JPH0284499A - Bleaching agent and bleaching detergent composition - Google Patents

Abstract

PURPOSE:To obtain a bleaching agent and bleaching detergent composition, containing a peroxide, alkaline agent and granulated organic peracid precursor having specific physical properties with excellent bleaching power without deteriorating the bleaching power even after storing for a long period. CONSTITUTION:The objective bleaching agent and composition containing (A) a peroxide capable of forming hydrogen peroxide in dissolving in water, (B) an alkaline agent consisting of preferably a water-soluble alkaline inorganic salt and (C) a substance prepared by granulating an organic peroxide precursor satisfying all the following conditions with an organic substance having 40 deg.C melting point. Reactive with hydrogen peroxide and forming an organic peracid having cationic group, having 50-500ng/cm<2> adsorption on cellulose and >=0.1mol/l micelle forming concentration or without forming the micelles. Having nitrile, ester or imide groups which are peracid forming parts with >=50% peracid forming ratio in the case of nitrile groups and >=50% peracid forming ratio, further solid at 80 deg.C in the case of ester or imide groups.

Description

[Detailed description of the invention] [Industrial application field] TECHNICAL FIELD This invention relates to bleaching agents and bleaching detergent compositions.

[Prior art and problems to be solved by the invention] Chlorine bleach has limitations on the types of fibers that can be used, cannot be used on colored or patterned fabrics, and has a unique odor. Oxygen bleaches that do not have these drawbacks have recently become very popular.

As the oxygen bleach, sodium percarbonate and sodium perborate are particularly used from the viewpoint of bleaching performance and stability.

Oxygen bleach has a weaker bleaching blade than chlorine bleach, and various organic peracid precursors (bleach activators) are used in combination. Nitriles such as acetonitrile, malonitrile, phthalonitrile, benzoyliminodiacetonitrile,
glucose pentaacetate, octaacetyl sucrose, triacetin, sorbitol hexaacetate,
acetoxybenzenesulfonate, or triacetyl cyanuric acid, 0-acetylated products such as methyl chloroformate, N, N, N', N'-tetraacetylethylenediamine, or tetraacetylglycolyluril, N
- N-acylated products such as benzoylimidazole, di-N-acetyldimethylglyoxime, l-phenyl-3-acetylhydantoin, N,N-diacetylaniline, N-acetyldiglykolimide, diacetylmethylene diformamide, and anhydrous acid anhydrides, such as phthalic acid, succinic anhydride, benzoic anhydride, glutaric anhydride, alkyl sulfuric anhydrides, carboxylic acid and organic sulfonic acid anhydrides;
Sulfonyloximes such as di(methanesulfonyl)dimethylglyoxime, acylated phosphates such as di-ethylbenzoyl phosphate, phenylsulfonate esters, organophosphoric acid azides such as diphenylphosphinic azide, disulfones such as diphenyldisulfone. , various other organic peracid precursors such as N-sulfonylimidazole, cyanamide, and halogenated triazine have been studied.

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

An object of the present invention is to obtain a bleaching agent and a bleach cleaning agent that have excellent bleaching blades and do not deteriorate in bleaching blades even after being stored for a long period of time.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventors found that
The present invention has been completed by discovering that a bleaching agent and a bleaching detergent that meet the above-mentioned problems can be obtained by using an organic peracid precursor that satisfies specific conditions.

That is, the present invention comprises (a) a peroxide that dissolves in water to produce hydrogen peroxide, (b) an alkaline agent, and (c) an organic peracid that satisfies all of the following conditions (1) to (5). Precursor granulated with an organic substance with a melting point of 40°C or higher (1) Reacting with hydrogen peroxide to produce an organic peracid having a cationic group (2) Organic peracid precursor and the produced organic peracid The amount of adsorption to cellulose is 50 to 5000 ng/clIz (3) The concentration of micelles forming is 0.1 mol/I! , or above, or do not form micelles. (4) The peracid generating site is a nitrile group, ester group, or imide group, and in the case of a nitrile group, the peracid generation rate is 5% or more; If the peracid production rate is 50%
(5) The present invention provides a bleaching agent characterized by being solid at 80°C, and a bleach cleaning composition characterized by containing this bleaching agent.

Component (a) used in the present invention, a peroxide that dissolves in water to produce hydrogen peroxide, includes organic and inorganic hydrogen peroxide adducts such as sodium carbonate/hydrogen peroxide adduct (soda percarbonate); Sodium tripolyphosphate/hydrogen peroxide adduct, sodium birophosphate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct, or 4NatSO4/2H2O1
-NaCl etc. are exemplified. Inorganic peroxides such as sodium perborate hydrate, sodium perborate tetrahydrate, sodium peroxide, and calcium peroxide can also be used.

Among these, particularly preferred are sodium carbonate/hydrogen peroxide adduct, sodium perborate hydrate, and sodium perborate tetrahydrate.

Component (a), peroxide, is blended in the bleaching agent of the present invention in an amount of 1 to 90% by weight.

The alkaline agent used in the present invention is preferably a water-soluble alkaline inorganic salt, such as carbonate, bicarbonate, silicate, orthophosphate, metaphosphate, hexametaphosphate, pyrophosphate, tripolyphosphate. Examples include acid salts.

As the salt, alkali metal salts such as sodium and potassium are preferred. C) component is blended in the bleaching agent of the present invention in an amount of 2 to 70% by weight or 5 to 50% by weight, resulting in improved bleaching performance and stabilization of bleaching performance.

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

Conditions (1) and (2) are that the organic peracid precursor and the organic peracid produced by reacting it with hydrogen peroxide have a cationic group and are adsorbent to cellulose fibers or dirt. shows. Adsorption amount to cellulose is 50ng/
If the amount is less than 5000 ng/cm, the bleaching efficiency on clothing or soiled surfaces will be insufficient, and the adsorption amount should not exceed 5000 ng/cm in order to prevent stains from re-attaching to clothing and rinsing away from clothing. . Preferably the adsorption amount is 200 to 2000
ng/cm".

Condition (3) relates to the rate of production of organic peracid.

If the micelle formation concentration is less than 0.1 mol/l, the reaction in the solution will be slow and bleaching will not be carried out sufficiently within the bleaching or washing time.

Condition (4) is the required amount of organic peracid to effect sufficient bleaching. This value varies depending on the structure of the peracid-generating site, but it is thought to be related to the oxidation rate of the organic peracid generated. When the peracid generating site is a nitrile group, the peracid generating rate is 5% or more, preferably 10% or more, and when it is an ester group or an imide group, the peracid generating rate is 50% or more, preferably 70% or more. Bleaching is sufficient.

The conditions (1) to (4) above are essential requirements for the organic peracid precursor to obtain an excellent bleaching blade, but in addition, the organic peracid precursor is stable in bleaching agents and bleaching cleaning agents. is required to be stable to bleach and alkali. For this reason, the organic peracid precursor must be granulated and blended, but in order to be granulated and stabilized, the organic peracid precursor must be
It has been found that it is necessary not to liquefy up to 0°C.

In the present invention, the granulated material of component (c) has a melting point of 40°C.
By granulating the organic peracid precursor by a known method using the above organic substances, such as nonionic surfactants, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, higher alcohols, higher fatty acids, etc., as granulation aids. can get. Organic peracid precursors that liquefy at 80°C are unstable with bleach or alkaline systems even after granulation. This is presumed to be because a part of the organic peracid precursor is dissolved together with the granulation aid during granulation, making it susceptible to contact with bleach and alkaline agents.

The organic peracid precursor used in the present invention is as described above (1)
Although it is not particularly limited as long as it satisfies all the conditions of ~(5), specifically, for example, the following formula [wherein R is an alkyl group having 1 to 22 carbon atoms, R2+R3 is a lower alkyl group, n is an integer from 1 to 5. Amphoteric compound represented by the formula (II) R7 R,0 (wherein RI+ R,, R3, n are as described above), an amphoteric compound represented by the formula (DI) Rs R3 (wherein R2, (R3 is as described above) Examples include compounds represented by the following.

In the present invention, the blending amount of these organic peracid precursors is such that the molar ratio of peroxide (a) and organic peracid precursor is peroxide/organic peracid precursor = 99.910.1 to 20/80. , preferably in an amount ranging from 99/l to 50,150/l.

The bleaching detergent composition of the present invention can be obtained by mixing the bleaching agent of the present invention comprising components (a) to (c) as described above with common detergent ingredients.

Common detergent ingredients used in the present invention include the following.

Anions such as alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkanesulfonates, higher fatty acid salts, α-sulfo fatty acid salts or esters, carboxylates of alkyl or alkenyl ethers, etc. Nonionic surfactants such as surfactants, polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, fatty acid glycerol heptanoesters, alkyl amine oxides, Surfactants such as betaine type amphoteric surfactants, sulfonic acid type amphoteric surfactants, cationic surfactants; silicates, carbonates, sesquicarbonates (Na, K, Mg
alkaline agents such as salts) and neutral inorganic salts such as sulfates; orthophosphates, birophosphates, tripolyphosphates, citrates, isocitrates, polyacrylates, polyacetal carboxylates, zeolites Divalent metal ion scavengers; anti-recontamination agents such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, and polyethylene glycol; enzymes such as protease, esperase, lipase, and cellulase; other anti-caking agents, bleach activators, antioxidants,
Fluorescent dyes, blue tints, light activated bleaches, fragrances, etc.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

In addition, in the examples, the organic peracid precursors shown in the following (1) to (IX) were used.

H3 Table 1 shows the physical properties of these (I) to (IX) organic peracid precursors.
Shown below.

In addition, the physical properties were measured by the method shown below.

<Measurement of adsorption amount on cellulose> Sodium percarbonate was added to 0.0% so that effective oxygen was 0.013%.
Dissolve in water at ℃, add an organic peracid precursor to the solution so that the mole is equimolar to HzOz, and after dissolving, add 4 g1 of cellulose powder D (40 to 100 mesh) manufactured by Toyo Roshi ■.
After stirring for 15 minutes, H3 was added at a ratio of 50 to 50%, and after stirring for 15 minutes, H3 was added using a glass filter.For the Kjeldahl nitrogen in the filtrate and powder, after decomposing the organic oxygen, the carboxylic acid in the filtrate was analyzed by ion chromatography. The amount of adsorption was determined from the amount of change.

<Measurement of Micelle Formation Concentration> The micelle formation concentration of the organic peracid precursor was determined by surface tension measurement at 20° C. using a Kyowa CBVP type surface tension meter A-3 manufactured by Kyowa Kagaku ■.

<Peracid production rate measurement method> Sodium percarbonate 0.3g and the following anionic detergent 1)
An organic peracid precursor was dissolved in a solution of 3 g of Q in 75-g of tap water in an amount of 1716 equivalents to hydrogen peroxide in sodium percarbonate, and after reacting at 20°C for 3 minutes, 0. After adding 2.5-3% catalase solution and stirring for 1 minute,
Add 0% sulfuric acid 10a7.10% potassium iodide solution, titrate with 1/ION sodium thiosulfate solution, and determine the peracid production rate using the following formula.

Peracid production rate (%) = l) Anionic detergent alkyl sodium sulfate (c+4~l,) 8% soda carbonate
20% mirabilite balance 2) Peracid production rate when using sodium percarbonate with 13.5% effective oxygen
0% titration.

Example 1 (Bleaching effect of immersion bleaching) The bleaching agent composition shown in Table 2 was dissolved in 300°C of water at 20°C to give an effective oxygen concentration of 0.013%, and black tea stained cloth (8X 8c+) prepared by the following method was prepared. *”, 5 sheets) to 3
After immersion bleaching for 0 minutes, washing with water, and drying, the bleaching rate was determined using the following formula. In addition, the bleaching rate was measured for the composition immediately after adjustment, 4
Two compositions were tested after storage at 0''C for 11 weeks. The organic peracid precursor used in this experiment was 15% valmitic acid granules.

The results are shown in Table 2.

Bleaching rate of black tea contaminated cloth: Reflectance is 460 for NDR-101DP manufactured by Nippon Heavy Industries Ltd.
Measured using a nm filter.

Tea-contaminated cloth: Boil 80g of Nitto black tea (yellow package) in 32 ion exchange water for about 15 minutes, strain it through desized dry cotton cloth, dip a cotton gold cloth 112003 cloth into the liquid and boil it for about 15 minutes. . Remove from heat, 2
After leaving it for about an hour, let it dry naturally, wash it with water until the washing liquid is no longer colored, dehydrate it, and press it, 10cm x 10c.
The test piece (2) was used for the experiment.

(Note) (1) Nα (2) to (4) are products of the present invention, and the others are comparative products.

(2) The content of the organic peracid precursor is equivalent to the amount of hydrogen peroxide produced from sodium percarbonate.

(3) ml Use the composition immediately after blending.

The composition was used after being stored at 240°C/l for a week.

Example 2 Bleach composition k (1) listed in Table 2 was added to a heavy duty detergent having the following composition.
~0ω was blended so that the sodium percarbonate content was 10% by weight to obtain a bleaching detergent composition.

0.133 for the bleaching detergent composition stored at 40°C for one week.
After washing with a turbotometer at 20°C for 10 minutes using black tea-stained cloth (8 x 8C11!, 5 pieces) prepared in the same manner as in Example 1 in a cleaning solution containing %, after washing with water and drying,
The bleaching rate was determined by the same method as in Example 1.

The results are shown in Table 3.

<Heavy detergent composition>

Claims (1)

[Scope of Claims] 1 (a) a peroxide that dissolves in water to produce hydrogen peroxide; (b) an alkaline agent; and (c) an organic filtrate that satisfies all of the following conditions (1) to (5). (1) Reacts with hydrogen peroxide to produce an organic peracid having a cationic group (2) Organic peracid precursor and the produced organic peracid The adsorption amount of acid to cellulose is 50 to 5000 ng/cm^2 (3) The micelle formation concentration is 0.1 mol/l or more or no micelles are formed (4) The peracid generating site is a nitrile group, It is an ester group or an imide group, and in the case of a nitrile group, the peracid production rate is 5% or more, and in the case of an ester group or an imide group, the peracid production rate is 50% or more. (5) It is solid at 80 ° C. A bleaching agent characterized by containing. 2. A bleach cleaning composition comprising the bleaching agent according to claim 1.