JPH047400A - Bleaching agent and bleaching detergent composition - Google Patents

Abstract

PURPOSE:To obtain a bleaching agent exhibiting excellent bleaching effect, providing excellent detergent effect against staining caused by sebum and mud, and having high safety to the human body by using a specified org. peroxy acid or org. peroxy precursor. CONSTITUTION:A bleaching agent is obtd. by using an org. peroxy acid or an org. peroxy precursor or formula I, wherein R1 is a 1-20C (substd.) alkyl, aryl or alkaryl; R2 is a 1-20C (substd.) alkylene or arylene; X and Y are each O, =N-R3 (wherein R3 is H, a 1-20C alkyl, aryl or alkaryl); (m) and (n) are each 0 or 1 (provided that (m) and (n) are not 0 at the same time); L is OOH or an eliminative group reacting with H2O2 and forming an org. peroxy acid, e.g. formula II (wherein (s) and (t) are each H, SO3M, COOM, OH, a halogen, etc., and M is an alkali metal, an alkali earth metal, etc.) or formula III (wherein R2 and R3 are as defined in R1. This bleaching agent exhibits excellent bleaching effect, provides excellent detergent effect against staining caused by sebum and mud, and furthermore exhibits high safety to the human body.

Description

[Detailed description of the invention] [Industrial application field] TECHNICAL FIELD This invention relates to bleaching agents and bleaching cleaning 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, 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 bleaching agent has a weaker bleaching blade than the chlorine bleaching agent, 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 discovered that a specific compound is extremely excellent as a bleaching agent or bleach activator, and the present invention completed.

That is, the present invention provides the following general formula (1) [wherein R8: optionally substituted alkanol group, aryl group, or alkaryl group having 1 to 2 carbon atoms R2: optionally substituted carbon number 1 to 20 alkylene, arylene, or alkanolene groups X, Y: respectively 10- or -N- (R3 is H or carbon R
1 An alkyl group, aryl group, or alkaryl group having a prime number of 1 to 20. ) m, n: Q or l (however, - and n cannot be 0 at the same time) L-00H or means a leaving group that reacts with hydrogen peroxide to produce an organic peracid. ] A bleaching agent and a bleach cleaning composition containing an organic peracid or an organic peracid precursor represented by these are provided.

In the present invention, the "optionally substituted" substituent typically represents a hydroxyl group, a lower alkyl group, etc.

Examples of the leaving group of L in general formula (1) include the following.

S and t are respectively −〇, −303M, −COOM,
-COOR', -OH, halogen atom, -〇R1, -R
1 or -N(R')s・A, where H represents an alkali metal, alkali [metal, ammonium salt, alkanol ammonium salt, R1 is H1 alkyl group having 1 to 20 carbon atoms, alkenyl group, hydroxy Alkyl group, -(
C! 840) r~, H or -(C3H&0) l~
Representing Sn, A represents an inorganic or organic anion.

Furthermore, S and t may be the same or different.

1 here! , R1 has 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.

Here, R1 has the same meaning as above, Y is an alkylene group having 1 to 9 carbon atoms which may have a hydroxyl group, -(CJa
O) +-5-cJ4- Also bar (C3H60) 1
-s-CsHb is shown.

d) Alkanesulfonic acid represented by -0-Y-3O3M.

Here, Y and M have the same meanings as above.

e) −0(CHzCOO)J? ``Represented Lerholig''
) Call x Stell.

Here, k represents a number from 1 to 1o.

f> Acid anhydride represented by -0-C-R'.

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

-NOx or -SO,R', which may be the same or different.

Here, R' and Y have the same meanings as above.

enol derivatives.

Here, R6 represents R1 excluding H.

- In formula (1), L is preferably a pyrrolidone carboxylic acid derivative represented by.

Here, R5 represents H or R1.

Here, II has the same meaning as above, - is -1; -0-M
'-C-N-(R'J heat, -C-1 -C=N.

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, the blending ratio of hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution (a) and the organic peracid precursor (b) is usually (a)/(b) (molar ratio ) =9
9.910.1 to 20/80 is preferable, and 99/1 to 50150 is more preferable.

As peroxides, sodium percarbonate, sodium tripolyphosphate/hydrogen peroxide adduct, sodium pyrophosphate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct, or 4
Examples include NaxSOa' 28zOz .NaC1° 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 a builder, in addition to water-soluble inorganic builders such as sulfates, carbonates, bicarbonates, silicates, and phosphates, water-insoluble inorganic builders such as zeolites, ethylenediaminetetraacetate, nitrilotriacetate, tartrate, Organic builders 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 fluorosilicate, magnesium oxide, and magnesium hydroxide, and silicate acids such as sodium silicate. Salts can be used. Furthermore, if necessary, redepositing inhibitors such as carboxymethylcellulose, 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 provides an excellent cleaning effect on sebum stains and mud stains.

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

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

Example The following bleaching test was conducted using the compounds (1-a) to (I-d) shown below.

I-a: 1-c; (MW = 501) I-d; (MW = 454) TAED; (MW = 463) 1-b; (MW = 345) <Bleaching test> [Lfl Watarai Zainao 20 Sodium percarbonate was dissolved in 300 d of water at ℃ so that the effective oxygen content was 0.05%, and compounds (1-a) to (I-
d) and tetraacetylethylenediamine (TAED) for comparison were added in the proportions shown in Table 1, and immersed and bleached for 30 minutes using 5 black tea-stained cloths prepared in the following manner, washed with water, After drying, the bleaching rate was determined using the following formula.

Bleaching rate of black tea stained cloth: Bleaching rate (%) - After pressing, it was made into a test piece of 8 cll x 8 CII+ and used for the experiment.

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

Table 1 reflectance is 46 for NDR-1001DP manufactured by Nippon Heavy Industries Ltd.
Measured using on-filter. The higher this number, the higher the bleaching rate.

Black tea contaminated cloth: Boil 80g of Nitto black tea (yellow package) in 31 ion-exchanged water for about 15 minutes, then strain it through a desized dry cotton cloth, soak a cotton gold cloth 112003 cloth in this liquid, and boil it for about 15 minutes. . Remove from the heat, leave to stand for about 2 hours, then air dry, rinse with water until the washing liquid is no longer colored, and dehydrate.Example 2 Commercially available heavy detergent 0.0833%, sodium percarbonate 0
．． ■-a, to the cleaning solution containing 0833%;
I-b, I-c, I-d and TAED at 0.0042%
Dissolve the black tea contaminated cloth prepared in Example 1 (
1 with a turbotometer using
After washing with 00rpn+ at 20°C for 110 minutes, washing with water,
After drying, the bleaching rate was determined by the same method as in Example 1.

In addition, the mud-stained fabrics (5 pieces) and sebum-stained fabrics (5 pieces) prepared using the method below were washed in the same manner, and the reflectance was measured using the method below, and the cleaning rate was calculated to evaluate the cleaning performance. We conducted an evaluation.

Akadama soil for Kokanuma gardening was dried for 4 hours at 120°C ± 5°C, then crushed, and 12 pieces of 150 mesh (100 m) pass were obtained.
After drying for 2 hours at 0℃±5'C, 1000g of ±150g
7! The dispersion liquid is removed and excess dirt is removed by contacting and brushing with a #2023 metal cloth (Japanese Patent Application Laid-Open No. 55-26473).

*Model sebum stain composition Cottonseed oil 60% Cholesterol 10% Oleic acid 10% Palmitic acid 10% Liquid and solid paraffin 10% 2 g of model sebum stain with the above composition is evenly applied to a 10 x 10 aw cotton cloth.

The reflectance of the washed contaminated cloth was measured using NOR10 manufactured by Nippon Denshoku Kogyo.
Using 0IDP, measurements were made using a filter of 460 nt* for mud-stained cloth and 550 na+ for sebum-stained cloth, and the cleaning rate was determined using the following formula to evaluate the cleaning performance.

The results at this time are shown in Table-2.

Table 2 Example 3 A bleach composition of the present invention containing the following phosphorus-free, low-phosphorus, and phosphorus-containing detergents was obtained.

All of the obtained bleach compositions exhibited good bleaching properties and detergency.

[Phosphorus-free formulation]

Hydrogenated beef tallow fatty acid sodium No. 2 sodium silicate sodium carbonate 4A type zeolite sodium sulfate balance [Low phosphorus formulation] sodium dodecyl sulfate Hydrogenated beef tallow fatty acid sodium No. 1 sodium silicate sodium carbonate 4A type zeolite Sodium pyrosulfate sodium sulfate sodium perborate protease water sodium sulfite protease water [Phosphorus-containing combination] Hydrogenated beef tallow fatty acid sodium Sodium tripolyphosphate sodium perborate No. 2 sodium silicate sodium carbonate sodium sulfite protease water sodium sulfate balance

Claims (1)

[Claims] The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ (I) [In the formula, R_1: an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group, or Alkaryl group R_2: An optionally substituted alkylene group, arylene group, or alkaryl group having 1 to 20 carbon atoms. It is an alkyl group, aryl group or alkaryl group having 1 to 20 carbon atoms.) m, n: 0 or 1 (however, m and n cannot be 0 at the same time) L: - Reacts with OOH or hydrogen peroxide refers to a leaving group that produces an organic peracid. ] A bleaching agent and a bleach cleaning composition containing an organic peracid or an organic peracid precursor represented by the following.