JP2523817B2 - Bleaching agent and bleaching detergent composition - Google Patents

Description

The present invention relates to bleaching agents and bleaching cleaning compositions.

[Problems to be Solved by Prior Art and Invention]

Chlorine bleach has limited fibers that can be used,
Oxidizing bleaching agents, which do not have these drawbacks, have recently come into widespread use because they cannot be used for colors and patterns and have unique odors.

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

Oxygen-based bleaching agents have weaker bleaching power than chlorine-based bleaching agents, and various organic peracid precursors (bleaching activators) are used together.
For example, acetonitrile, malonnitrile, phthalonitrile, nitriles such as benzoyliminodiacetonitrile, glucose pentaacetate, octaacetylsucrose, triacetin, sorbitol hexaacetate, acetoxybenzene sulfonate, or triacetolucyanuric acid, such as methyl chloroformate. 0-acetylated product, N, N, N ', N'-tetraacetylethylenediamine, or tetraacetylglycolyluril, N-benzoylimidazole, di-N-acetyldimethylglyoxime, 1-phenyl-3-acetylhydantoin, N , N
-Diacetylaniline, N-acetyldiglycolimide,
N-acylated products such as diacetylmethylenediformamide, and acid anhydrides such as phthalic anhydride, succinic anhydride, benzoic anhydride, glutaric anhydride, alkylsulfuric anhydride, carboxylic acid and organic sulfonic anhydrides, Sulfonyl oximes such as di- (methanesulfonyl) dimethylglyoxime, acylated phosphates such as di-ethylbenzoyl phosphate, phenyl sulfonate esters, organophosphorus azides such as diphenylphosphinic azide, diphenyldisulfone such as Various organic peracid precursors such as disulfone, other N-sulfonylimidazoles, dianamides and halogenated triazines have been studied.

However, even if these organic peracid precursors were used in combination, the bleaching power was still insufficient.

An object of the present invention is to obtain a bleaching agent and a bleaching detergent which have excellent bleaching power and whose bleaching power does not decrease even after being stored for a long time.

[Means for solving the problem]

As a result of intensive research to solve the above problems, the present inventors have found that a bleaching agent and a bleaching detergent satisfying the above problems can be obtained by using an organic peracid precursor that satisfies specific conditions. completed.

That is, the present invention relates to (a) a peroxide that dissolves in water to generate hydrogen peroxide, (b) an alkaline agent, and (c) an organic peracid that satisfies all of the following conditions (1) to (5). Granulation of a precursor with an organic substance having a melting point of 40 ° C. or higher (1) Reaction with hydrogen peroxide to produce an organic peracid having a cation group (2) Organic peracid precursor and the produced organic peracid Adsorption amount of cellulose to cellulose is 50 to 5000 ng / cm ² (3) Micelle formation concentration is 0.1 mol / l or more or micelles are not formed (4) Peracid generation site is nitrile group, ester group or It is an imide group and the peracid generation rate is 5% or more in the case of a nitrile group, and the peracid generation rate is 50% in the case of an ester group or an imide group.
(5) A bleaching agent characterized by containing a solid at 80 ° C., and a bleaching detergent composition containing the bleaching agent.

The component (a) used in the present invention, which is dissolved in water to generate hydrogen peroxide, is an organic or inorganic hydrogen peroxide adduct, sodium carbonate / hydrogen peroxide adduct (sodium percarbonate), Examples include sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide adduct, or 4Na ₂ SO ₄ · 2H ₂ O ₂ · NaCl. Inorganic peroxides such as sodium perborate monohydrate, sodium perborate tetrahydrate, sodium peroxide and calcium peroxide can also be used. Among these, sodium carbonate / hydrogen peroxide adduct, sodium perborate monohydrate, and sodium perborate tetrahydrate are particularly preferable.

The peroxide as the component (a) is incorporated in the bleaching agent of the present invention in an amount of 1 to 90% by weight.

As the alkali agent of the component (b) used in the present invention, a water-soluble alkaline inorganic salt is preferable, for example, carbonate,
Bicarbonates, silicates, orthophosphates, metaphosphates, hexametaphosphates, pyrophosphates, tripolyphosphates and the like can be mentioned. As the salt, alkali metal salts such as sodium and potassium are preferable. The component (b) is contained in the bleaching agent of the present invention in an amount of 2 to 70% by weight, preferably 5 to 50% by weight, which improves the bleaching performance and stabilizes the bleaching performance.

The organic peracid precursor, which is a raw material of the granulated product of the component (c) used in the present invention, must satisfy all the conditions (1) to (5).

Conditions (1) and (2) are that the organic peracid precursor and the organic peracid produced by the reaction of this with hydrogen peroxide have a cation group and are adsorbable to cellulose fibers or stains. Indicates. Adsorption amount to cellulose is 50ng / cm ²
If the amount is less than the above, the bleaching efficiency on the clothes or stain surface is insufficient, and the adsorption amount should not exceed 5000 ng / cm ² from the viewpoints of redeposition of stains on the clothes and rinsing detachability from the clothes.
The adsorption amount is preferably 200 to 2000 ng / cm ² .

The condition (3) is related to the production rate of the organic peracid. If the micelle formation concentration is less than 0.1 mol / l, the reaction in the solution is slow,
Not enough bleaching within the bleaching or washing time.

The condition (4) is a necessary amount of organic peracid for performing sufficient bleaching. This value depends on the structure of the peracid generation site, but it is considered that this value is related to the oxidation rate of the generated organic peracid. If the peracid generation site is a nitrile group, the peracid generation rate is 5% or more, preferably 10% or more, and if the peracid generation site is an ester group or an imide group, the peracid generation rate is 50% or more, preferably
If it is 70% or more, bleaching is sufficiently performed.

The above conditions (1) to (4) are indispensable requirements for the organic peracid precursor for obtaining excellent bleaching power, but the organic peracid precursor is further stable in the bleaching agent and the bleaching detergent. Is required to be stable to bleach and alkali. Therefore, the organic peracid precursor must be granulated and blended, but in order to granulate and stabilize the organic peracid precursor,
It turns out that it is necessary not to liquefy up to 80 ° C.

In the present invention, the granulated product of component (c) has a melting point of 40 ° C.
The above organic substances, for example, nonionic surfactant, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, higher alcohol, higher fatty acid, etc. are used as a granulation aid, and the organic peracid precursor is granulated by a known method. It is obtained by An organic peracid precursor that liquefies at 80 ° C is unstable in a bleaching agent or an alkaline system even after granulation. It is presumed that this is because a part of the organic peracid precursor is dissolved together with the granulation aid during granulation, so that the organic peracid precursor is easily brought into contact with the bleaching agent and the alkaline agent.

The organic peracid precursor used in the present invention is not particularly limited as long as it satisfies all of the above conditions (1) to (5). Specifically, for example, the following formula (I) [In the formula, R ₁ is an alkyl group having 1 to 22 carbon atoms, R ₂ and R ₃ are lower alkyl groups, and n is an integer of 1 to 5. ] An amphoteric compound represented by the formula (II) (Wherein R ₁ , R ₂ , R ₃ and n are as described above), and an amphoteric compound represented by the formula (III) (Wherein R ₂ and R ₃ are as described above) and the like.

In the present invention, the blending amount of these organic peracid precursors is such that the molar ratio of the peroxide (a) to the organic peracid precursor is peroxide /
Organic peracid precursor = 99.9 / 0.1 to 20/80, preferably 99/1 to 5
The amount is in the range of 0/50.

A bleaching detergent composition of the present invention is obtained by mixing the bleaching agent of the present invention comprising the above-mentioned components (a) to (c) with a detergent common component.

Examples of the detergent common ingredient used in the present invention include the following.

Alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate,
Anionic surfactants such as olefin sulfonate, alkane sulfonate, higher fatty acid salt, α-sulfo fatty acid salt or ester, carboxylate of alkyl or alkenyl ether, polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether , Higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid glycerin monoester, nonionic surfactant such as alkylamine oxide, betaine-type amphoteric surfactant, sulfonic acid-type amphoteric surfactant, cationic surface-active agent Surfactants such as activators; silicates, carbonates, sesquicarbonates (Na, K, Mg salts, etc.)
Neutral inorganic salts such as alkaline agents and sulfates; orthophosphate, pyrophosphate, tripolyphosphate, citrate, isocitrate, polyacrylate, polyacetalcarboxylate, divalent metal ion such as zeolite Scavenger; Recontamination inhibitors such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, polyethylene glycol; Enzymes such as protease, esperase, lipase, cellulase; Other anti-caking agents, bleach activators, antioxidants, fluorescent dyes, Bluing agents, light activated bleaching agents, perfumes, etc.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

In the examples, organic peracid precursors shown in (I) to (IX) below were used.

Table 1 shows the physical properties of these organic peracid precursors (I) to (IX).
Shown in

 The physical properties were measured by the methods described below.

<Measurement of the amount adsorbed on cellulose> Sodium percarbonate is adjusted to 0 ° C so that the available oxygen becomes 0.013%
Dissolved in water, and an organic peracid precursor was added to this so as to be equimolar to H ₂ O _2, and after dissolution, 4 g of Cellulose Powder D (40-100 mesh) manufactured by Toyo Roshi Kaisha, Ltd. Add at a rate of 50 ml, stir for 15 minutes, then filter using a glass felter, For those with, the adsorption amount was determined by analyzing Kjeldahl nitrogen in the filtrate and powder, With regard to those which produce peracids having no carboxylic acid, after decomposing organic oxygen, the carboxylic acid in the filtrate was analyzed by ion chromatography, and the amount of adsorption was determined from the amount of change.

<Measurement of Micelle Forming Concentration> The micelle forming concentration of the organic peracid precursor was determined by measuring the surface tension at 20 ° C. using a Kyowa CBVP type surface tensiometer A-3 manufactured by Kyowa Scientific Co., Ltd.

<Peracid generation rate measurement method> 0.3 g of sodium percarbonate and the following anionic detergent ₁₎ 0.
The organic peracid precursor was dissolved in a solution prepared by dissolving 3 g in 75 ml of tap water so as to be 1/16 equivalent to hydrogen peroxide in sodium percarbonate, and after reacting at 20 ° C. for 3 minutes, 0.3% of Catalase solution 2.5
After adding 1 ml and stirring for 1 minute, 10% 20% sulfuric acid and 10% potassium iodide solution were added and titrated with a 1 / 10N sodium thiosulfate solution, and the peracid production rate is determined by the following formula.

1) anionic detergents linear sodium alkylbenzenesulfonate (C _{12 ~ 13)} when using a 25% alkyl sulfate sodium (C _{14 ~ 15)} 8% sodium carbonate 20% sodium sulfate Balance 2) available oxygen 13.5% sodium percarbonate Titration with 100% peracid production.

Example 1 (Bleaching Effect of Immersion Bleaching) The bleaching agent composition shown in Table 2 was dissolved in 300 ml of water at 20 ° C. so that the available oxygen was 0.013%, and the tea-contaminated cloth (8 × 8 cm ² , (5 sheets) were used for immersion bleaching for 30 minutes, washed with water and dried, and then the bleaching rate was calculated by the following formula. still,
The bleaching rate was measured in two ways, the composition immediately after preparation and the composition after storage at 40 ° C. for 1 week. The organic peracid precursor used in this experiment was 15% granulated palmitic acid.

 The results are shown in Table 2.

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 in 3l of deionized water for about 15 minutes, then rubbed with desalted cotton, soak a cotton gold cloth # 2003 cloth in this liquid, and boil 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 10 cm × 10 cm was used for the experiment.

Example 2 A bleaching agent composition No. shown in Table 2 was added to a heavy-duty detergent having the following composition.
(1) to (10) were blended so that the sodium percarbonate content was 10% by weight to obtain a bleaching detergent composition.

A cleaning solution containing 0.133% of the bleaching detergent composition stored at 40 ° C. for 1 week was treated with a black tea-contaminated cloth (8 × 8 cm ² , 5 sheets) prepared in the same manner as in Example 1 using a tergotometer.
After washing at 0 ° C. for 10 minutes, washing with water and drying, the bleaching rate was determined by the same method as in Example 1.

 Table 3 shows the results.

<Heavy Detergent composition> linear alkyl benzene sulfonic acid sodium (C _{12 ~ 13)} 25
% Alkyl sulfate sodium (C _{14 ~ 15)} 7 Polyoxyethylene alkyl ether (C _{12 ~ 13,} ▲
＝ 10 ▼) 3% Sodium tallow fatty acid 3 Zeolite 28 Sodium silicate 10 Sodium carbonate 10 Sodium sulfate balance Polyethylene glycol (▲ ▼ 13000) 2 Sodium ethylenediaminetetraacetate 3 Moisture 5 100

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C11D 7/34 C11D 7/34 D06L 3/02 D06L 3/02

Claims (2)

(57) [Claims] 1. An organic peracid precursor which satisfies all of the following conditions (1) to (5): (a) a peroxide that dissolves in water to produce hydrogen peroxide; (b) an alkaline agent; Granulated body with an organic substance having a melting point of 40 ° C or higher (1) Reacting with hydrogen peroxide to produce an organic peracid having a cation group (2) Organic peracid precursor and produced organic peracid Adsorption amount to cellulose is 50 to 5000 ng / cm ² (3) Micelle forming concentration is 0.1 mol / l or more or does not form micelles (4) Peracid generation site is nitrile group, ester group or imide Group, the nitrile group has a peracid production rate of 5% or more, and the ester group or the imide group has a peracid production rate of 50% or more.
(5) A bleaching agent characterized by being solid at 80 ° C. 2. A bleaching detergent composition comprising the bleaching agent according to claim 1.