JPH0689358B2 - 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, malonnitrile, phthalonitrile, nitriles such as benzoyliminodiacetonitrile, glucose pentaacetate, actaacetyl sucrose, triacetin, sorbitol hexaacetate, acetoxybenzene sulfonate, or triacetyl cyanuric acid, methyl chloroformate. O-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-acetyldiglycolimide, diacetylmethylenediformamide, and anhydrous phthalates. Acids, succinic anhydride, benzoic anhydride, glutaric anhydride, alkylsulfuric acid anhydrides, acid anhydrides such as anhydrides of carboxylic acids and organic sulphonic acids, sulphonyls such as di- (methane sulphonyl) dimethylglyoxime Oximes, acylated phosphates such as di-ethylbenzoyl phosphate, phenyl sulfonate esters, organic phosphoric acid azides such as diphenylphosphinic azide, disulphones such as diphenyldisulphone, other N-sulfonyl imidazoles, dianamides, Halogenated triazine, N, N-dimethyl Studies of N- octyl -N-10- carbophenoxy dodecyl ammonium chloride various bleach activators such as ride have been made. 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 and a specific cation activator in combination. Was completed.

That is, the present invention relates to at least one in the peroxide and molecular structure.
More than [However, Y is -CH ₂ - groups or on the carbon atom of the -C≡N group linking group imparting a positive charge] provides a bleaching agent composition containing alkylenediamine derivative or a polyalkylene polyamine derivative having the.

In the present invention, the peroxide anion resulting from the peroxide attacks the carbon atom of the -C≡N group. Therefore,
The linking group Y must provide a positive charge on the carbon atom of the -C≡N group. When the linking group Y is a -CH ₂ -group, the carbon atom of the -C≡N group has a sufficient δ ⁺ property for attacking the peroxide anion due to the adjacent cation group. Another example of the linking group Y has an electron-withdrawing group such as halogen on the carbon atom adjacent to the -C≡N group. Having an electron-withdrawing group via a conjugated system Can be mentioned. However, in the formula, X is an electron-withdrawing group and Y ′ is a connecting group, and is not particularly limited, and examples thereof include a C _{2 to} C ₁₀ substituted or unsubstituted linear or branched alkylene group, alkenylene group, and polyoxy group. It may be an alkylene group or the like.

As described above, the linking group Y may be one that satisfies the condition that it gives sufficient δ ⁺ property for the peroxide anion to attack on the carbon atom of —C≡N.

The activators of the present invention are derived from alkylenediamines or polyalkylenepolyamines. Alkylenediamine,
The polyalkylene polyamine has the formula (R ₁ is H or a lower alkyl group, R ₂ is a C _{2 to} C ₁₀ linear or branched alkylene group, n is 2 to 1,000) and the alkylenediamine or polyalkylenepolyamine is the activator of the present invention. It is useful as a raw material. Specifically, alkylenediamine is ethylenediamine, and polyalkylenepolyamine is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc., which is a relatively low molecular weight polyethylene polyamine having a molecular weight of up to 1000, tripropylenetetramine, tetrabutylenepentamine, diethylenetriamine. Examples include butylenetriamine, dihexylenetriamine, and trihexylenetetramine.

The introduction of the group can be easily obtained by quaternizing the nitrogen of the alkylenediamine or polyalkylenepolyamine with X'-Y-C≡N (X 'is halogen). X '
As -Y-C≡N, chloroacetonitrile is costly,
It is advantageous in terms of supply.

A method for obtaining the activator of the present invention using ethylenediamine as a starting material will be described.

This example shows one example of the present invention, and the present invention is not limited to this. The alkylenediamine or polyalkylenepolyamine as the raw material may be a primary amine as shown in this example, or a secondary amine or a tertiary amine. Activators having various structures can be obtained depending on the number of moles of chloroacetonitrile or alkyl halide used.

In short, the activator of the present invention comprises one or more, preferably two or more nitrogen atoms in the alkylenediamine or polyalkylenepolyamine structure. It has a structure.

The mechanism of action of the activator used in the present invention is as follows. Since the activator according to the present invention has a cationic group, it is easily adsorbed on the article to be washed. That is, it is presumed that the bleaching power is remarkably enhanced because the bleaching active species on the surface of the object to be washed increases. In addition, since the polyamine has many nitrogen atoms, the desired number of functional groups of the structure of the present invention can be introduced, and it is presumed that the bleaching activity effect is remarkably enhanced as compared with the conventional activator.

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 activator are usually peroxide / activator = 99.9 / 0.1 to 20/80, preferably 99/1 to 50 /
Used in a molar ratio of 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 sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium salts such as 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, alkylbenzene sulfone having about 9 to 15 alkyl groups. Acid salts, 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.

The activator described above is prepared into a granular form by a known method,
It can be blended with a peroxide. For example, activator 10
Granulate by adding 5 to 200 parts by weight, preferably 10 to 100 parts by weight, of a mixture of one or more binders having fluidity at 5 to 60 ° C., preferably 10 to 40 ° C. to 0 part by weight. Is preferred.

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 activators according to the invention, including organic peracids, have enabled strong bleaching unattainable with conventional oxygen-based bleach cleaners.

〔Example〕

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

(1) Preparation of Activator Reference Example 1 < Synthesis of N> N, N ′, using a 1000 ml three-necked flask equipped with a cooling tube
N'-tetramethylethylenediamine 100g ethanol 4
It is dissolved in 00cc and 195g of chloroacetonitrile is added dropwise at room temperature while stirring with a magnetic stirrer. After heating under reflux for 15 hours, the produced white crystals were collected by filtration, washed with ethanol and dried to obtain 146 g of (Ia).
Yield 63.5%.

Reference Example 2 <Synthesis of (Ib)> 100 g of an amine represented by the following formula using a 1000 ml three-necked flask equipped with a cooling tube. Is dissolved in 400 cc of ethanol and chloroacetonitrile 1
31.3 g was added dropwise. After dripping, oil bath (temperature 90
(° C) was used and the mixture was heated under reflux with ethanol for 24 hours. Then, the ethanol is distilled off to remove the quaternary salt of the above formula.
177.3 g was obtained. Quaternization rate 76.6%.

(2) Bleaching agent composition The bleaching agent composition shown in Table 1 was prepared using the activators Ia and Ib obtained by the above preparation method, and the bleaching effect was evaluated by the following method. 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. An activator was added so that the -CN groups of the agent became equimolar, and the black tea-contaminated cloth (8 x 8 cm ² , 5
Soak and bleach for 30 minutes, wash with water and dry,
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,
Rinse with water until the washing liquid is no longer colored, dehydrate, press,
A test piece of 8 × 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, washed with water and dried, and the bleaching rate was determined by the above method.

Claims (1)

[Claims] 1. (a) a peroxide and (b) at least one or more in the molecular structure [However, Y is -CH ₂ - group or a linking group to provide a positive charge on the carbon atom of the -C≡N group] bleach composition characterized by containing the alkylenediamine derivative or a polyalkylene polyamine derivative having object.