JPH075914B2 - Bleach composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an oxygen-based bleaching agent which has no pungent odor and is excellent in bleaching power and stability, and a bleaching agent composition used therefor.

[Prior Art] Conventionally, chlorine-based bleaching agents and oxygen-based bleaching agents are known, but the former is strongly irritating to chlorine-specific odors, eyes, skin, etc. There is a problem that toxic gas is generated when used in combination with a detergent.

Therefore, in recent years, such an oxygen-based bleaching agent which has no danger has been widely used. Then, in order to enhance the bleaching activity, a technique is disclosed in which a first agent containing hydrogen peroxide or a peroxide that produces a peracid in an aqueous solution and a second agent containing an organic peracid precursor are used in combination. There is. For example, JP-A-62-4794 describes tetraacetylethylenediamine, tetraacetylglycoluril, pentaerythritol tetraacetate and the like as organic peracid precursors.

[Problems to be Solved by the Invention] However, since these organic peracid precursors generate peracetic acid as a bleaching active species, they have a strong pungent odor and are difficult to put into practical use. Further, during storage, decomposition occurs due to the presence of slight amounts of water, air (oxygen), trace metals, and light, and as a result, acid or peracid is generated, which causes further decomposition.

[Means for Solving the Problems] In such circumstances, the present inventors have conducted diligent research to solve the above-mentioned problems, and as a result, the specific organic peracid has no irritating odor and exhibits excellent bleaching power, The present invention has been completed by finding that the stability of the precursor is improved by using an antioxidant together with the organic peracid precursor that produces the precursor.

That is, the present invention provides the following general formula (I) by reacting with (a) hydrogen peroxide or a peroxide that produces hydrogen peroxide in an aqueous solution. [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 1 to 5 carbon atoms, and R ² represents a linear or branched alkylene group having 1 to 5 carbon atoms or 1 to 5 carbon atoms. Represents a phenylene group which may be substituted with a linear or branched alkyl group, n of A are the same or different, each represents an alkylene group having 2 to 4 carbon atoms, and n is a number of 0 to 20. Indicates. ] It provides the composition for bleaching agents containing the organic peracid precursor which produces | generates the organic peracid represented by these, and (b) antioxidant.

Examples of the peracid (I) include methoxyperacetic acid, 2-methoxyperpropionic acid, p-methoxyperbenzoic acid, ethoxyperacetic acid, 2-ethoxyperpropionic acid, p-ethoxyperbenzoic acid, propoxyperacetic acid, 2 -Propoxy perpropionic acid,
p-propoxyperbenzoic acid, butoxyperacetic acid, 2-butoxyperpropionic acid, p-butoxyperbenzoic acid, 2-methoxyethoxyperacetic acid, 2-methoxy-1-methylethoxyperacetic acid,
2-methoxy-2-methylethoxy peracetic acid, 2-ethoxyethoxy peracetic acid, 2- (2-ethoxyethoxy) perpropionic acid, p- (2-ethoxyethoxy) perbenzoic acid, 2-ethoxy-1-methylethoxy Peracetic acid, 2-ethoxy-2-methylethoxyperacetic acid, 2-propoxyethoxyperacetic acid, 2-propoxy-1-methylethoxyperacetic acid, 2-propoxy-2-methylethoxyperacetic acid, 2-butoxyethoxyperacetic acid, 2-butoxy-1-methylethoxyperacetic acid, 2-butoxy-2-methylethoxyperacetic acid, 2- (2-methoxyethoxy) ethoxyperacetic acid, 2- (2-methoxy-1-methylethoxy) ethoxyperacetic acid, 2- (2-methoxy-2-methylethoxy) ethoxyperacetic acid, 2- (2-ethoxyethoxy) ethoxyperacetic acid and the like can be mentioned.

Examples of the organic peracid precursor that reacts with hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution to generate the organic peracid (I) include the following.

(1) The following general formula (II) [In the formula, R ¹ , R ² , A and n have the same meanings as described above. ] The acid anhydride of the organic acid represented by these.

Organic acids (II) include methoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid, 2-propoxypropionic acid, p-propoxy. Benzoic acid, butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid, 2-methoxyethoxyacetic acid, 2-methoxy-1-
Methylethoxyacetic acid, 2-methoxy-2-methylethoxyacetic acid, 2-ethoxyethoxyacetic acid, 2- (2-ethoxyethoxy) propionic acid, p- (2-ethoxyethoxy) benzoic acid, 2-ethoxy-1-methylethoxy Acetic acid, 2-ethoxy-
2-methylethoxyacetic acid, 2-propoxyethoxyacetic acid, 2-
Propoxy-1-methylethoxyacetic acid, 2-propoxy-2-
Methylethoxyacetic acid, 2-butoxyethoxyacetic acid, 2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid, 2- (2-methoxyethoxy) ethoxyacetic acid,
2- (2-methoxy-1-methylethoxy) ethoxyacetic acid, 2-
(2-Methoxy-2-methylethoxy) ethoxyacetic acid, 2-
(2-Ethoxyethoxy) ethoxyacetic acid and the like can be mentioned.

(2) Organic acid (II) and the following general formula (III) [In the formula, R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and 1 represents a number of 1 to 10. ] An ester with an alcohol represented by:

Examples of the alcohol (III) include alkylene glycols such as trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol and sorbitol.

(3) Organic acid (II) and the following general formula (IV) [In formula, 1 shows the same meaning as the above. ] An ester with an alcohol represented by:

Examples of the alcohol (IV) include glycerin and polyglycerins such as diglycerin and triglycerin.

(4) Organic acid (II) and the following general formula (V) [In the formula, R ³ , R ⁴ and l have the same meanings as described above. ] An ester with an alcohol represented by:

Examples of the alcohol (V) include polyethylene glycols such as ethylene glycol, diethylene glycol and triethylene glycol.

(5) Organic acid (II) and the following general formula (VI) [In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms or a hydroxyalkyl having 1 to 3 carbon atoms. Represents a group, at least one of which is a hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom. ] An ester with an alcohol represented by:

Alcohol (VI) includes N, N, N-trimethyl-N-hydroxymethylammonium chloride, N, N, N-trimethyl-N-hydroxyethylammonium chloride, N-oleyl-N, N-dimethyl-N-hydroxy. Examples thereof include hydroxyalkyl ammoniums such as methyl ammonium bromide.

(6) An ester of an organic acid (II) with a cyclic alcohol or a cyclic polyhydroxy alcohol.

Examples of the cyclic alcohol or cyclic polyhydroxy alcohol include 3,9-bis (1-hydroxymethyl-1-methylpropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and 3,9-bis (1 -Ethyl-1-hydroxymethylpropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and other spiroglycols; sorbitan; sugars such as glucose, maltose and lactose; alkyl groups having 1 to 18 carbon atoms And the like.

(7) Organic acid (II) and the following general formula (VIII) [In the formula, R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, or They may combine to form a saturated or unsaturated ring. However, at least 1 of R ⁹ and p R ¹⁰
Each represents a hydrogen atom. R ¹¹ represents an arylene group having 1 to 3 carbon atoms or an oxyalkylene group having 1 to 3 carbon atoms, and p is 1
Indicates a number of ~ 3. ] An acid amide with an amine represented by

As the amine (VIII), ethylamine, isopropylamine, 2-ethylhexylamine, oleylamine, diethylamine, diisopropylamine, diisobutylamine, monoethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, piperidine,
Examples include monophorine, pyrrole, imidazole and the like.

Among these organic peracid precursors, esters of organic acid (II) with ethylene glycol, diethylene glycol or glycerin or acid amides with ethylenediamine are particularly preferable.

Any conventionally known antioxidant can be used as an antioxidant, but preferred antioxidants are phenolic antioxidants such as 3,5-di-tert-butyl-4-hydroxytoluene and 2,5-di-tert-butylhydroquinone. Agents; amine antioxidants such as N, N'-diphenyl-p-phenylenediamine and phenyl-4-piperidinyl carbonate; didodecyl-3,3'-thiodipropionate, ditridecyl-3,3'-thio Sulfur-based antioxidants such as dipropionate; phosphorus-based antioxidants such as tris (isodecyl) phosphite and triphenylphosphite; natural antioxidants such as L-ascorbic acid and its sodium salt, DL-α-tocopherol Can be used alone or in combination of two or more. Of these, 3,5-di-tert-butyl-4-
Hydroxytoluene, 2,5-di-tert-butylhydroquinone and DL-α-tocopherol are particularly preferred.

These antioxidants, in the bleach composition of the present invention,
It is preferable to add 0.01 to 1.0% by weight, particularly 0.05 to 0.5% by weight of the organic peracid precursor.

The composition for a bleaching agent of the present invention is mixed with an oxidizing agent consisting of hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution separately packaged immediately before use (adding water if necessary). Then, the solution, slurry or paste is used and immediately sprayed, sprayed or the like on the target surface, or immersed in the target object. That is, it is preferably provided in the form of a bleaching agent comprising a first agent containing hydrogen peroxide or a peroxide that produces hydrogen peroxide in an aqueous solution and a second agent containing the composition for a bleaching agent. .

The peroxide used herein, sodium percarbonate, sodium tripolyphosphate-hydrogen peroxide adduct, sodium pyrophosphate-hydrogen peroxide adduct, urea-hydrogen peroxide adduct, 4Na ₂ SO ₄ · 2H ₂ O ₂ .NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium persilicate, sodium peroxide, calcium peroxide and the like can be mentioned. These may be used alone or in combination of two or more. Of these, sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferable.

Hydrogen peroxide or peroxide is present in the mixture at 0.5-9
8% by weight, especially 1 to 50% by weight, effective oxygen concentration of 0.1
It is preferable that the amount is ˜3% by weight, particularly 0.2 to 2% by weight. The organic peracid precursor is preferably added to the mixture at the time of use in an amount of 0.1 to 50% by weight, particularly 0.5 to 30% by weight.

The bleaching composition of the present invention has a pH of
Is preferably adjusted to 5 to 13, particularly 5 to 10, and a buffering agent can be added for this purpose. As a buffer,
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; amine derivatives such as ammonium hydroxide, mono-, di- and triethanol; alkali metal carbonates such as sodium carbonate and calcium carbonate; sodium silicate, potassium silicate, etc. Alkali metal silicates; silicates such as ammonium silicate and the like. In addition, alkali metal sulfates such as sodium sulfate, potassium sulfate, lithium sulfate; ammonium sulfate; alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, lithium bicarbonate; ammonium bicarbonate It can also be used for improvement. These are preferably added to the bleaching composition in an amount of 0 to 30% by weight.

In addition, it is preferable to add a surfactant to the bleaching composition of the present invention for the purpose of promoting penetration of bleaching active species into soil. As the surfactant, an alkyl glycoside,
Nonionic surfactants such as polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, oxyethyleneoxypropylene block polymer (pluronic), fatty acid monoglyceride, amine oxide; soap, alkyl sulfate Anionic surfactants such as salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate ester salts, and sulfosuccinic acid monoesters; mono- or dialkylamines and polyoxyethylene adducts thereof; mono- or di-long-chain alkyl quaternary ammonium salts And cationic surfactants; amphoteric surfactants such as carbobetaine, sulfobetaine, hydroxysulfobetaine and the like. These are preferably incorporated in the bleaching composition in an amount of 0.1 to 5% by weight.

In the bleaching composition of the present invention, if necessary, n-
Soluble agents such as sodium toluene sulfonate, sodium xylene sulfonate, sodium alkenyl succinate, and uric acid; penetrants; suspending agents such as clay; abrasives; pigments; dyes; It can be blended within the range not present.

The bleaching composition of the present invention can be used as a bleaching agent for clothing, as well as a mold removing agent, a cleaning agent for drainage pipes, a cleaning agent for toilets, a cleaning agent for ventilation fans, and the like.

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

The "bleaching power" and "smell" in the examples were evaluated as follows.

《Bleaching power measurement method》 Mold bleaching power Cladosporium herbaru
m) inoculated and cultured at 30 ° C for 14 days.
(Made of BS resin) is used as a model mold plate, which is placed horizontally, 40 μl of an aqueous bleach solution is dropped, allowed to stand for 30 minutes, washed with water, air-dried, and then lightness is measured using a colorimeter 1001DP manufactured by NEC Corporation. L value) was measured. Here, the higher the L value, the better the mold bleaching power.

The L value of the plastic plate was 92.4, and the L value of the model mold plate was 65 to 75.

Stain Bleaching Power A tea-contaminated cloth was immersed in an aqueous bleaching solution, and the bleaching power after 10 minutes was calculated from the measured reflectance by the following formula.

<< Odor >> The odor of the bleach solution was sensory evaluated by 10 panelists.

◯: There is no irritating odor or bad odor ×: There is irritating odor or bad odor Example 1 A composition for bleaching agent having the composition shown in Table 1 was prepared and stored at 50 ° C. for 5, 20 or 60 days, and then bleaching agent. Composition 10% by weight
An aqueous bleaching agent solution containing 3% by weight of hydrogen peroxide and hydrogen peroxide (effective oxygen concentration: about 0.5%) was prepared and subjected to a test for mold bleaching power and odor. The results are shown in Table 1.

Example 2 A composition for bleaching agent having the composition shown in Table 2 was prepared and stored at 50 ° C. for 20
After storage for a day, an aqueous bleaching solution containing 10% by weight of the bleaching composition and 3% by weight of hydrogen peroxide (effective oxygen concentration of about 0.
5%) was prepared and subjected to a test for mold bleaching power and odor.
The results are shown in Table 2.

Example 3 A bleaching agent composition having the composition shown in Table 3 was prepared, and the composition was maintained at 50 ° C. for 20
After storing for a day, a bleaching solution containing 10% by weight of a bleaching composition, 10% by weight of sodium percarbonate and 2% by weight of sodium dodecylsulfate (effective oxygen concentration of about 1.35%) was prepared, and the stain bleaching power and odor Was subjected to the test. The results are shown in Table 3.

Example 4 A composition for bleaching agent having the composition shown in Table 4 was prepared and stored at 50 ° C. for 20 hours.
After storage for a day, an aqueous bleach solution containing 10% by weight of a bleaching composition, 15% by weight of sodium perborate monohydrate and 2% by weight of sodium dodecyl sulfate (effective oxygen concentration of about 2.25
%) Was prepared and subjected to a stain bleaching power and odor test. The results are shown in Table 4.

EFFECTS OF THE INVENTION As described above, the bleaching composition of the present invention has no pungent odor, is stable for long-term storage, and has sufficient bleaching power even on a solid surface or at a lower temperature. Is to demonstrate.

Claims (5)

[Claims] 1. A compound represented by the following general formula (I) which reacts with (a) hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution. [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 1 to 5 carbon atoms, and R ² represents a linear or branched alkylene group having 1 to 5 carbon atoms or 1 to 5 carbon atoms. Represents a phenylene group which may be substituted with a linear or branched alkyl group, n of A are the same or different, each represents an alkylene group having 2 to 4 carbon atoms, and n is a number of 0 to 20. Indicates. ] The composition for bleaching agents containing the organic peracid precursor which produces | generates the organic peracid represented by these, and (b) antioxidant. 2. An organic peracid precursor comprises: (1) the following general formula (II) [In the formula, R ¹ , R ² , A and n have the same meanings as described above. ] An acid anhydride of an organic acid represented by: or (2) an organic acid of the general formula (II) and the following compounds (III) to (V
III) Esters or acid amides [In the formula, R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and 1 represents a number of 1 to 10. ] [In formula, 1 shows the same meaning as the above. ] [In the formula, R ³ , R ⁴ and l have the same meanings as described above. ] [In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms or a hydroxyalkyl having 1 to 3 carbon atoms. Represents a group, at least one of which is a hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom. ] (VII) Cyclic alcohol or cyclic polyhydroxy alcohol [In the formula, R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, or They may combine to form a saturated or unsaturated ring. However, at least 1 of R ⁹ and p R ¹⁰
Each represents a hydrogen atom. R < ¹¹ > shows a C1-C3 alkylene group or a C1-C3 oxyalkylene group, and p shows the number of 1-3. ] The composition for bleaching agents according to claim 1. 3. The antioxidant is 3,5-di-tert-butyl-4-
Hydroxytoluene, DL-α-tocopherol and 2,5-
The bleaching composition according to claim 1 or 2, which is selected from di-tert-butylhydroquinone. 4. The antioxidant is an organic peracid precursor 0.01-1.
The composition for a bleaching agent according to claim 1, 2 or 3, which is blended in an amount of 0% by weight. 5. A bleaching agent comprising a first agent containing hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution, and a second agent containing the composition according to claim 1.