JPH047399A - Bleaching agent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an oxygen-based bleach that has no irritating odor and has excellent bleaching blades and stability, and a bleaching composition used therefor.

[Prior Art] Conventionally, chlorine bleach and oxygen bleach are known as bleaching agents, but the former has a chlorine-based odor and is highly irritating to the eyes, skin, etc. There is a problem with the generation of toxic gas when used in conjunction with detergents.

For this reason, in recent years, oxygen-based bleaches that are free from such dangers have come into wide use.

In order to increase the bleaching activity, a technique is disclosed in which a first agent containing hydrogen peroxide or a peroxide that generates peracid in an aqueous solution is used in combination with a second agent containing an organic peracid precursor. There is. For example, JP-A-62-4794 describes tetraacetylethylenediamine, tetraacetylglycoluril, pentaerythritol tetraacetate, etc. as organic peracid precursors.

[Problems to be Solved by the Invention] However, since these organic peracid precursors produce peracetic acid as a bleaching active species, they have a strong irritating odor and are difficult to put into practical use. Further, there is a problem that decomposition occurs during storage due to the presence of a small amount of moisture, air (oxygen), trace metals, and the influence of light, resulting in generation of acid or peracid, which further progresses decomposition.

[Means for Solving the Problems] Under these circumstances, the present inventors conducted intensive research to solve the above problems, and as a result, a specific organic peracid has no irritating odor and exhibits an excellent bleaching blade. The present invention was completed based on the discovery that the stability of the organic peracid precursor can be improved by using an antioxidant in combination with the organic peracid precursor.

That is, the present invention provides (a) hydrogen peroxide or a peroxide that produces hydrogen peroxide in an aqueous solution to react with the following general formula (I
) R"0-(AO), -R"-COOH(I) [wherein, R
1 represents a straight chain or branched alkyl group or alkenyl group having 1 to 5 carbon atoms, and R2 represents a straight chain or branched alkylene group having 1 to 5 carbon atoms, or a straight chain or branched chain having 1 to 5 carbon atoms. represents a phenylene group optionally substituted with an alkyl group, n A's are the same or different and each represents an alkylene group having 2 to 4 carbon atoms, and n represents a number of 0 to 20. ] An organic peracid precursor that produces an organic peracid represented by: and (b) an antioxidant is provided.

Examples of the peracid (I) include methoxyperacetic acid, 2-methoxyperpropionic acid, p-methoxyperbenzoic acid, ethoxyperacetic acid, 2-ethoxyperpropionic acid, p-ethoxyperbenzoic acid, propoxyperacetic acid, -propoxyperpropionic acid, p-propoxyperbenzoic acid, butoxyperacetic acid,
2-butoxyperpropionic acid, p-butoxyperbenzoic acid, 2-methoxyethoxyperacetic acid, 2-methoxy-1-methylethoxyperacetic acid, 2-methoxy-2-methylethoxyperacetic acid, 2-ethoxyethoxyperacetic acid, 2-(2-ethoxyethoxy)perpropionic acid, p-(2-ethoxyethoxy)perbenzoic acid, 2-ethoxy-1-methylethoxyperacetic acid, 2-ethoxy-2-methylethoxyperacetic acid, 2-propoxyethoxy Peracetic 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-(2methoxy-1-methylethoxy)ethoxyperacetic acid, 2(2-methoxy-2-methylethoxy)ethoxyperacetic acid, 2- Examples include (2-ethoxyethoxy)ethoxyperacetic acid.

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

(1) The following general formula (II) R''0-(AO), -R'-COH(II) [in the formula, R
1, R2, A and n have the same meanings as above. ] An acid anhydride of an organic acid represented by

Examples of organic acids (n) include methoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid, ethoxyacetic acid,
-Ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic 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
-Methylethoxyacetic 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- Examples include ethoxyethoxy)ethoxyacetic acid.

(2) Organic acid (II) and the following general formula (III) HOCH
*-(C)□-CH20H(II) [wherein, R3 and R
4 are the same or different and represent 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 1O. ] An ester with an alcohol represented by

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

(3) Organic acid (n) and the following general formula (IV) [wherein 1 has the same meaning as above. ] An ester with an alcohol.

Examples of the alcohol (TV) include glycerin and polyglycerin such as diglycerin and triglycerin.

(4) Organic acid (II) and the following general formula (V) ■ [In the formula, R'', R' and 1 have the same meanings as above.] Esters with alcohols represented by

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

(5) Organic acid (n) and the following general formula (VI) [wherein R5
, R6, R7 and R8 are the same or different and are hydrogen atoms,
It represents 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, at least one of which is a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom. shows. ] 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-hydroxymethylammonium bromide and the like.

(6) Ester of organic acid (II) and cyclic alcohol or cyclic polyhydroxy alcohol.

As the cyclic alcohol or cyclic polyhydroxy alcohol, 3,9-bis(1-hydroxymethyl-1-methylpropyl)-2,4,8,10-tetraoxaspiro[5,5oundecane, 3,9-bis( 1-ethyl-1
Spiroglycols such as -hydroxymethylpropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane; Sorbitan; Saccharides such as glucose, maltose, and lactose; Substituted with an alkyl group having 1 to 18 carbon atoms Examples include sugars.

(7) Organic acid (II) and the following general formula (■) [wherein R9
and R'' are the same or different and represent 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 are bonded to each other to form a saturated or An unsaturated ring may be formed. However, at least one of R9 and p R'' represents a hydrogen atom. R'' represents an alkylene group having 1 to 3 carbon atoms or an oxyalkylene group having 1 to 3 carbon atoms, and p is 1 to 3
Indicates the number of ] An acid amide with an amine represented by

Examples of amines (■) include ethylamine, isopropylamine, 2-ethylhexylamine, oleylamine, diethylamine, diisopropylamine, diisobutylamine, monoethanolamine, jetanolamine, ethylenediamine, diethylenetriamine, piperidine,
Examples include morpholine, pyrrole, imidazole and the like.

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

Any conventionally known antioxidant can be used, but preferred ones include 3.5-di-tert-butyl-4-hydroxytoluene and 2.5-di-tert-
Phenolic antioxidants such as butylhydroquinone N, N
'-diphenyl-p-phenyl diamine, phenyl-
Amine-based antioxidants such as 4-piperidinyl carbonate; Sulfur-based antioxidants such as didodecyl-3,3°-thiodipropionate and ditridecyl-3,3°-thiodipropionate; Phosphate-based antioxidants such as phytophyte and triphenylphosphite; natural antioxidants such as L-ascorbic acid and its sodium salt, and DL-α-tocopherol, which may be used alone or in combination of two or more. be able to. Among these, 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butylhydroquinone and DL-α-tocopherol are particularly preferred.

These antioxidants are included in the bleach composition of the present invention.
0.01 to 10% by weight of organic peracid precursor, especially 0.05
It is preferable to mix it in a proportion of ~0.5% by weight.

The bleach composition of the present invention is mixed with separately packaged hydrogen peroxide or an oxidizing agent consisting of a peroxide that produces hydrogen peroxide in an aqueous solution, and water is added if necessary. ), in the form of a solution, slurry or paste, and immediately sprinkled or sprayed on the target surface, or used by dipping the target. That is, it is preferably provided in the form of a bleaching agent consisting of a first agent containing hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution and a second agent containing the above bleach composition. .

Peroxides used here include sodium percarbonate, sodium tripolyphosphate/hydrogen peroxide adduct, sodium pyrophosphate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct, 4Na, SO, ・2H20□ - NaCQ, sodium perborate hydrate, sodium perborate tetrahydrate, sodium persilicate, sodium peroxide, calcium peroxide, and the like.

These can be used alone or in combination of two or more. Among these, especially sodium percarbonate,
Sodium perborate hydrate and sodium perborate tetrahydrate are preferred.

Hydrogen peroxide or peroxide should be present in the mixture at the time of use at a concentration of 0.5
It is preferable that the amount of active oxygen is 98% by weight, particularly 1-50% by weight, and the effective oxygen concentration is 0.1-3% by weight, particularly 0.2-2% by weight. In addition, the organic peracid precursor may be present in the mixture at the time of use in an amount of 0.1 to 50% by weight, particularly 0.5 to 30% by weight.
It is preferable to mix it by weight%.

In order to further enhance the effect of the bleach composition of the present invention, p
It is preferable to adjust H to 5 to 13, especially 5 to 1O,
Buffers may be included for this purpose. Buffers include 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 potassium carbonate; sodium silicate. , alkali metal silicates such as potassium silicate; silicates such as ammonium silicate. In addition, if necessary, alkali metal sulfates such as sodium sulfate, potassium sulfate, and lithium sulfate; ammonium sulfate salts; alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, and lithium bicarbonate; ammonium bicarbonate, etc. It can also be used for improvement. These are preferably blended in the bleach composition in an amount of 0 to 30% by weight.

Further, it is preferable to incorporate a surfactant into the bleach composition of the present invention for the purpose of promoting the penetration of bleaching active species into stains. As surfactants, alkyl glycosides,
Nonionic surfactants such as polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, oxyethylene oxypropylene block polymer (Pluronic), fatty acid monoglyceride, amine oxide; soap, alkyl sulfuric acid Anionic surfactants such as salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, sulfosuccinic acid monoesters; mono- or dialkylamines and their polyoxyethylene adducts; mono- or di-long-chain alkyl quaternary ammonium salts and amphoteric surfactants such as carbobetaine, sulfobetaine, and hydroxysulfobetaine. These are preferably blended in the bleach composition in an amount of 0.1 to 5% by weight.

In the bleach composition of the present invention, p
- Solubilizing agents such as sodium toluenesulfonate, sodium xylene sulfonate, sodium alkenylsuccinate, uric acid, etc.; Penetrants; Suspending agents such as clay; Abrasives; Pigments;
Dyes, fragrances, etc. may be added within a range that does not impair the effects of the present invention.

The bleach composition of the present invention can be used as a bleach for clothing, a mold remover, a drain pipe cleaner, a toilet cleaner, a ventilation fan cleaner, and the like.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

In addition, the evaluation of "bleaching blade" and "smell" in Examples was performed as follows.

(Method for measuring bleaching power) Cladosporium herbalum (C1ados ori
A plastic plate (made of ABS resin) inoculated with M. umherbarum and cultured at 30°C for 14 days was used as a model mold plate, placed horizontally, and soaked with an aqueous bleach solution for 40 d.
After dropping and leaving for 30 minutes, wash with water, air dry, and measure the brightness (L value) using a colorimeter 1001DP manufactured by NEC Corporation.
was measured. Here, the higher the L value, the better the mold bleaching blade.

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

Kushu Hoshisako J A cloth stained with black tea was immersed in an aqueous bleach solution, and the bleached blade after 10 minutes was calculated from the measured reflectance using the following formula.

Bleaching rate (%) = (smell) The smell of the bleach aqueous solution was sensory evaluated by a panel of 10 people.

O: There is no irritating odor or malodor ×: There is an irritating odor or malodor Composition 10
An aqueous bleach solution (available oxygen concentration: 0.5%) containing % by weight and 3% by weight of hydrogen peroxide was prepared and subjected to mold bleaching blade and odor tests. The results are shown in Table 1.

(Margin below) Table 1 Example 2 A bleach composition having the composition shown in Table 2 was prepared and stored at 50°C for 20 days, and then 10% by weight of the bleaching composition and 3% by weight of hydrogen peroxide were An aqueous bleach solution (0.5% effective oxygen concentration) was prepared and subjected to mold bleaching blade and odor tests. The results are shown in Table 2.

(Leaving space below) *1: Diester of ethoxyacetic acid and ethylene glycol *2 = Diester of 2-ethoxyethoxyacetic acid and ethylene glycol *3: Triester of butoxyacetic acid and glycerin *4 = Acid anhydride of 2-ethoxyethoxyacetic acid * 5
: Diester of ethoxy acetic acid and triethylene glycol *6: 3,5-di-tert-butyl-4-hydroxytoluene (blank below) Table Example 3 A bleach composition having the composition shown in Table 3 was prepared and heated to 50°C. After being stored for 20 days at
Aqueous bleach solution containing % by weight (available oxygen concentration approximately 1.3
5%) was prepared and subjected to stain bleaching blade and odor tests.

The results are shown in Table 3.

(Leaving space below) *1: Diester of 2-ethoxyethoxyacetic acid and ethylene glycol *2: Triester of butoxyacetic acid and glycerin *3: Acid anhydride of 2-ethoxyethoxyacetic acid *4
:Tetraacetylethylenediamine*5:35-di-t
ert-butyl-4-hydroxytoluene (blank below) Table 3 Example 4 A bleach composition having the composition shown in Table 4 was prepared and stored at 50°C for 20 days, and then 10% by weight of the bleach composition, An aqueous bleach solution (approximately 225% effective oxygen concentration) containing 15% by weight of sodium perborate hydrate and 2% by weight of sodium dodecyl sulfate was prepared and subjected to stain bleaching blade and odor tests. The results are shown in Table 4.

(Leaving space below) *l: Diester of ethoxyacetic acid and ethylene glycol *2: Diester of 2-ethoxyethoxyacetic acid and ethylene glycol *3: Triester of butoxyacetic acid and glycerin *4: Acid anhydride of 2-ethoxyethoxyacetic acid * 5
: Diester of ethoxyacetic acid and triethylene glycol It has no irritating odor, is stable for long-term storage, and exhibits sufficient bleaching properties even on solid surfaces and at low temperatures.

that's all

Claims (1)

[Scope of Claims] 1. (a) Reacts with hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution by the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [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 straight chain or branched alkyl group having 1 to 5 carbon atoms.
Straight chain or branched alkylene group or carbon number 1-5
represents a phenylene group optionally substituted with a linear or branched alkyl group, n A's are the same or different and each represents an alkylene group having 2 to 4 carbon atoms, n is 0
Indicates a number of ~20. A bleaching agent composition comprising: an organic peracid precursor that produces an organic peracid represented by the above formula; and (b) an antioxidant. 2. The organic peracid precursor is (1) General formula (II) below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R^1, R^2, A and n are the same as above. Show meaning. ] An acid anhydride of an organic acid represented by (2) an organic acid of general formula (II) and the following compounds (III) to (
VIII) Esters or acid amides (III) ▲ Numerical formulas, chemical formulas, tables, etc. Carbon number 1
~3 hydroxyalkyl group, l represents a number from 1 to 10. ] (IV) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, l has the same meaning as above. ] (V) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^3, R^4 and l have the same meanings as above. ] (VI) ▲ Numerical formulas, chemical formulas, tables, etc. 1~
22 alkyl group or alkenyl group or carbon number 1-
3, 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 (VIII) ▲ Numerical formulas, chemical formulas, tables, etc. It may represent an alkyl or alkenyl group having 1 to 22 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms in the chain, or may be bonded to each other to form a saturated or unsaturated ring. However, R^9 and p R^1
At least one of ^0 represents a hydrogen atom. R^1^
1 represents an alkylene group having 1 to 3 carbon atoms or an oxyalkylene group having 1 to 3 carbon atoms, and p represents a number of 1 to 3. ] The bleach composition according to claim 1. 3. The antioxidant is 3,5-di-tert-butyl-4
3. The bleach composition according to claim 1, wherein the bleach composition is selected from -hydroxytoluene, DL-α-tocopherol and 2,5-di-tert-butylhydroquinone. 4. The bleach composition according to claim 1, 2 or 3, wherein the antioxidant is blended in an amount of 0.01 to 10% by weight of the organic peracid precursor. 5. A bleaching agent comprising a first agent containing hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution, and a second agent containing the composition according to claim 1.