JPH02132196A - Bleaching agent and bleaching cleansing agent composition - Google Patents

Abstract

PURPOSE:To provide an oxygenic bleaching agent and a bleaching cleansing agent composition exhibiting an improved bleaching power by containing hydrogen peroxide, etc., and a cationic compound as a bleaching-activating agent. CONSTITUTION:The objective bleaching agent and bleaching-activating agent composition contains (A) hydrogen peroxide or a peroxide generating the hydrogen peroxide in an aqueous solution and (B) cationic compounds of formula I [R1 and R2 are (hydroxy)alkyl; R3 is -CH2-O-CH2-, -CH2CH2-O-CH2CH2-, group of formula II-IV, -CH2-CH=CH-CH2-, group of formula V-VII or -CH2-S-CH2-; X is inorganic or organic counter ion] and/or formula VIII [Y is group of formula IX, R4-O- or group of formula X (R4 is alkyl; R5 is H or alkyl)] as bleaching-activating agents.

Description

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

[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 weaker bleaching power than chlorine bleach, and various bleach activators are used in combination.

Typical bleach activators used include tetraacetylethylenediamine, acetoxybenzenesulfonate, tetraacetylglycolyluril, and glucose pentaacetate.
Its bleach activation effect is still insufficient.

[Means to solve the problem]

As a result of intensive research to obtain oxygen-based bleaches and bleach detergents with higher bleaching power, the present inventors discovered that the following specific cationic compounds are extremely excellent as bleach activators. Completed the invention.

That is, the present invention contains (a) hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution, and (b) a cationic compound represented by the following general formula (I) or (II). A bleach composition and a bleach cleaning composition are provided.

(In the formula, R,, R2 is an alkyl group or a hydroxyalkyl group, R3 is -CH2-0-CH, -CH2CH
2-0-CH, CH2-, CI. -S-CH2-
(X represents an inorganic or organic counterion) (In the formula, R., R2 are the same as above, Y is R.-C-, R
．． -0 alkyl group, X represents an inorganic or organic counterion) In these cationic compounds, the bleaching active species has a cationic group. Therefore, the rate of generation of bleaching active species is fast;
Since the bleaching active species is present in an adsorbed or concentrated state on the fiber surface, it is presumed that the bleaching power is significantly improved.

In the above formula, R,, R2 is a lower alkyl group, R4 has 1 carbon number
~14 alkyl groups, preferably lower alkyl groups, R5
is hydrogen or an alkyl group having 1 to 14 carbon atoms, preferably hydrogen or a lower alkyl group.

In the present invention, peroxides that generate hydrogen peroxide in an aqueous solution include sodium percarbonate, sodium tripolyphosphate/hydrogen peroxide adduct, sodium pyrophosphate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct, or 4Na2
SO4.2H20.NaCl, sodium perborate} IJ-um hydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide, etc. are exemplified. Among these, particularly preferred are sodium percarbonate, sodium perborate hydrate, and sodium perborate tetrahydrate.

Hydrogen peroxide in the bleach composition and bleach cleaning composition of the present invention or peroxide (a) that generates hydrogen peroxide in an aqueous solution
) and the cationic compound (l)) represented by general formula (I) or (II) is usually (a)/(b).
(Molar ratio) -99. 1/0. The ratio is preferably 1 to 20/80, and more preferably 99/1 to 50/50.

In addition to the above-mentioned essential components, the bleach composition and bleaching detergent composition of the present invention may contain known components that are usually added to bleaching compositions or bleaching detergent compositions. For example, building materials include water-soluble inorganic builders such as sulfates, carbonates, bicarbonates, silicates, and phosphates, water-insoluble inorganic builders such as zeolites, ethylenediaminetetraacetate, nitrilo+J acetate, and tartaric acid. Organic bilges such as salts, citrates, etc. 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, redeposition inhibitors such as carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycol, alkyl sulfates, alkanesulfonates,
Alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, anionic surfactants such as higher fatty acid soaps, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl ethers, mono- or diethanolamides of higher fatty acids, amines Nonionic surfactants such as oxides, amphoteric surfactants such as betaine, enzymes such as protease, lipase, amylase, cellulase, optical brighteners, dyes, pigments, fragrances, etc. can be added.

Further, the bleach composition of the present invention can be appropriately mixed with conventionally known granular laundry detergents to obtain a bleach cleaning composition.

〔Example〕

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

First, a synthesis example of the bleach activator used in the present invention will be shown as a reference example.

Reference example 1 Diamine IOg (62.5 mmol) of the above formula (V)
was added to a 100-liter three-necked flask with 30 ml of acetone, and while stirring with a magnetic cooler, added 10. 4
g (68.8 mmol) was added dropwise, and the temperature was raised to room temperature.
The reaction was carried out under reflux for 3 hours, and the resulting crystals were filtered and washed with acetone.
7. I got 8g. Yield 90.0%.

Reference example 2 Vista mouth methyl ether Log (0.12 mol)
was dissolved in 50 ml of acetone, put into a three-necked flask, and while stirring with a magnetic cooler, dimethylaminoacetonitrile 14. was added using a water-cooled dropping funnel. 6
23. g (0.24 mol) was added dropwise and reacted at room temperature for 3 hours, and the crystals were filtered off to obtain the compound of formula (I-b) above as white crystals. I got 7g. Yield 96.3%.

Reference Example 3 10 g of dimethylaminoacetonitrile hydrochloride (83.
0mol) in acetone 5omf! While stirring with a magnetic cooler, butadiene diepoxide was added dropwise at room temperature, and the mixture was allowed to react at room temperature for 3 days. After the reaction, the reaction solution is removed by decantation and washed with acetone. At this time, the washing solution is also removed by decantation. The solvent was completely removed using a rotary evaporator, and the compound of formula (I-c) above was obtained as a white solid.
4. I got 2g. Yield 93.2%.

Reference example 4 tJH 10 g (68.5 mmo) of diamine of the above formula (Vl)
1) was dissolved in 30 ml of acetone, and while stirring with a magnetic cooler using a 100 rnl three-necked flask, 11. 4g (I50.
7 mmol) was added dropwise and allowed to react at room temperature for 5 hours. By removing the reaction solution and washing with acetone in the same manner as in Reference Example 3, the compound of formula (I-d) above was obtained as a white solid in 18. I got 2g. Yield 89.1%.

Reference example 5 α,α-dichloroparaxylene log (57.1 mm
ol) in acetone, and using a three-necked flask, add dimethylaminoacetonitrile while stirring with a magnetic cooler. 6g (I14.2mrn
ol) was added dropwise at room temperature. The reaction was allowed to proceed for 3 days at room temperature, and the mixture was filtered to obtain 17.9 g of the compound of the above formula (■-e) as white crystals. Yield 91.3%.

Reference example 6 1.4-dichloro-2-butene Log (80.0m
mol) in 30 ml of acetone, and using a three-necked flask, add 13. mol of dimethylaminoacetonitrile while stirring with a magnetic stirrer. 4g (I60.0
mmol) was added dropwise at room temperature, reacted at room temperature for 3 days, and filtered to obtain the compound of formula (I-f) above as white crystals.
I got 9g. Yield 93.5%0 Reference Example 7 10 g (0. llmol) of monochloroacetone was dissolved in 30 mf of acetone, and dimethylaminoacetonitrile 9. 1 g (0. llmo!) was added dropwise at room temperature, reacted at room temperature for 3 hours, and the solvent was distilled off to give the compound of formula (I-g) as a colorless oil. 5g
Obtained. Yield 97.0%.

Reference Example 8 10 g (0.12 mol) of black methyl methyl ether
) was dissolved in 30 mm of acetone, and while stirring with a magnetic cooler using a three-necked flask, 10 mm of dimethylaminoacetonitrile was added. 1g (0.12mol
) under ice-cooling. After stirring for 2 hours under water cooling, washing is performed by decantation. As a white solid, the above formula (I
-h) Compound 20. I got 4g.

Yield 100. 0%.

Reference Example 9 Benzyl chloride Log (79.1 mmol) was dissolved in 50 mmol of acetone, placed in a three-necked flask, and mixed with 6 mmol of dimethylaminoacetonitrile at room temperature while stirring with a magnetic stirrer. By dropping 6 g (79.1 mmol) and reacting at 40°C for 3 hours, the solvent was distilled off.
16.0 g of the compound of formula (I-i) above as white crystals
Obtained. Yield 96.0%.

Reference Example 10 10g (58.5mmol) of monochrome acetic anhydride mixed with 50ml of acetone! 9. Dissolve dimethylamine in acetonitrile, place in a three-necked flask, and stir with a magnetic cooler at room temperature. 8g (I17mmol)
was added dropwise and allowed to react overnight at room temperature. By distilling off the solvent, the compound of the above formula (I-J) was obtained as a crude brown oil. Yield 55%.

Example 1 Bleaching effect of immersion bleaching with bleach> Sodium percarbonate was dissolved in 300 bottles of water at 20°C so that the effective oxygen content was 0.05%, and the amount was 1716 equivalents to the hydrogen peroxide in this solution. Activators (I-a) to (I-j) obtained in Reference Examples 1 to 10 above and tetraacetylethylenediamine (TAED) for comparison were added in the proportions shown in Table 1, and the following Using the tea-stained cloth (5 sheets) prepared in the method, immersion bleaching was performed for 30 minutes, and after washing with water and drying, the bleaching rate was determined using the following formula.

Bleaching rate of black tea contaminated cloth: Bleaching rate (%) = Reflectance is 460 for Nippon Denshoku Kogyo Wa-made NDR IOIDP
Measured using a nm filter.

Tea-contaminated cloth: Boil 80g of Nitto black tea (yellow package) in 31 ion exchange water for about 15 minutes, then strain it through a desized dry cotton cloth, soak a cotton gold cloth #2003 in this liquid, and boil it for about 15 minutes. . Remove from the heat, let stand for about 2 hours, then dry naturally. Rinse with water until the washing liquid is no longer colored, dehydrate,
After pressing, a test piece of 8 cm x 8 CI'I1 was prepared and used for an experiment.

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

Example 2 Effect of bleaching detergent using bleach and detergent> 0.133% of commercially available heavy detergent (based on anionic activator) and 0.1% of sodium percarbonate. 0.013% and 0.013% of the compound of formula (I-a) or TAED, respectively.
After washing for several minutes, washing with water, and drying, the bleaching rate was determined.

Bleaching rate is 5.8% when compound of formula (I-a) is added
, when TAED was added, it was 3.9%.

Claims (1)

[Claims] Contains (a) hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution, and (b) a cationic compound represented by the following general formula (I) or (II). A bleach composition and a bleach cleaning composition characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 and R_2 are alkyl groups or hydroxyalkyl groups, R_3 is -CH_2-O-CH_2, -CH_
2CH_2-O-CH_2CH_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -CH_2CH=CH-CH_2-, ▲ Mathematical formulas ,Chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or -CH_2-S-CH_2-, X represents an inorganic or organic counter ion) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1, R_2 is the same as above, Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R_4-O- or R_5 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R_4 is an alkyl group, R
_5 represents H or an alkyl group, X represents an inorganic or organic counterion)