JPH0428799A - Bleaching agent and bleaching detergent composition - Google Patents

Abstract

PURPOSE:To provide the title composition having high bleaching effects, excellent in sebum/soil stain detergency and storage stability, biodegradable, thus high in the safety to human health, containing hydrogen peroxide, etc., and a specific cyclic imide group-contg. organic peracid precursor. CONSTITUTION:The objective composition containing (A) hydrogen peroxide or a peroxide capable of generating hydrogen peroxide in its aqueous solution and (B) an organic peracid precursor of the formula (R1-R4 are each H, 1-20C alkyl, alkenyl, may form ring; R5 is 1-15C alkylene which may contain branched chain or aromatic ring; L is eliminable group forming organic peracid when allowed to react with hydrogen peroxide) at the molar ratio (A/B) of normally (99.9:0.1) to (20:80) [pref. (99:1) to (50:50)].

Description

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

[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, which have no disadvantages, 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.

However, this oxygen bleach has a weaker bleaching edge than chlorine bleach, and various bleach activators are used in combination.

Tetraacetylethylenediamine, acetoxybenzenesulfonate, tetraacetylglycolyluril, glucose pentaacetate, and the like have been used as typical bleach activators, but their bleach activation effects are still insufficient.

[Means to solve the problem]

As a result of intensive research to obtain oxygen-based bleaches and bleaching detergents with higher bleaching blades, the present inventors have found that organic peracid precursor compounds having a specific cyclic imide group are extremely excellent as bleach activators. The present invention was completed based on this discovery.

That is, the present invention provides (a) hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution, and (b) the following formula (1) [wherein R+''R4: H, linear or branched An alkyl group or alkenyl group having a chain of 1 to 20 carbon atoms, or R5 which may form a ring: a chain having 1 to 20 carbon atoms and which may include a branched chain or an aromatic ring.
Alkylene group L in 15: means a leaving group that generates an organic peracid by reaction with hydrogen peroxide. ] The present invention provides a bleaching agent and a bleaching detergent composition characterized by containing an organic peracid precursor represented by the following.

Examples of the leaving group in general formula (I) include the following.

S and t are respectively −〇, −503M, −COOM,
-COOR', OH, halogen atom, -〇R1, -R1
or -NCR') represents 3.8. Here, H represents an alkali metal, an alkaline earth metal, an ammonium salt, an alkanol ammonium salt, or a negative charge itself, and R1 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a hydroxyalkyl group, -(C2H40), ~ 5H or (C31(
60) r~ represents H. 8 represents an inorganic or organic anion. Furthermore, S and t may be the same or different.

Here, R2 and R3 have the same meaning as R1, and may be the same or different at the same time, but at least one of them is H
isn't it.

d) e) Here, R1 has the same meaning as above, and Y is an alkylene group having 1 to 9 carbon atoms which may have a hydroxyl group, -(C2H
40) I~5-CtHa- or (C3H60) 1-5
-C2H4 is shown.

Alkanesulfonic acid represented by 0-Y-3OffM.

Here, Y means ``old'' and has the same meaning as above.

o (CHzCOO) Polyglycol ester represented by hH.

Here, k represents a number from 1 to 10.

f) An acid anhydride represented by O-C-R'.

Here, R4 represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group, or an optionally substituted phenyl group.

R’　　0 or -N-C-R Imide represented by.

1ll here Y has the same meaning as above.

pylori expressed as Doncarboxylic acid derivative.

Here R5 is n or R represents.

1? ’ here, R1 has the same meaning as above, -ha NO2 or 5O21? ’ and same or different You can leave it there.

enol derivatives.

The organic peracid precursor in the present invention is used in combination with hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution. In this case, hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution (a) and an organic peracid precursor (b)
The mixing ratio is usually (a)/(b) (molar ratio)
=99.910.1 to 20/80 is preferable, and more preferably 99/1 to 50150. As peroxides, sodium percarbonate, sodium tripolyphosphate/hydrogen peroxide adduct, sodium pyrophosphate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct, or 4NazSO4.2
Examples include H20□.NaCl, sodium perborate hydrate, sodium perborate tetrahydrate, sodium peroxide, and calcium peroxide. Among these, particularly preferred are sodium percarbonate, sodium perborate hydrate, and sodium perborate tetrahydrate.

In addition to the above-mentioned essential components, the bleaching agent and bleaching detergent composition of the present invention may contain known components that are usually added to bleaching agents or bleaching detergent compositions. For example, as building goo, in addition to water-soluble inorganic building goo such as sulfate, carbonate, bicarbonate, silicate, phosphate, water-insoluble inorganic building goo such as zeolite, ethylenediaminetetraacetate, nitrilotriacetate, tartrate, Organic virgoos such as citrate can be used. Also known as stabilizers for peroxides or hydrogen peroxide adducts are magnesium salts such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicate, magnesium oxide, and magnesium hydroxide, and silicate acids such as sodium silicate. Salts can be used. Furthermore, if necessary, redeposition inhibitors such as carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene glycol, alkyl sulfates, alkanesulfonates, alkyl ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates, higher grade Anionic surfactants such as fatty acid soaps, nonionic surfactants such as polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl ethers, mono- or jetanolamides of higher fatty acids, amine oxides, amphoteric surfactants such as betaine, proteases , enzymes such as lipase, amylase, and cellulase, optical brighteners, dyes, pigments, fragrances, and the like can be added.

Further, the bleaching agent of the present invention can be appropriately mixed with a conventionally known granular laundry detergent to obtain a bleaching detergent composition.

〔Effect of the invention〕

The bleaching (cleaning) agent of the present invention not only exhibits an excellent bleaching effect, but also has excellent cleaning performance against sebum stains and mud stains, and excellent storage stability.

Furthermore, the bleach activator used in the bleach (cleaning) agent composition of the present invention is biodegradable and highly safe for the human body.

〔Example〕

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

Synthesis Example 1 Synthesis of Compound (■ a) (1-a) 11 Put 70 g of ASAN-PT (propylene tetramer) and 34 g of ε-aminocaproic acid into an eggplant flask.
Heated at 160-170°C for 3 hours. When cooled as it is, 95.0 g of carboxylic acid represented by the following formula (II-a)
was gotten. Yield 95%.

(IF-a) Next, using a 300 m eggplant flafco, (II-a) 30
Dissolve 0g in 5011 dichloromethane and add 12g at room temperature.
All! of thionyl chloride was added dropwise. 1 hour 30
After reacting for several minutes, the solvent and excess thionyl chloride were distilled off to obtain 33.0 g of a compound represented by the following formula (■-a) as a yellow oily substance. Yield 100%.

II (III-a) Using 30 flasks of 300d, 31.4g of (■-a
) was dissolved in 40 ml of N,N-dimethylacetamide, 17.1 g of p-phenolsulfonic acid disodium salt (dehydrated) was added, and the mixture was reacted under reflux in a suspended state for 2 hours. I let it happen.

After the reaction solution was cooled, it was added to 50M acetone and the generated precipitate was collected by filtration to obtain 20.3 g of a mixture of sodium chloride and (I-a).

Synthesis Example 2 Synthesis of Compound (1-b) (1-b) 26 g of methylsuccinic anhydride in a 5001d eggplant flask
and 30g of ε-aminocaproic acid, 160-170
Heated at ℃ for 2 hours. If it is cooled as it is, the following formula (II-
49.7 g of carboxylic acid represented by b) was obtained. Yield 96%.

(ff-b) Next, using a 300d eggplant fluffco, 30g of (II-b) was
0al+ dichloromethane and 20 ml of thionyl chloride was added dropwise at room temperature. After reacting for 1 hour and 30 minutes, the solvent and excess thionyl chloride were distilled off to obtain 32 g of a compound represented by the following formula (III-b) as a yellow oily substance.

Yield 100%.

(III-b) Using a 500d three-lough flask, 32g of the acid chloride represented by (■b) was converted into N,N-dimethylacetamide 8
28.8 g of P-phenolsulfonic acid disodium salt (dehydrated) was added thereto, and the mixture was reacted in a suspended state under reflux for 2 hours.

After cooling the reaction solution, l! was added to acetone and the resulting precipitate was collected by filtration to obtain 33.5 g of a mixture of sodium chloride and (I-b).

Synthesis Example 3 Synthesis of Compound (I-C) (1-c) 148 g of scophthalic acid and 131 g of ε-aminocaproic acid were placed in an lffi trifushiro flask and heated at 140 to 160°C for 1 hour. After cooling, the solidified product is recrystallized using methanol-water as a solvent, and the white crystals (II-C) are converted to 16
9 g was obtained. Yield 64.6%.

(II-c) Next, using a 300i eggplant flafco, 20g of (Il-c)
was suspended in 50H1 of dichloromethane and diluted with 1
2M1 of thionyl chloride was added dropwise.

After reacting for 1 hour and 30 minutes, the solvent and excess thionyl chloride were distilled off, leaving a yellow oily substance with the following formula (II
21.4g of the compound represented by [-c) was obtained. Yield 100%.

(II [-C) 21.4 g of (■-
The acid chloride represented by C) was dissolved in 40 WIl of N,N-dimethylacetamide, 18.4 g of p-phenolsulfonic acid disodium salt (dehydrated) was added, and the mixture was suspended under reflux for 2 hours. Made it react.

After cooling the reaction solution, it was added to 500 d of acetone and the resulting precipitate was collected by filtration to obtain 31.8 g of a mixture of sodium chloride and (1-C).

Examples Compounds (I-a) to (1-C) obtained in Synthesis Examples 1 to 3
The following bleaching test was conducted using

Bleaching test> ・Measurement of bleaching effect Sodium percarbonate was dissolved in 300°C of water at 20°C so that the effective oxygen content was 0.05%, and sodium percarbonate was dissolved so that the effective oxygen content was 0.05%. Activators 1-a to ■-
c and tetraacetylethylenediamine for comparison (
TAED) were added in the proportions shown in Table 1, and immersion bleaching was performed for 30 minutes using 5 black tea-stained cloths prepared in the following manner. After washing with water and drying, the bleaching rate was determined by the following formula.

Bleaching rate of black tea contaminated fabric: Bleaching rate (%) = Reflectance is 460 for NDR100IDP manufactured by Nippon Denshoku Kogyo ■
Measured using a nl11 filter.

Black tea contaminated cloth: Boil 80 g of Nitto black tea (yellow pancake) in 31 ion-exchanged water for about 15 minutes, strain it through desized dry cotton, soak a cotton training camp 112003 cloth in this liquid, and boil for about 15 minutes. The sample was removed from the heat, left to stand for about 2 hours, then air-dried, washed with water until the washing solution became colorless, dehydrated, and pressed to form a test piece of 8 cm x 8 cm for use in experiments.

The results of the bleaching test are shown in Table 1.

No. table Next, we will show the results when detergent was used in combination.

Commercially available heavy detergent 0.0833%, sodium percarbonate 0
．． 0833% in water, I-a to I-C and T
Using black tea-stained cloth (8x8as, 5 pieces) prepared in the above method, the cleaning solution containing AED at 0.0047% was washed in a turbotometer at 20°C for 110 minutes, washed with water, dried, and then washed with the above method. The bleaching rate was measured using the same method as above.

The results are shown in Table 2.

No. table

Claims (1)

[Claims] 1 (a) Hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution, and (b) the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 to R_4: H, linear or branched carbon number 1 to 20
R_5 which may form an alkyl group or alkenyl group or a ring: 1 carbon number which may contain a branched chain or an aromatic ring
~15 alkylene group L: means a leaving group that generates an organic peracid by reaction with hydrogen peroxide. ] A bleach and bleach cleaning composition characterized by containing an organic peracid precursor represented by the following.