JPS62149800A - Bleaching 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 Field of Industrial Application The present invention contains a peroxide that releases hydrogen peroxide in an aqueous solution, and is used for various purposes such as household and industrial purposes. The present invention relates to an oxygen-based bleach composition.

Conventional technology Δ2 (Problem that Ming tried to solve) There are two types of bleaching agents: reducing bleaching agents and oxidizing bleaching agents, which are highly effective.
Oxidized bleach is widely used. Acid 4'L bleaches are further divided into two types: chlorine bleaches and oxygen bleaches, but chlorine bleaches change the material being treated. and disadvantages such as having a characteristic odor). On the other hand, oxygen bleach can be used in a wider range of applications than chlorine bleach.

It is superior in that it does not have the characteristic odor that chlorine bleaching l'・j does and is easy to use.

However, among oxygen bleaches, hydrogen peroxide, pernoate salts, perborate hydrates, pyrophosphates, citrates, sodium sulfate, urea, sodium silicate, etc. Peroxides that release hydrogen peroxide in aqueous solution, such as adducts, have inferior bleaching properties compared to chlorine bleach;
It has the disadvantage that a sufficient bleaching effect cannot be obtained with a short bleaching treatment, and that a considerably long treatment is required to obtain a sufficient bleaching effect, especially at low temperatures.

In addition, conventionally, hydrogen peroxide and peroxide have been combined with bleach activators such as TAED (tetraacetylethylenediamine), TAGU (tetraacetylglycoluril), and PAG (pentaacetylglucose) to enhance the bleaching effect. It is. However, the activation effects of these conventional bleach activators are not sufficient, and when these activators are used, the object to be treated may change color or fade due to the bleaching agent. The reality is that oxygen bleaches have not yet achieved a satisfactory bleaching effect compared to chlorine bleaches.

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

Means and Action for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive research on improving the bleaching blade of oxygen bleach.
For bleach compositions containing peroxides that release hydrogen peroxide in aqueous solution, the peroxide activator may be one of the following:
It has been found that when one or more of the compounds of ~I-I are blended and a peroxide and these compounds A~1 are used in combination, the bleaching edge is significantly improved.

Therefore, in a bleach composition containing a peroxide that releases hydrogen peroxide in an aqueous solution, the present invention provides a compound of the following A-H as an activator for the peroxide, that is, (A) the following formula ( 1) (However, R represents a lower alkyl group or a lower alkoxy group, and n=o~4.m=1~4.1≦n+m≦8.

) Naphthonitriles represented by (B) Isophthalonitriles represented by the following formula (2) (However, R is the same as above and is Q0 to 4.); (However, R and Q represents the same as above); (D) alkali metal cyanate; (E) ammonium cyanate; (F) the following formula (4) (However, R is the same as above. Showing the same thing, p=Q~4, q
=l~3, 1≦P+q≦5. ) Cyanopyridines represented by the above; (G) acid neutralized product of the cyanopyridines represented by the above formula (4); and (H) the following formula (5) (However, R + P and q are the same as above) Show.

R' is an alkyl group or alkenyl group having 1 to 18 carbon atoms,
X is halogen, an alkylsulfonic acid group having 1 to 3 carbon atoms, or phenylsulfone M! It is. The present invention provides a bleach composition characterized by containing one or more compounds selected from the group consisting of cyanopyridinium salts shown in (a).

According to the composition of the present invention, the bleaching blade of peroxide that releases hydrogen peroxide in an aqueous solution is significantly impaired by the activating action of the compounds A to H, and as a result, the object to be treated can be bleached in a short time. can be processed.

In this case, in addition to such effects, especially A to E and I
] Compounds have a good effect of preventing discoloration and fading of the treated material, and compounds F and G have an excellent bleaching effect at low temperatures.

The present invention will be explained in more detail below.

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, any peroxide can be used as long as it dissolves in water and releases hydrogen peroxide. 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, percarbonates such as 1-lium percarbonate, and perborates such as sodium perborate hydrate.

The present invention uses the following A-H as an activator for the peroxide.
One or more of these compounds are used in combination.

(A) The following formula (1) (However, R represents a lower alkyl group or a lower alkoxy group, n = O ~ 4, m = 1-4, 1≦n
+m≦8. ) Naphthonitriles represented by: (B) Isophthalonitriles represented by the following formula (2) (wherein R represents the same as above and is Q0-4); (C) Isophthalonitriles represented by the following formula ( 3) Terephthalonitriles represented by (however, R and Q are the same as above); (D) alkali metal cyanate salt; (E) ammonium cyanate salt; (F) the following formula (4) ) (However, R indicates the same as above, p = 0 to 4, (
cyanopyridines represented by 1=1 to 3, 1≦P+ (1≦5); (G) acid neutralized product of cyanopyridines represented by the above formula (4); and (H) the following formula (5) (However, R, I) and q are the same as above, and R
' is an alkyl group or alkenyl group having 1 to 18 carbon atoms, X
is a halogen, an alkylsulfonic acid group having 1 to 3 carbon atoms, or a phenylsulfonic acid group. ) Cyanopyridinium salts.

In this case, naphthonitriles (
A) includes 1-naphthonitrile, 2-naphthonitrile, 1,3-dicyano-naphthalene, 1,6-dicyatunaphthalene, 1-cyano-2-methyl-naphthalene,
1-cyano-2-methoxy-naphthalene and the like are preferably used, and among these, 1-naphthonitrile and 2-naphthonitrile are most preferably used. As the isophthalonitrile (B) represented by the formula (2), isophthalonitrile, 1-methyl-2,4-dicyano-benzene, etc. are preferably used, and isophthalonitrile is particularly preferred. Terephthalonitriles (C) represented by formula (3)
Examples include terephthalonitrile, 1-methyl-2,5-
Dicyano-benzene and the like are preferably used, with terephthalonitrile being particularly preferred.

Furthermore, as the alkali metal cyanate salt (D).

Examples include potassium cyanate, sodium cyanate, lithium cyanate, and the like.

Further, the cyanopyridines CF) represented by formula (4) include 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine,
Cyanopyridine, 3-cyano-6-methylpyridine, 3
-Cyano-6-nitoxypyridine and the like are preferably used, but among these, 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, especially 2-cyanopyridine is highly effective and is most preferably used. . As the acid neutralized product (G) of cyanopyridine represented by the formula (4),
Acid neutralized products of the same cyanopyridine compounds as above are used, especially 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine,
-Acid neutralized products of cyanopyridine, especially their hydrochlorides, sulfates, etc., are preferably used.

The cyanopyridinium salt (H) represented by the formula (5) is particularly suitable for 2 in which R' is an alkyl group having 1 to 12 carbon atoms.
-cyanopyridinium salt, 3-cyanopyridinium salt,
4-cyanopyridinium salt is preferably 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, etc. can be mentioned.

In the present invention, the molar ratio of the above-mentioned peroxide and activator is preferably 20:1 to 1:2, and if it is out of the above range, a sufficient bleaching blade may not be obtained. . In addition, a more preferable blending molar ratio of peroxide and activator is 10:1 to 1:1.

The bleach composition of the present invention can be prepared by a conventional method by adding appropriate other known components shown below as necessary. For example, a bleach composition can be prepared by adding inorganic/organic builders, anionic/nonionic surfactants, enzymes, fragrances, pigments, fluorescent agents, etc. to the composition of the present invention. Here, as inorganic/organic builders, sodium sulfate,
These include sodium silicate, sodium tripolyphosphate, sodium ethylenediaminetetraacetate, sodium nitrotriacetate, 1-hydroxyethane-1,1-diphosphonic acid and its salts. Examples of anionic surfactants include sulfonates and sulfates having an alkyl group of 8 to 22 carbon atoms, alkylbenzene sulfonates having an alkyl group of about 9 to 15, and α-olefin sulfones having an alkyl group of 8 to 22 carbon atoms. There are acid salts and fatty acid soaps with 10 to 22 carbon atoms. Preferred salts are alkali metal salts, particularly preferred are sodium salts. Examples of nonionic surfactants include ethylene oxide condensates of alkylphenols having a linear or branched alkyl group having about 6 to 12 carbon atoms and condensing 5 to 25 moles of ethylene oxide to 1 mole of alkylphenol;
An ethylene oxide condensate of an aliphatic alcohol in which 5 to 30 moles of ethylene oxide is condensed to 1 mole of a linear or branched aliphatic alcohol having about 8 to 22 carbon atoms, propylene oxide condensed to propylene glycol, and A nonionic surfactant with the trade name "Pluronic" obtained by condensing ethylene oxide, a mono- or jetanolamide of a fatty acid with an acyl moiety of about 8 to 18 carbon atoms, and a carbon number of about 8
There are amine oxides having ~24 alkyl groups and methyl and/or ethyl groups.

The bleach composition contains builder in an amount of 0 to 80% by weight, especially 1 to 50% by weight, anionic surfactant in 0 to 30% by weight, especially 0.5 to 20% by weight, and nonionic surfactant. is 0
It can be blended in an amount of up to 10% by weight, particularly 0.5 to 5% by weight.

In addition, enzymes that can be incorporated into the bleach composition include hydrolytic enzymes that promote the addition and removal of water, oxidoreductases that promote redox, and enzymes that transfer groups from one molecule to another.
Transferase, which alters dirt and promotes its removal; gauze, which breaks down intermolecular bonds and decomposes dirt, and promotes removal; lyase, which isomerizes molecules and chemically alters dirt, promoting removal. Enzymes can be used, and among these, hydrolytic enzymes are preferred, and among the hydrolytic enzymes, proteases are particularly preferred. Specific examples of proteases include serine protease, pepsin, trypsin, chymotrypsin, collagenase, keratinase, esterase, subtilisin, papain, carboxypeptidase A and B, and aminopeptidase. Preferred proteases are serine proteases. These include, for example, "Alcalase": Novo Industries "Esperase": Novo Industries "Viroplase":
Nagase Sangyo Co., Ltd. “Maxatase”: Gist Procades rALP
-2 - Meiji Seika Co., Ltd. "Sperase": Easily produced by hand as a commercially available product from Pfizer and others. When blending an enzyme, the blending amount in the bleach composition is 0.01 to 5% by weight.
A range of is preferred.

Note that one or more of the above-mentioned activators can be prepared in granular form and blended with the peroxide.

In this granulation, 5 to 6 parts per 100 parts by weight of the activator.
It is suitable to perform granulation by adding 5 to 200 parts by weight, preferably 10 to 100 parts by weight, of one or more binders having fluidity at 0°C, preferably 10 to 40°C.

Here, the binder is one or two selected from nonionic surfactants, polyethylene glycol, polypropylene glycol, liquid paraffin, and higher alcohols, which have fluidity at 5 to 60°C, preferably 10 to 40°C.
Mixtures of more than one species may be used. For example, preferred nonionic surfactants include those shown in (1) to (VI) below.

(1) Polyoxyethylene alkyl or alkenyl ether (II) having an alkyl group or alkenyl group with an average carbon number of 10 to 20 and to which 1 to 20 moles of ethylene oxide is added. death,
Polyoxyethylene alkyl phenyl ether (III) to which 1 to 20 moles of ethylene oxide has been added Polyoxypropylene alkyl or Alkenyl ether (IV) Polyoxybutylene alkyl or alkenyl ether (V) Having an alkyl group or alkenyl group with an average carbon number of 10 to 20 and added with 1 to 20 moles of butylene oxide (V) An alkyl group with an average carbon number of 10 to 20 Or a nonionic activator having an alkenyl group and adding a total of 1 to 20 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide.

Here, the ratio of ethylene oxide/propylene oxide or butylene oxide is 0.1/9.9 to 9.9.
10.1.

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

Granulation methods include extrusion granulation method and rolling granulation method.

A known method such as a compression granulation method may be employed, and an appropriate method may be selected depending on the type of activator and binder. For example, when granulating using an extrusion granulator, as a pre-granulation step, the activator is finely pulverized to a particle size of 150p or less and mixed uniformly in a known mixer, and then a binder is gradually added to the powder. Thoroughly knead the body and binder. next,
After the kneaded mixture is charged into an extrusion granulator and granulated, it is sieved. If necessary, in order to improve particle properties, the surface of the granulated material may be coated with an inorganic fine powder having an average dimensional diameter of 0.1 p or less, such as fine silica powder, before 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 ordinary laundry detergents can be used. For example, the following (1)
) to (7) may be contained, and these are appropriately selected depending on the intended use. For granular detergent, slurry containing each component as shown below is made into particles with a particle size of 200 to 50.
0p-apparent can be obtained by spray drying to a specific gravity of 0.15 to 0., 40 g/ndl, and further powder blending of desired detergent components to the obtained spray dried product. You can also do it.

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

2) Contains a linear or branched alkyl group or alkenyl group with an average of 10 to 20 carbon atoms, with an average of 0.5 carbon atoms per molecule.
~8 moles of ethylene oxide, propylene oxide or butylene oxide or ethylene oxide/propylene oxide in a ratio of 0.1/9.9 to 9.910
．． Alkyl or alkenyl ether sulfates in a ratio of 1(7) or with addition of ethylene oxide/butylene oxide in a ratio of 0.1/9.9 to 9.910.1.

3) Alkyl 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) Alkanesulfonate 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 contains an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide, or ethylene oxide/propylene oxide in one molecule. ~9.910.1 or ethylene oxide/butylene oxide in a ratio of 0.1/9.
Added at a ratio of 9 to 9.910.1. Alkyl or alkenyl ether carboxylate.

8) α-Sulfofatty acid salt or ester R′-CHC02Y S○, Z (11) represented by the following general formula (11) (where Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, and Z is a counter ion) (R1, which is an ion, represents an alkyl group or an alkenyl group having 10 to 20 carbon atoms.) Here, examples of the ion include alkali metal ions such as sodium and potassium.

9) Polyoxyethylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 moles of ethylene oxide is added.

10) having an alkyl group with an average carbon number of 6 to 12, and 1 to 2
Polyoxyethylene alkylphenyl ether with 0 moles of ethylene oxide added.

11) Polyoxypropylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 mol of propylene oxide is added.

12) Polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 mol of butylene oxide is added.

13) A nonionic activator having an alkyl group or alkenyl group having an average carbon number of 10 to 20, to which a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are added. Here, the ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1/9.9 to 9.91.
0.1 is appropriate.

14) A fatty acid ester consisting of an aliphatic group having an average carbon number of 1 to 20 and sucrose.

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

1.6) Alkylamine oxide R"-N-+O(III) represented by the following general formula (■) (wherein, R2 is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R3 and R4 are 17) The groups represented by the following general formulas (IV) to (VI) are alkyl or alkenyl groups having 8 to 24 carbon atoms, and the others are alkyl groups having 1 to 5 carbon atoms. represents an alkyl group.X is (in the formula RS
, RG and X are as described above. R10 has 2 to 3 carbon atoms
alkylene group, n represents an integer of 1 to 20. ) (2) Divalent metal ion scavenger■) 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
, 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid and the like.

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

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

5) Nidonorotriacetate, ethylenediaminetetraacetate,
Aminopolyacetates such as diethylenetriaminepentaacetate.

As mentioned above, alkali metal salts are suitable as the salts 1) to 5).

6) Polymer electrolytes such as polyacrylic acid, polyfumaric acid, polymaleic acid, and 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. As the salt, an alkali metal salt is suitable.

8) Aluminosilicate general formula % formula % (In the formula, M' is an alkali metal, M' is an alkaline earth metal exchangeable with calcium, X + 3/ and W represent the number of moles of each component, Generally, X is 0.7
-1.5, y is 1 to 3. (w is an arbitrary number) A crystalline aluminosilicate or amorphous aluminosilicate or a mixture thereof.

(3) Alkaline agent or inorganic electrolyte silicate, sulfate. Alkali metals are preferred as salts.

(4) Anti-redeposition agents polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose.

(5) Enzyme Bratease, lipase, amylase, cellulase.

(6) Fluorescent dye 4.4'-bis-(2-sulfostyryl)-biphenyl salt, 4,4'-bis-(4-chloro-3-sulfostyryl)-biphenyl salt, 2-(stylphenyl)naphtho Thiazole derivative, 4,4'-bis(triazole-2-
yl) stilbene derivatives, bis(triazinylamino)
Stilbendisulfonic acid derivative.

(7) Fragrance, pigment When the bleach composition of the present invention is mixed with a granular detergent to form a bleaching detergent, peroxide accounts for 1 to 95% of the entire bleaching detergent.
It is preferable to mix it so that it becomes a heavy weight percentage.

As described in detail, the bleach composition of the present invention comprises a peroxide that releases hydrogen peroxide in an aqueous solution, a naphthonitrile of formula (1), an isophthalonitrile of formula (2), One type selected from terephthalonitriles of the formula (3), alkali gold crown salts of cyanate, ammonium cyanate salts, cyanopyridines of the formula (4) and their acid neutralized products, and cyanopyridinium salts of the formula (5) Or, by using two or more types of activators in combination, it has an excellent bleaching edge, and according to the composition of the present invention, the object to be treated can be bleached in a short time.

Next, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Example, comparative example ■]

Examples 1 to 1, in which sodium percarbonate or sodium perborate and the activator shown in Table 1 were blended at the molar ratio shown in Table 1.
After preparing the bleach compositions of Example No. 9 and Comparative Examples 1 to 4, the following bleaching effect test and discoloration/fading test were conducted using these bleach compositions. The results are shown in Table 1.

Bleaching effect test A plain woven cotton cloth (#100) was washed in a washing machine at 50°C for 15 minutes at a bath ratio of 30 times using a commercially available detergent (Blue Diamond 0), and then dehydrated for 5 minutes.

Wash and dehydrate using the same procedure again. Next, overflow rinsing is performed for 15 minutes, followed by dehydration for 5 minutes. The overflow rinsing and dehydration operations are repeated a total of 5 times, and then air-dried to obtain a pretreated cloth.

Next, a 2% black tea solution was boiled for 5 minutes, and the pretreated cloth was immersed in it at a bath ratio of 30 times, boiled for 3 minutes, and further heated to 40°C.
After leaving it for 30 minutes, it was air-dried to obtain a test cloth (tea cloth).

The bleach compositions of Examples and Comparative Examples were added to tap water <20°C so that the bleach concentration was 0.5%, and polyoxyethylene nonylphenyl ether (P = 8 )0.5% respectively,
Soak a black tea cloth in this at 100 times the bath ratio for a specified period of time (30
minutes) Leave it alone. The thus treated test cloth was dehydrated in a washing machine for 1 minute, overflow rinsed for 1 minute, and dehydrated for 1 minute in sequence, and then dried by ironing to obtain a bleached cloth.

The reflective dust of the above-mentioned pre-treated cloth, black tea cloth and bleached cloth was measured using a photoelectric reflective dust altimeter (EL RE P HO, Carl Z
(manufactured by Eiss), and the bleaching effect was determined using the following formula.

A cloth dyed with the specified dye (Blue 27) is cut into 7×7 pieces, and the four corners of this contaminated cloth are fixed to a frame using pins. Each of the cloths was sprinkled with the bleaching detergent Log of Examples and Comparative Examples, and further sprayed with water, left for 15 minutes, washed with water, and air-dried.

The condition of the cloth after drying was evaluated according to the following criteria, and the degree of discoloration and fading was examined.

3 points: The area that came into contact with the bleaching detergent was significantly discolored and discolored, and many spots were observed.

2 points: f: A The area that came into contact with the self-cleaning agent was discolored and faded, and spots were clearly observed.

1 point: The area that came into contact with the bleaching detergent has slightly discolored and faded, and a few spots are observed.

0 point: The area that came into contact with the bleach cleaning agent did not change color at all, and many spots were not observed.

From the results in Table 1, it can be seen that the composition of the present invention in which sodium percarbonate or sodium perborate is used in combination with naphthonitriles, isophthalonitriles, or terephthalonitriles is different from Comparative Example 4, which does not use an activator, and benzene. Comparative Example 1 in which an aromatic nitrile other than the compounds represented by formulas (1) to (3) such as nitrile, phthalonitrile, etc. was used as an activator.
It was found that the bleaching properties were significantly improved compared to the bleaching agents No. 2 and 2, and the activation effect of isophthalonitriles and terephthalonitriles using a naphthonitrile lamp was excellent.

Furthermore, it was found that the composition of the present invention was less likely to cause discoloration or fading on the treated object than the bleaching agent of Comparative Example 3, which used TAED as an activator.

[Example, comparative example ■]

Example 10 in which sodium percarbonate or sodium perborate and the activator shown in Table 2 were blended at the molar ratio shown in Table 2.
-14 and Comparative Examples 5-7 were prepared, and then the same bleaching effect test and discoloration/fading test as in Section 2 were conducted using these bleach compositions. In addition, polyoxyethylene nonylphenyl ether was not added in the bleaching effect test. The results are shown in Table 2.

From the results in Table 2, it can be seen that the composition of the present invention in which sodium percarbonate or sodium perborate is used in combination with an alkali metal salt or ammonium cyanate, Comparative Example 5 in which potassium thiocyanate was used as an activator, and It was observed that the bleaching blade was significantly improved compared to the bleaching agent of Comparative Example 7 in which no agent was used, and the activation effect of the alkali metal cyanate and ammonium salt was excellent. Furthermore, it was found that the composition of the present invention was less likely to cause discoloration or fading on the treated object than the bleaching agent of Comparative Example 6, which used TAED as an activator.

[Example, comparative example ■]

Example 15 in which sodium percarbonate or sodium perborate and the activator shown in Table 3 were blended at the molar ratio shown in Table 3.
After preparing the bleaching compositions of Example 27 and Comparative Example 8, the following bleaching effect test was conducted using these bleaching compositions. The results are shown in Table 3.

A pretreated cloth and a black tea cloth were prepared in the same manner as described in the above Examples and Comparative Example 6. The bleach compositions of Examples and Comparative Examples were added to tap water at the temperature shown in Table 3 to a concentration of 0.5%, and a black tea cloth was immersed in the solution at a bath ratio of 100 times for a predetermined period of time. (15 minutes) Leave it alone. The thus treated test cloth was dehydrated in a washing machine for 1 minute, overflow rinsed for 1 minute, and dehydrated for 1 minute in sequence, and then dried by ironing to obtain a bleached cloth.

The reflective dust of the above-mentioned pre-treated cloth, black tea cloth and bleached cloth was measured using a photoelectric reflectivity altimeter (ELREPHO, CarlZeiss
manufactured by Iil! The bleaching effect was determined from the above formula.

From the results in Table 3, the composition of the present invention, which uses sodium percarbonate or sodium perborate in combination with cyanopyridines or an acid neutralized product of cyanopyridines, has a significantly improved bleaching edge compared to the bleaching agent of the comparative example. However, it was recognized that the activation effect of cyanopyridines was extremely excellent.

[Example, comparative example ■]

Example 28 in which sodium percarbonate or sodium perborate ζ was blended with the activator shown in Table 4 at the molar ratio shown in Table 4.
-36 and Comparative Examples 9 to 12 were prepared, respectively, and the bleaching effect test and discoloration/fading test of these compositions were conducted in the same manner as in Examples and Comparative Example (2). The results are shown in Table 4.

From the results in Table 4, it can be seen that the composition of the present invention using sodium percarbonate or sodium perborate in combination with a cyanopyridinium salt has the composition shown in formula (5), such as Comparative Example 12 which does not use an activator, and propylpyridinium chloride. Compared to the bleach compositions of Comparative Examples 9 and 10, which used pyridinium salts other than the above and other cationic surfactants, the bleaching blade was significantly improved, and it was recognized that the activation effect of the cyanopyridinium salts was excellent. Ta. Furthermore, it was found that the composition of the present invention was less likely to cause discoloration or fading in the treated object, compared to the composition of Comparative Example 11 in which TAED was used as an activator.

[Example, comparative example ■]

The granular detergent shown below and the bleach composition shown in Table 5 were
Bleach cleaning agents were prepared by uniformly blending the powders at the blending ratio shown in the table, and a bleach cleaning test was conducted using these. The results are shown in Table 5.

granular detergent The granular detergent used had the following composition.

LAS-Na 8%AS-Na
2
AOS-Na
12 Zeolite 16 Sodium silicate 1゜Sodium carbonate
8 Soap 1 Tinopal CBS-X O,1 Enzyme (Alcalase 2.0T) 0,5 Water
5 Sodium sulfate
balance total
100.0% bleach cleaning test A pretreated fabric and a black tea fabric were prepared in the same manner as described in Examples and Comparative Example I above.

After dissolving the bleaching detergents of Examples and Comparative Examples in tap water (25%) so that the bleaching detergent concentration was 0.75%,
Soak a black tea cloth in this at 100 times the bath ratio for a specified period of time (30
minutes) Leave it alone. after that.

Add tap water so that the bleach cleaning agent concentration is 0.15% and use Terg-0 from U.S. Testing.
- Using a Tometer, wash for 10 minutes at a rotation speed of 12 Qr, p, m. The thus treated test cloth was dehydrated in a washing machine for 1 minute, overflow rinsed for 1 minute, and dehydrated for 1 minute in sequence, and then dried by ironing to obtain a bleached and washed cloth.

The reflective dust of the pretreated cloth, black tea cloth, and bleached and washed cloth was measured using a photoelectric reflectance altimeter (ELREPI-(0°Carl).
(manufactured by Zeiss), and the bleaching effect was determined from the above formula.

From the results in Table 5, it can be seen that the bleach composition using sodium percarbonate, sodium perborate, and the activator of the present invention in combination with a granular detergent was the same as that of Comparative Example 13, in which no activator was used. It was observed that the bleaching blade was significantly improved compared to No. 14 bleach cleaning agent.

Claims (1)

[Claims] 1. In a bleach composition containing a peroxide that releases hydrogen peroxide in an aqueous solution, as an activator for the peroxide, the following formula (1) ▲ Numerical formula, chemical formula, table etc.▼...(1) (However, R represents a lower alkyl group or a lower alkoxy group, n = 0 to 4, m = 1 to 4, 1≦n+m≦8.) Naphthonitriles represented by ; Isophthalonitriles represented by the following formula (2) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(2) (However, R indicates the same thing as above, and n = 0 to 4.); Terephthalonitriles represented by the following formula (3) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(3) (However, R and l are the same as above.) Terephthalonitriles; alkali metal cyanate; cyanide Acid ammonium salt; Formula (4) below ▲Mathematical formulas, chemical formulas, tables, etc.▼...(4) (However, R indicates the same as above, p = 0 to 4, q
=1 to 3, 1≦p+q≦5. ) Cyanopyridines represented by the above formula (4); Acid neutralized products of the cyanopyridines represented by the above formula (4);
and the following formula (5) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(5) (However, R, p and q are the same as above, and R'
is an alkyl group or alkenyl group having 1 to 18 carbon atoms, and X is a halogen, an alkylsulfonic acid group having 1 to 3 carbon atoms, or a phenylsulfonic acid group. 1. A bleaching agent composition comprising one or more compounds selected from the group consisting of cyanopyridinium salts represented by the following. 2. The composition according to claim 1, wherein the molar ratio of the peroxide that releases hydrogen peroxide and the activator in an aqueous solution is 20:1 to 1:2. 3. The composition according to claim 1 or 2, wherein the naphthonitrile of formula (1) is 1-naphthonitrile or 2-naphthonitrile. 4. The composition according to claim 1 or 2, wherein the isophthalonitrile of formula (2) is isophthalonitrile. 5. The composition according to claim 1 or 2, wherein the terephthalonitrile of formula (3) is terephthalonitrile. 6. The composition according to claim 1 or 2, wherein the cyanopyridine of formula (4) is 2-cyanopyridine, 3-cyanopyridine or 4-cyanopyridine. 7. Claim 1, wherein the cyanopyridinium salt of formula (5) is a 2-cyanopyridinium salt, 3-cyanopyridinium salt, or 4-cyanopyridinium salt in which R' is an alkyl group having 1 to 12 carbon atoms. Or the composition according to item 2.