JPH0633426B2 - Bleach composition - Google Patents

Description

TECHNICAL FIELD The present invention contains a peroxide that releases hydrogen peroxide in an aqueous solution, and is excellent in bleaching power used for various purposes such as household use and industrial use. It relates to an oxygen-based bleaching composition.

BACKGROUND ART Problems to be Solved by Conventional Techniques and Inventions Bleaching agents include reduction-type bleaching agents and oxidation-type bleaching agents, and oxidation-type bleaching agents are widely used because of their excellent effects. Oxidative bleaching agents are roughly classified into chlorine bleaching agents and oxygen bleaching agents.Chlorine bleaching agents cannot be used in colored clothing because they discolor or discolor the object to be treated and have a unique odor. There are drawbacks such as having On the other hand, the oxygen-based bleaching agent has a wider usable range than the chlorine-based bleaching agent,
It is excellent in that it does not have the characteristic odor of chlorine bleach and is easy to use.

However, among the oxygen-based bleaching agents, hydrogen peroxide and percarbonate, perborate-hydrate, and hydrogen peroxide adducts such as pyrophosphate, citrate, sodium sulfate, urea, sodium silicate, etc. Peroxides that release hydrogen peroxide in aqueous solution have inferior bleaching power as compared with chlorine-based bleaching agents, and a sufficient bleaching effect cannot be obtained with a short-time bleaching treatment, especially at low temperatures. It has a drawback that it takes a considerably long time to obtain the effect.

Further, conventionally, hydrogen peroxide or peroxide has been used in combination with a bleaching activator such as TAED (tetraacetylethylenediamine), TAGU (tetraacetylglycoluril), PAG (pentaacetylglucose) to enhance the bleaching effect. It is being appreciated. However, the activating effects of these conventional bleach activators are not sufficient, and when these activators are used, the object to be treated may be discolored and discolored by the bleaching agent. The fact is that oxygen-based bleaching agents have not yet achieved a satisfactory bleaching effect as compared with chlorine-based bleaching agents.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oxygen-based bleaching agent composition which has an excellent bleaching effect and can bleach an object to be processed satisfactorily in a short processing time.

Means and Actions for Solving the Problems In order to achieve the above-mentioned object, the present inventors have conducted earnest research on enhancing the bleaching power of an oxygen-based bleaching agent, and as a result, released hydrogen peroxide in an aqueous solution. To the bleaching agent composition containing an oxide, one or more compounds of the following formula (1) are blended as the peroxide activator to obtain a peroxide and a compound of the formula (1). It was found that the bleaching power was remarkably enhanced when used together.

Therefore, the present invention relates to a bleaching composition containing a peroxide that releases hydrogen peroxide in an aqueous solution, wherein the compound of the following formula (1) is used as an activator of the peroxide: (However, R is a lower alkyl group or a lower alkoxy group,
R'is an alkyl or alkenyl group having 1 to 18 carbon atoms, X
Represents a halogen, an alkylsulfonic acid group having 1 to 3 carbon atoms or a phenylsulfonic acid group, and p = 0 to 4, q = 1 to 1
3,1 ≦ p + q ≦ 5. ) A bleaching agent composition comprising one or more cyanopyridinium salts represented by

According to the composition of the present invention, the bleaching power of the peroxide that releases hydrogen peroxide in an aqueous solution is remarkably improved by the activation action of the compound of the above formula (1), and thus the object to be treated is bleached in a short time. In addition to being able to be processed, it has the effect of favorably preventing discoloration and fading of the object to be processed.

Hereinafter, the present invention will be described in more detail.

In the bleaching agent of the present invention, a peroxide that releases hydrogen peroxide in an aqueous solution is blended as a bleaching agent. In this case, the peroxide is dissolved in water to form hydrogen peroxide. Any material that releases can be used. For example, one or more of hydrogen peroxide, percarbonate, perborate, and hydrogen peroxide adducts such as pyrophosphate, citrate, sodium sulfate, urea, and sodium silicate are preferably used. However, it is particularly preferable to use hydrogen peroxide, percarbonate such as sodium percarbonate, or perborate such as sodium perborate monohydrate.

The present invention uses the following formula (1) as an activator for the peroxide. (However, R is a lower alkyl group or a lower alkoxy group,
R'is an alkyl or alkenyl group having 1 to 18 carbon atoms, X
Represents a halogen, an alkylsulfonic acid group having 1 to 3 carbon atoms or a phenylsulfonic acid group, and p = 0 to 4, q = 1 to 1
3,1 ≦ p + q ≦ 5. ) Is used together with the cyanopyridinium salt.

In this case, as the cyanopyridinium salt represented by the formula (1), 2-cyanopyridinium salt, 3-cyanopyridinium salt, and 4-cyanopyridinium salt in which R ′ is an alkyl group having 1 to 12 carbon atoms are particularly preferable. Used. Examples of such compounds include methyl-2-cyanopyridinium chloride, propyl-2-cyanopyridinium chloride, ethyl-3-cyanopyridinium bromide, ethyl-4-cyanopyridinium methylsulfonate, dodecyl-2-cyanopyridinium phenylsulfonate and the like. Is mentioned.

In the present invention, the mixing ratio of the above-mentioned peroxide and activator is preferably a molar ratio of 20: 1 to 1: 2,
If the amount is out of the above range, sufficient bleaching power may not be obtained. The more preferable mixing molar ratio of the peroxide and the activator is 10: 1 to 1: 1.

The bleaching agent composition of the present invention can be prepared by a conventional method by adding appropriate other known components shown below as needed. For example, a bleaching composition can be prepared by adding an inorganic / organic builder, an anion, a nonionic surfactant, an enzyme, a fragrance, a pigment, a fluorescent agent, etc. to the composition of the present invention. Here, as the inorganic / organic builder, sodium sulfate,
Anionic surfactants such as sodium silicate, sodium tripolyphosphate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, 1-hydroxyethane-1,1-diphosphonic acid and salts thereof have about 8 to 22 carbon atoms. Sulfonates and sulfates having an alkyl group, alkylbenzene sulfonates having an alkyl group of about 9 to 15, α-olefin sulfonates having about 8 to 22 carbon atoms,
There are fatty acid soaps with about 10 to 22 carbon atoms. Preferred salts are alkali metal salts, particularly preferred sodium salts. As the nonionic surfactant, an ethylene oxide condensate of an alkylphenol having a linear or branched alkyl group having about 6 to 12 carbon atoms and condensing 5 to 25 mol of ethylene oxide to 1 mol of the alkylphenol, About 8 carbon atoms
Ethylene oxide condensate of aliphatic alcohol obtained by condensing 5 to 30 moles of ethylene oxide to 1 mole of aliphatic alcohol having 22 straight or branched chains, propylene glycol is condensed with propylene oxide, and further ethylene oxide is condensed. The nonionic surfactant obtained under the trade name of "Pluronic", a mono- or diethanolamide of a fatty acid having an acyl moiety having about 8 to 18 carbon atoms, an alkyl group having about 8 to 24 carbon atoms and a methyl group and / or ethyl There are amine oxides that represent groups.

In the bleaching composition, the builder is 0 to 80% by weight, particularly 1 to 50% by weight, the anionic surfactant is 0 to 30% by weight, especially 0.5 to 20% by weight, and the nonionic surfactant is 0 to 10% by weight, particularly 0.5 to 5% by weight can be blended.

In addition, as the enzyme that can be added to the bleach composition, a hydrolase that promotes addition and removal of water, a redox enzyme that promotes redox, and a group that transfers a group from one molecule to another molecule,
Transferase that modifies dirt and promotes removal, ligase and lyase that breaks bonds between molecules to promote dirt removal, and isomerizes molecules to chemically modify dirt to promote removal. Can be used, and among these, hydrolases are preferable, and protease among hydrolases is particularly preferable. Specific examples of the protease include serine protease, pepsin, trypsin, chymotrypsin, collagenase, keratinase, esterase, subtilisin, papain, carboxypeptidases A and B, and aminopeptidase. A preferred protease is serine protease. These are, for example, "Alcalase": Novo Industry "Esperase": Novo Industry "Vioplase": Nagase & Co., Ltd. "Maxatase": Gist Brocades "ALP-2": Meiji Seika Co., Ltd. "Superase": easily available as a commercial product such as Pfizer. When the enzyme is blended, the blending amount in the bleaching agent composition is preferably 0.01 to 5% by weight.

Incidentally, one or more of the above-mentioned activators can be prepared in a granular form and blended with the peroxide. In this granulation, 5 to 60 ° C, preferably 1 to 100 parts by weight of the activator is used.
It is suitable to add 5 to 200 parts by weight, preferably 10 to 100 parts by weight, of a mixture of one or more binders having fluidity at 0 to 40 ° C. to granulate.

Here, the binder is 5 to 60 ° C., preferably 10
One or a mixture of two or more selected from nonionic surfactants, polyethylene glycols, polypropylene glycols, liquid paraffins and higher alcohols which are fluid at -40 ° C can be used. For example, preferable nonionic surfactants include those shown in the following (I) to (VI).

(I) A polyoxyethylene 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 ethylene oxide added thereto.

(II) A polyoxyethylene alkyl phenyl ether having an alkyl group having an average carbon number of 6 to 12, to which 1 to 20 mol of ethylene oxide has been added.

(III) 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.

(IV) A polyoxybutylene 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 butylene oxide added thereto.

(V) A nonionic activator having an alkyl group or an alkenyl group having an average carbon number of 10 to 20 and having 1 to 20 mol of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added in total. Here, the ratio of ethylene oxide / propylene oxide or butylene oxide is 0.1 to 9.9 to 9.9 / 0.1.

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

As the granulation method, a known method such as an extrusion granulation method, a tumbling granulation method, or a compression granulation method may be adopted, and an appropriate method may be selected according to the type of activator or binder. You can
For example, when granulating using an extrusion granulator, as a pre-step of granulation, an activator finely pulverized to a particle size of 150 μm or less is uniformly mixed with a known mixer, and then a binder is gradually added to form a powder. Knead the body and binder thoroughly. Next, the kneaded mixture is charged into an extrusion granulator, granulated, 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, finely divided silica before the sieving.

The bleaching composition of the present invention can be suitably mixed with a granular detergent to obtain a bleaching detergent.

In this case, as the granular detergent, those used as a usual clothing detergent and the like can be used. For example, the following (1)
Each of the components exemplified in (7) to (7) can be contained, and these are appropriately selected according to the purpose of use. The granular detergent is a slurry containing the following components having a particle size of 200 to 500 μm,
It can be obtained by spray drying so that the apparent specific gravity becomes 0.15 to 0.40 g / ml, and the spray-dried product obtained can be further powder-blended with a desired detergent component.

(1) Surfactant 1) A linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16.

2) Having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20 and having an average of 0.5 to 8 mol of ethylene oxide, propylene oxide or butylene oxide or ethylene oxide / propylene in one molecule. Alkyl added with oxide in the ratio of 0.1 / 9.9 to 9.9 / 0.1 or ethylene oxide / butylene oxide in the ratio of 0.1 / 9.9 to 9.9 / 0.1. Or alkenyl ether sulfate.

3) An alkyl group or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20.

4) Olefin sulfonate having an average carbon number of 10 to 20.

5) Alkane sulfonate having an average carbon number of 10 to 20.

6) Saturated or unsaturated fatty acid salt having an average carbon number of 10 to 24.

7) It has an alkyl group or an alkenyl group having an average carbon number of 10 to 20, and an average of 0.5 to 8 mol of ethylene oxide, propylene oxide or butylene oxide or ethylene oxide / propylene oxide in one molecule is 0.1 / 9. At a ratio of 9.9 to 9.9 / 0.1 or 0.1 / 9.9 to ethylene oxide / butylene oxide.
Alkyl or alkenyl ether carboxylate salt added at a ratio of 9.9 / 0.1.

8) An α-sulfo fatty acid salt or ester represented by the following general formula (II).

(In the formula, Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z
Is a counterion. R ¹ represents an alkyl amount having 10 to 20 carbon atoms or an alkenyl group. Here, examples of the ions include alkali metal ions such as sodium and potassium.

9) A polyoxyethylene alkyl or alkenyl ether having an alkyl group or an alkenyl group having an average carbon number of 10 to 20, to which 1 to 20 mol of ethylene oxide is added.

10) A polyoxyethylene alkyl phenyl ether having an alkyl group having an average carbon number of 6 to 12, to which 1 to 20 mol of ethylene oxide is added.

11) 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.

12) 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.

13) A nonionic activator having an alkyl group or an alkenyl group having an average carbon number of 10 to 20, to which 1 to 30 mol of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are added in total. Here, the ratio of ethylene oxide to propylene oxide or butylene oxide is suitably 0.1 / 9.9 to 9.9 / 0.1.

14) A sucrose fatty acid ester consisting of a fatty acid having an average carbon number of 10 to 20 and sucrose.

15) Fatty acid glycerin monoester consisting of fatty acid having an average carbon number of 10 to 20 and glycerin.

16) An alkylamine oxide represented by the following general formula (III).

(In the formula, R ² is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, and R ³ and R ⁴ are alkyl groups having 1 to 3 carbon atoms.) 17) The following general formulas (IV) to ( A cationic surfactant represented by VI).

(In the formula, at least one of R ⁵ , R ⁶ , R ⁷ , and R ⁸ has 8 carbon atoms.
~ 24 alkyl or alkenyl groups, others have 1 to 5 carbon atoms
Is an alkyl group. X represents halogen or methyl sulfate. ) (In the formula, R ⁵ , R ⁶ , R ⁷ and X are as described above.) (In the formula, R ⁵ , R ⁶ and X are as described above. R ¹⁰ is a carbon number of 2 to 3
And an n is an integer of 1 to 20. (2) Divalent metal ion scavenger 1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate.

2) ethane-1,1-diphosphonic acid, ethane-1,2-
Triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,
Phosphonates such as 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid.

3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-
Phosphonocarboxylic acid salts such as phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid.

4) Amino acid salts such as glycine, aspartic acid and glutamic acid.

5) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate and diethylenetriaminepentaacetate.

As the salts 1) to 5) above, alkali metal salts are preferable.

6) Polyacrylic acid, polyfumaric acid, polymaleic acid,
Polyelectrolytes such as poly-α-hydroxyacrylic acid.

7) Organic acid salts such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid and carboxymethyltartaric acid. Alkali metal salts are suitable as the salt.

8) aluminosilicate formula x (M _'2 O or _{M "O) · Al 2 O} 3 · y (SiO 2) · w (H 2O) ... (V
I) (wherein M ′ is an alkali metal, M ″ is an alkaline earth metal that can be exchanged with calcium, x, y and w represent the number of moles of each component, and generally x is 0.7 ~ 1.
5, y is 1 to 3, and w is an arbitrary number. ) A crystalline aluminosilicate or an amorphous aluminosilicate represented by or a mixture thereof.

(3) Alkaline agent or inorganic electrolyte Silicate or sulfate. Alkali metal is preferable as the salt.

(4) Anti-redeposition agent Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose.

(5) Enzymes Protease, ribase, amylase, cellulase.

(6) Fluorescent dye 4,4'-bis (2-sulfostyryl) -biphenyl salt, 4,4'-bis (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (stilphenyl) naphthothiazole derivative , 4,4'-bis (triazole-2-
Yl) stilbene derivative, bis (triazinylamino)
Stilbene disulfonic acid derivative.

(7) Fragrance, Dye In addition, when the bleaching agent composition of the present invention is mixed with a granular detergent to form a bleaching detergent, the peroxide may be blended so as to be 1 to 95% by weight of the whole bleaching detergent. preferable.

EFFECTS OF THE INVENTION As described above, the bleaching composition of the present invention comprises one or more activators of a peroxide that releases hydrogen peroxide in an aqueous solution and a cyanopyridinium salt of the formula (1). By using in combination, it has an excellent bleaching power, and the composition of the present invention can bleach the object to be processed in a short time and can favorably prevent discoloration and fading of the object to be processed. it can.

Next, the present invention will be specifically described by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples and comparative examples]

After preparing the bleaching compositions of Examples 1 to 9 and Comparative Examples 1 to 4 in which sodium percarbonate or sodium perborate and the activator shown in Table 1 were blended at the molar ratio shown in Table 1, respectively,
Using these bleaching agent compositions, the following bleaching effect test and discoloration test were conducted. The results are shown in Table 1.

Bleaching effect test A plain woven cotton cloth (# 100) is washed with a commercially available detergent (blue diamond) in a washing machine at a bath ratio of 30 times at 50 ° C for 15 minutes and then dehydrated for 5 minutes. Washing and dehydration are performed again by the same operation. Then, overflow rinsing is performed for 15 minutes and then dehydration is performed for 5 minutes. The overflow rinsing and dehydration operations are repeated 5 times in total, and then air-dried to obtain a pretreated cloth.

Next, a 2% black tea solution is boiled for 5 minutes, and the above pretreatment is dipped in this at a bath ratio of 30 times, boiled for 30 minutes, left at 40 ° C for 30 minutes, and then air-dried to give a test cloth (black cloth). ).

The bleaching agent compositions of Examples and Comparative Examples were added to tap water (20 ° C.) so that the concentration of the bleaching agent was 0.5%, and polyoxyethylene nonylphenyl ether (= 8) was added to the tap water. After adding 0.5% of each, a tea cloth is soaked in this at a bath ratio of 100 times and left for a predetermined time (30 minutes). The test cloth thus treated is subjected to a washing machine for 1 minute of dehydration, 1 minute of overflow rinse and 1 minute of dehydration, and then dried by ironing to obtain a bleached cloth.

The reflectance of each of the pretreated cloth, the black tea cloth and the bleached cloth was measured using a photoelectric reflectance altimeter (ELREPHO, manufactured by Carl Zeiss), and the bleaching effect was calculated by the following formula.

Discoloration test A cloth dyed with a predetermined dye (Blue 27) is cut into 7 × 7 cm, and the four corners of this contaminated cloth are fixed to the frame with pins. 10 g of the bleaching detergent of each of Examples and Comparative Examples is sprinkled on the cloth, water is further sprayed on the cloth, and the cloth is left for 15 minutes, washed with water and air-dried. The condition of the dried cloth was evaluated according to the following criteria, and the degree of discoloration was examined.

3 points: The part in contact with the bleaching detergent is markedly discolored, and many spots are observed.

2 points: The part in contact with the bleaching detergent is discolored and faded, and spots are clearly observed.

1 point: The part in contact with the bleaching detergent was discolored and fading, and spots were slightly observed.

0 point: The part in contact with the bleaching detergent is not discolored at all, and no spots are observed.

From the results of Table 1, the composition of the present invention in which sodium percarbonate or sodium perborate and a cyanopyridinium salt are used in combination is represented by the formula (1) like Comparative Example 4 or propylpyridinium chloride which does not use an activator. The bleaching power is remarkably improved as compared with the bleaching agent compositions of Comparative Examples 1 and 2 using other pyridinium salts and other cationic surfactants,
It was confirmed that the activating effect of the cyanopyridinium salt was excellent. The composition of the present invention also contains TA as an activator.
It turns out that it is hard to cause discoloration and fading in the object to be treated, as compared with the composition of Comparative Example 3 using ED.

Claims (3)

[Claims] 1. A bleaching agent composition containing a peroxide that releases hydrogen peroxide in an aqueous solution, wherein the peroxide activating agent is represented by the following formula (1): (However, R is a lower alkyl group or a lower alkoxy group,
R'is an alkyl or alkenyl group having 1 to 18 carbon atoms, X
Represents a halogen, an alkylsulfonic acid group having 1 to 3 carbon atoms or a phenylsulfonic acid group, and p = 0 to 4, q = 1 to 1
3,1 ≦ p + q ≦ 5. ) A bleaching agent composition comprising one or more cyanopyridinium salts represented by 2. A compounding ratio of a peroxide that releases hydrogen peroxide and an activator in an aqueous solution is 20: 1 to 1: 2 as a molar ratio.
The composition of claim 1 which is: 3. A cyanopyridinium salt of formula (1) is R '.
The composition according to claim 1 or 2, wherein is a 2-cyanopyridinium salt, a 3-cyanopyridinium salt, or a 4-cyanopyridinium salt, which is an alkyl group having 1 to 12 carbon atoms.