JPH0678555B2 - Bleach composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a bleach composition.

[Conventional technology and its problems]

Since chlorine-based bleaching agents have limited fibers that can be used, cannot be used for colors and patterns, and have unique odors, oxygen-based bleaching agents that do not have these drawbacks have become very popular recently. It is starting.

As the oxygen-based bleaching agent, sodium percarbonate and sodium perborate are particularly used in terms of bleaching performance and stability.

The oxygen-based bleaching agent has a weaker bleaching power than the chlorine-based bleaching agent, and various bleaching activators are used together. For example, acetonitrile, nitriles such as malonnitrile, phthalonitrile, benzoyliminodiacetonitrile, glucose pentaacetate, octaacetylsucrose, triacetin, sorbitol hexaate, acetoxybenzene sulfonate, or triacetyl cyanuric acid, methyl chloroformate. 0-acetylated compounds such as, N, N, N ′,
N′-tetraacetylethylenediamine or tetraacetylglycolyluril, N-benzylimidazole,
N-acylated compounds such as di-N-acetyldimethylglyoxime, 1-phenyl-3-acetylhydantoin, N, N-diacetylaniline, N-acetyldiglycolamide, diacetylmethyldiformamide, and anhydrous phthalates Acid, succinic anhydride, benzoic anhydride, glutaric anhydride,
Alkyl sulfuric acid anhydrides, acid anhydrides such as carboxylic acid and organic sulfonic acid anhydrides, di- (methanesulfonyl)
Sulphonyl oximes, such as dimethylglyoxime
An acylated phosphate such as di-ethylbenzoyl phosphate,
Phenyl sulfonate ester, organic phosphoric acid azide such as diphenyl phosphinic azide, disulfone such as diphenyl disulfone, and other N-sulfonyl imidazole, dianamide, halogenated triazine, N, N-dimethyl-N-octyl-N- Various bleach activators such as 10-carbophenoxide dodecyl ammonium chloride have been studied. However, even if these activators were used together, the bleaching power was still insufficient.

[Means for solving problems]

As a result of earnest research to obtain an oxygen-based bleaching agent having higher bleaching power, the present inventors have found that the purpose can be achieved by using a peroxide in combination with a specific cationic organic peracid precursor. The present invention has been completed.

That is, the present invention provides a bleaching composition containing a peroxide and an organic peracid precursor represented by the following formula (I).

X-Y-C≡N Z  (I) [where X is(In the above general formula, R₁Is an optionally substituted straight chain
And branched chain C₁~ C_{twenty four}Alkyl and alkenyl groups,
Lucaryl group (wherein the alkyl group has 1 to 24 carbon atoms)
What I have), R₂, R₃Is C₁~ C₃Alkyl group of hydr
Roxyalkyl group,-(C₂H_FourO)_1-5H, or -Y-
C≡N, Y is -CH₂Positive charge on the carbon atom of the group or CN group
And a Z is an anion.] As the linking group which gives a positive charge on the carbon atom of the CN group,
For example, if a halogen atom or the like is charged on the carbon atom adjacent to the C≡N group,
Having a child-attractive groupHaving an electron-withdrawing group via a conjugated systemIs mentioned. In the formula, X is an electron-withdrawing group and Y'is a linking group.
Yes, but not limited to, for example, C₂~ C_TenReplacement of
Is an unsubstituted linear or branched alkylene group, alkenylene
A group, a polyoxyalkylene group or the like may be used.

Preferred as the organic peracid precursor represented by the formula (I) is that X is Provided that R ₁ is an alkyl group or a hydroalkyl group having 1 to 22 carbon atoms, R ₂ and R ₃ are alkyl groups having 1 to ₃ carbon atoms, Y is an alkylene group having 1 carbon atom, and Z is a halogen. Is.

Such ammonium salts are readily obtained by reaction with the corresponding amine and nitrile halides, for example:

The peroxide used in the present invention is preferably hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution.

As peroxides that generate hydrogen peroxide in aqueous solution, sodium carbonate / hydrogen peroxide adduct, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide adduct , Or 4Na ₂ SO ₄
· 2H ₂ O ₂ · NaCl, sodium monohydrate perborate, sodium tetrahydrate perborate, sodium peroxide, calcium peroxide and the like. Among these, sodium carbonate / hydrogen peroxide adduct, sodium perborate monohydrate, and sodium perborate tetrahydrate are particularly preferable.

In the present invention, the peroxide and the organic peracid precursor are usually
The peroxide / organic peracid precursor is used in a molar ratio of 99.9 / 0.1 to 20/80, preferably 99/1 to 50/50.

The bleaching agent composition of the present invention may contain, in addition to the above-mentioned essential components, known components usually added to the bleaching agent composition.
For example, as a builder, sulfate, carbonate, bicarbonate,
In addition to water-soluble inorganic builders such as silicates and phosphates, organic builders such as ethylenediaminetetraacetic acid salts, nitrilotriacetic acid salts, tartrates and citrates can be used.
Also known as stabilizers of peroxides or hydrogen peroxide adducts are magnesium salts such as magnesium sulfate, magnesium silicate, magnesium oxide, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and silicic acid such as sodium silicate. Salts can be used. Further, if necessary, anti-redeposition agents such as carboxymethyl cellulose, polyvinylpyrrolidone, and polyethylene glycol, sulfonates and sulfates having an alkyl group having about 8 to 22 carbon atoms, and alkylbenzenes having about 9 to 15 alkyl groups. Sulfonates, α-olefin sulfonates having about 8 to 22 carbon atoms, anionic surfactants such as fatty acid soap having 10 to 22 carbon atoms, and linear or branched alkyl groups having about 6 to 12 carbon atoms And an ethylene oxide condensate of an alkylphenol obtained by condensing 5 to 25 mol of ethylene oxide with respect to 1 mol of alkylphenol, and 5 to 30 ethylene oxide in 1 mol of a linear or branched aliphatic alcohol having about 8 to 22 carbon atoms. Ethylene oxide condensate of aliphatic alcohol condensed with moles,
Nonionic surfactants under the trade name of "Pluronic" obtained by condensing propylene oxide with propylene glycol and then with ethylene oxide, mono- or diethanolamides of fatty acids having 8 to 18 carbon atoms in the acyl moiety, carbon Nonionic surfactants such as amine oxides having about 8 to 24 alkyl groups and methyl and / or ethyl groups, amphoteric surfactants such as betaine, enzymes such as protease, lipase, amylase and cellulase, fluorescent Whitening agents, dyes, pigments, fragrances and the like can be added.

In addition, the above-mentioned organic peracid precursor can be prepared into a granular form by a known method and can be mixed with the peroxide. For example, 5 to 60 ° C, preferably 10 to 40 ° C per 100 parts by weight of the organic peracid precursor.
It is preferable to add 5 to 200 parts by weight, preferably 10 to 100 parts by weight of a mixture of one or more binders having fluidity and 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.

As the granulation method, a known method such as an extrusion granulation method, a tumbling granulation method, or a compression granulation method can be adopted, and an appropriate method is selected depending on the type of the organic peracid precursor or the binder. can do. For example, when granulating using an extrusion granulator, as a pre-step of granulation, the organic peracid precursor 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. Knead the powder and binder thoroughly.
Next, the kneaded mixture is charged into an extrusion granulator, granulated, and then sieved. In addition, if necessary, in order to improve the particle characteristics, the average primary particle diameter of 0.1
The surface of the granulated product may be covered with an inorganic fine powder having a particle size of not more than μm, for example, finely divided silica.

The bleaching composition of the present invention can be appropriately mixed with a conventionally known granular detergent for clothing to obtain a bleaching detergent.

〔The invention's effect〕

The organic peracid precursor according to the present invention, including the organic peracid, enables strong bleaching that cannot be achieved by conventional oxygen-based bleaching detergents.

〔Example〕

Hereinafter, the present invention will be described with reference to Examples.
It is not limited to these.

(1) Preparation of Organic Peracid Precursor Reference Example 1 Chloroacetonitrile was dissolved in 20 cc of acetone using a 100 ml three-necked flask, and dry trimethylamine gas was bubbled with N ₂ as a carrier gas while stirring with a magnetic stirrer. Trimethylamine was passed into chloroacetonitrile for 2 hours in an amount of 2 equivalents, and the mixture was sealed and stirred at room temperature overnight. The generated white crystals were filtered off, and 8.93 g of (Ia) was obtained. Yield 95.3%.

Reference example 2 Using a 100 ml two-necked flask equipped with a cooling tube, 10.7 g of dimethyloctylamine was dissolved in 20 ml of ethanol, and 5.42 g of chloroacetonitrile was added dropwise. After completion of the dropping, the temperature was raised using an oil bath (temperature 90 ° C.), and the reaction was carried out under reflux of ethanol until the starting amine was consumed while checking by TLC. After that, ethanol was distilled off to obtain 15.76 g of the above quaternary salt.
was gotten. Yield 99.3%.

(2) Bleaching agent composition Organic peracid precursors Ia and Ib obtained by the above preparation method
Was used as an activator to prepare the bleaching composition shown in Table 1, and the bleaching effect was evaluated by the following method. The results are shown in Tables 1 and 2.

<Bleaching effect of immersion bleaching (Table 1)> Sodium percarbonate was dissolved in 300 ml of water at 20 ° C so that the available oxygen was 0.05%, and activated with 1/16 equivalent of hydrogen peroxide in this solution. A tea-contaminated cloth (8 × 8c) prepared by the following method by adding an activator such that the C≡N groups of the agent are equimolar
Immersion bleaching was carried out for 30 minutes using m ² , 5 sheets, washed with water, dried, and then the bleaching rate was calculated by the following formula.

Bleaching rate of black tea cloth: The reflectance was measured with NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

Black tea contaminated cloth: 80g of Nitto black tea (yellow package) is boiled with ion-exchanged water of 3 for about 15 minutes, then rubbed with desalted cotton and soaked in cotton gold cloth # 2003 cloth and boiled for about 15 minutes. . Remove from heat as it is, let stand for about 2 hours and let it air dry,
Wash the washing liquid until it becomes colorless, dehydrate and press, then 8
A test piece of × 8 cm was used for the experiment.

<When used in combination with detergent (Table 2)> 0.6% commercial heavy-duty detergent (non-ionic activator base: does not include anionic activator), sodium percarbonate, and activators and organic peracids shown in Table 1 As shown in Table 2, black tea-contaminated cloth (8 x 8 cm ² , 5 pieces) prepared by the above method in the washing liquid added
Was washed with a tergotometer at 20 ° C. for 10 minutes, then washed with water and dried, and the bleaching agent ratio was determined by the above method.

Claims (1)

[Claims] 1. A peroxide and an organic compound represented by the following formula (I):
A bleaching composition comprising a peracid precursor. X-Y-C≡N Z  (I) [where X is(In the above general formula, R₁Can be replaced
Chains and branched chains C₁~ C_{twenty four}Alkyl and alkenyl groups,
Alkaryl groups (wherein the alkyl group has 1 to 24 carbon atoms)
Have), R₂, R₃Is C₁~ C₃Alkyl group of
Droxyalkyl group,-(CH₂H_FourO)_1-5H or -Y
-C≡N, Y is -CH₂On the carbon atom of the -group or -C≡N group
A linking group that gives a positive charge to Z, and Z represents an anion]