It is preferable to select the kind and amount of the pH adjuster so that the pH adjuster can be maintained at 8 to 12.

The surfactant is preferably added to the bleaching composition of the present invention because it promotes the penetration of the bleaching active species into soil. Examples of surfactants 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 ethers, sorbitan. Fatty acid ester, alkyl glycoside,
Nonionic surfactants such as alkyl glycoside fatty acid ester, polyoxyethylene fatty acid ester, fatty acid glyceride, oxyethyleneoxypropylene block polymer, long-chain mono- or dialkyl quaternary ammonium salt, cationic surfactant such as amine oxide, 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-diphosphonic acid and salts thereof, and particularly chelate builder. Examples thereof include phosphates, polyacrylates, polycarboxylic acids, zeolites and the like.

Examples of the water-soluble solvent include methanol,
Ethanol, 2-propanol, 1-propanol and other monohydric alcohols, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and other dihydric alcohols, glycerin and other three Examples thereof include polyhydric alcohols, mono- or diethers of these dihydric alcohols and trihydric alcohols. Examples of the solubilizer include urea and p-toluenesulfonate.

As the enzyme, a hydrolase that promotes the addition and removal of water, a redox enzyme that promotes redox, a group is transferred from one molecule to another, and the stain is altered to remove it. A transferase that promotes the cleavage, a ligase or lyase that breaks the bond between molecules to decompose the dirt and promotes the removal, an enzyme that isomerizes the molecule and chemically alters the dirt to promote the removal, and the like can be used. Of these, hydrolases are preferable, and among them, protease is particularly preferable.

Examples of the protease include serine protease, pepsin, trypsin, chymotrypsin, collagenase, keratinase, esterase, sptilisin, papain, carboxypeptidases A and B, and aminopeptidase. Among them, serine protease is preferable. Examples of commercially available products thereof include Alcalase (manufactured by Novo Industry Co., Ltd.), Esperase (manufactured by Novo Industry Co., Ltd.), Pyroplase (manufactured by Nagase Sangyo Co., Ltd.), Maxatase (manufactured by Gist Procades Co., Ltd.), and ALP-2 (Meiji Seikasha Co., Ltd.). Commercially available), Superase (manufactured by Pfizer) and the like are easily available. The enzyme content is preferably in the range of 0.01 to 5% by weight.

When the bleaching composition of the present invention is in the form of a solution in which the component (A) and the component (B) are coexistent, the storage stability decreases when the solution has a pH of 6 or more.
It is necessary to adjust H to be less than 6. In order to prevent the problem of storage stability, it is preferable that the component (A) and the component (B) are separately stored in the form of a set product. In this case, it is preferable that each component be in the form of a solution because it is easy to use.

Further, in the bleaching agent composition of the present invention, the component (A) and the component (B) can coexist without forming a solution form. In this case, it is preferable that the bleaching activator as the component (B) is prepared by mixing one or more kinds in a granular form. At the time of this granulation, it is preferable to add 5 to 200 parts by weight, preferably 10 to 100 parts by weight of a mixture of one or more binders to 100 parts by weight of the bleaching activator for granulation.

The binder used in this case is 5 to 6
It is preferable to use a nonionic surfactant, polyethylene glycol, polypropylene glycol, liquid paraffin, higher alcohol, etc., which have fluidity at 0 ° C., preferably 10 to 40 ° C., alone or in a mixture of two or more kinds. Preferred examples of the nonionic surfactant include the following (1) to
Examples include those shown in (6).

(1) A polyoxyethylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of ethylene oxide added thereto.

(2) A polyoxyethylene alkylphenyl ether having an alkyl group having an average carbon number of 6 to 12 and having 1 to 20 mol of ethylene oxide added thereto.

(3) A polyoxypropylene alkyl or alkenyl ether having an alkyl group or an alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of propylene oxide added thereto.

(4) A polyoxybutylene alkyl or alkenyl ether having an alkyl or alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of butylene oxide added thereto.

(5) A polyoxyalkylene alkyl or alkenyl ether having an alkyl group or an alkenyl group having an average carbon number of 10 to 20 and having a total of 1 to 20 mol of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added (here And the molar ratio of ethylene oxide to propylene oxide or butylene oxide is 1:99 to 99: 1).

(6) A copolymer of ethylene oxide and propylene oxide, or a copolymer of ethylene oxide and butylene oxide.

As the granulation method, known methods such as an extrusion granulation method, a tumbling granulation method, and a compression granulation method are used. A suitable one may be adopted. For example, when granulating using an extrusion granulation method, a bleaching activator finely ground to a particle size of 150 μm or less is uniformly mixed with a known mixer as a pre-step of granulation, and then a binder is gradually added to form a powder. The body and the binder are sufficiently kneaded, and the kneaded mixture is extruded and charged in a granulator to granulate, and then sieved. If necessary, in order to improve the particle characteristics, the surface of the granulated product may be coated with an inorganic fine powder having an average primary particle diameter of 0.1 μm or less, for example, fine silica powder, before sieving.

In the bleaching method using the bleaching agent composition of the present invention, for example, when each component is a solution, a mixed solution of each component is used as it is, or each component solution is mixed in a set in which each composition is stored individually. Add pH adjuster to the prepared liquid
After adjusting to, apply this solution to the soil around the house. Alternatively, each component solution may be individually applied to the stain so that the stains are mixed together. The application of these solutions to dirt is preferably carried out by spraying using a spray container or the like. In addition, the method of applying to the stain may be a form of application such as application using a foam or the like, or application by blending an adhesive or the like. When any of the components is solid, it is applied as a solution, slurry, paste or the like by adding a necessary amount of water.

[0035]

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

[0036]

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

Examples 1 to 8 and Comparative Example 1 A sample for comparison consisting of 3 wt% hydrogen peroxide and 2 wt% sodium carbonate, and a bleaching agent containing 2 wt% of each bleach activator shown in Table 1 in the sample. The antifungal effect of the composition was examined by the following evaluation method. The results are shown in Table 4.

In each sample, mold (Cladospor)
The test cloth prepared by culturing ium cladosporioides) on a cotton cloth was immersed, placed in a constant temperature bath at 25 ° C, left for 15 minutes, and then the test cloth was taken out and washed with water. Then, the bleaching rate was obtained.

[0039]

[Table 1]

The bleaching agent compositions prepared by using each of the bleaching activators shown in Table 1 did not generate an irritating odor upon use.

Examples 9 to 16 and Comparative Example 2 A male urinal in a toilet was used for 2 weeks without running water, and a sample for comparison consisting of 3 wt% of hydrogen peroxide and 2 wt% of sodium carbonate was used. 10 ml of a bleaching agent composition containing 2% by weight of each bleaching activator shown in Table 2 was sprayed on a toilet urinal, washed 15 minutes later with water, and the bleaching effect was evaluated according to the following criteria. This operation was repeated 10 times (n = 10). The average value of the results is shown in Table 2.

<Judgment Criteria> 5: The stain was completely removed. 4: Most of the dirt was removed. 3: About half the dirt was removed. 2: A little dirt was removed. 1: No dirt came off.

[0043]

[Table 2]

The bleaching compositions prepared by using the bleaching activators shown in Table 2 did not generate an irritating odor upon use.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takao Osugi 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 Main Office, Sumida-ku, Tokyo Within Lion Co., Ltd.

Claims (3)

[Claims] 1. A peroxide-based bleaching agent (A) and (B) (b)
-1) General formula: (In the formula, X ¹ and Y ¹ are an alkylene group which may be interrupted by a carbon ring, an alkenylene group, a cycloalkylene group, or an arylene group, which may have a substituent and are the same as each other. Or different, R
¹ , R ² and R ³ are the same or different lower alkyl groups,
Z ¹ represents a counter ion), (b-2) general formula: (In the formula, X ² , X ³ , Y ² and Y ³ are an alkylene group which may be interrupted by a carbocycle or an alkenylene group, a cycloalkylene group or an arylene group, which have a substituent. And R ⁴ and R ⁵ are the same or different, and R ⁴ and R ⁵ are the same or different lower alkyl groups, Z ² represents a counter ion), and (b-3) the general formula: (In the formula, X ⁴ , X ⁵ , X ⁶ , Y ⁴ , Y ⁵ and ⁶ are an alkylene group which may be interrupted by a carbocycle or an alkenylene group, a cycloalkylene group or an arylene group, which are substituted. At least one bleaching activator selected from the compounds represented by the formula (I), which may have the same or different groups, R ⁶ is a lower alkyl group, and Z ³ is a counter ion. A residential bleaching composition comprising: 2. The bleaching composition according to claim 1, wherein the peroxide bleaching agent is hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aqueous solution. 3. The bleaching composition according to claim 1, wherein the mixing ratio of the peroxide bleaching agent and the bleaching activator is 20: 1 to 1: 2 in a molar ratio.