JPH02169698A - Bleaching agent composition - Google Patents

Abstract

PURPOSE:To obtain an oxygen-base bleaching agent having enhanced bleaching power by mixing a peroxide and an organic peracid precursor having a specified cationic group. CONSTITUTION:A peroxide (a) (e.g. a sodium carbonate/hydrogen peroxide adduct) is mixed with a compound (b) of formula I {wherein A is of formula II, III or IV [wherein R1 and R2 are each (substituted) 1-30C alkyl, alkenyl, arylalkyl or a 4-6C heterocyclic group selected from those having two R groups bound to N, S or P: R3 is (substituted) alkyl, alkenyl, arylalkyl or a 4-6C heterocyclic group having two R groups bound to N, S or P, or a group of formula V (wherein m is 1 to 20)]; R is (substituted) 1-22C alkyl, alkenyl or (substituted) phenyl; n is 1 to 10; X is halogen} (e.g. a compound of formula VI), giving an oxygen-base bleaching agent having higher bleaching power than those conventionally used.

Description

[Detailed description of the invention] [Industrial application field] TECHNICAL FIELD This invention relates to bleach compositions.

[Conventional technology and its problems]

Chlorine bleach has restrictions on the types of fibers it can be used on, cannot be used on colored or patterned fabrics, and has a unique odor, so oxygen bleach, which does not have these drawbacks, has become extremely popular recently. I'm starting.

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 bleach activators are used in combination.

For example, nitriles such as acetonitrile, malonitrile, phthalonitrile, benzoyliminodiacetonitrile, glucose pentaacetate, octaacetyl shephrose, triacetin, sorbitol hexaacetate, acetoxybenzenesulfonate, or triacetyl cyanuric acid, methyl chloroformate, O-acetylated products such as N,N,N',N"-tetraacetylethylenediamine or tetraacetylglycolyluril, N
- N-acylated products such as benzoylimidazole, diN-acetyldimethylglyoxime, 1-phenyl-3-acetylhydantoin, N,N-diacetylaniline, N-acetyldiglykolimide, diacetylmethylene diformamide, and Phthalic anhydride, succinic anhydride,
Benzoic anhydride, glutaric anhydride, alkyl sulfuric anhydride,
acid anhydrides such as anhydrides of carboxylic acids and organic sulfonic acids; sulfonyloximes such as di(methanesulfonyl)dimethylglyoxime; acylated phosphates such as di-ethylbenzoyl phosphate; phenylsulfonate esters; Organic phosphoric acid azides such as diphenylphosphinic azide, disulfones such as diphenyldisulfone, other N-sulfonylimidazoles, cyanamides, halogenated triazines, N,N-dimethyl-
Various bleach activators, such as N-octyl-N-10-carbophenoxidedecylammonium chloride, have been investigated. However, even when these activators were used in combination, the bleaching blade was still insufficient.

[Means for solving problems]

As a result of intensive research to obtain an oxygen bleaching agent with higher bleaching properties, the present inventors discovered that the objective could be achieved by using a combination of peroxide and an organic peracid precursor having a cationic group. Completed the invention.

That is, the present invention provides a bleach composition characterized by containing a peroxide and a compound represented by the following general formula (I).

[A in formula (I) is Rz R+ Rz Rgo R, Rz (In the above general formula, R1 and R2 are optionally substituted linear and branched tJtc, ~C1° alkyl and alkenyl groups, aryl Alkyl groups (where the alkyl group has 1 to 24 carbon atoms) and C4
~ C & heterocyclic ring, in which two R groups are bonded to N, S, or P, and R1 is an optionally substituted linear or branched chain. Chain C7-C1° alkyl and alkenyl groups, arylalkyl groups (wherein the alkyl group has 1-16 carbon atoms), C1-C6 heterocycles in which the two R groups are N,
Those bonded to S or P, and -(C,H,0)
, H (having a value of 1 to 20), and R is an optionally substituted linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, Alternatively, it is a phenyl group which may be substituted, n is an integer of 1 to 10, and X represents a halogen.]Among these, preferable ones are those in formula (I) in which R+ has 1 to 1 carbon atoms;
22 alkyl group or hydroxyalkyl group, Rg, R
It is a cationic compound in which z is an alkyl group having 1 to 3 carbon atoms, and 8 is an alkyl group having 8 to 20 carbon atoms.

Such a cationic compound CI) is prepared, for example, by the following method.

A tertiary amine and a halocarboxylic acid ester are reacted using a solvent such as alcohol or acetone at room temperature or under reflux to obtain a quaternary amine compound (II).

Next, (II) is added to K in a solvent such as water or water/alcohol.
Hydrolysis is carried out using an alkali catalyst such as OJI or Na11 to obtain an amphoteric compound (nI).

Next, (III) is reacted with thionyl chloride using a solvent that does not contain a substance that reacts with acid chloride such as water or alcohol, such as dichloromethane or chloroform treated with ethanol, to obtain acid chloride (rV).

R,

R, C10 R, Cl0 (I) [R represents an optionally substituted alkyl or alkenyl group, or an optionally substituted phenyl group. ] The above-mentioned cationic organic peracid precursor used in the present invention dramatically improves the bleaching properties of peroxide.

In the present invention, the peroxide is preferably hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution.

Peroxides that generate hydrogen peroxide in aqueous solutions include organic and inorganic hydrogen peroxide adducts such as sodium carbonate/hydrogen peroxide adduct, sodium tripolyphosphate/hydrogen peroxide adduct, and sodium pyrophosphate/hydrogen peroxide. Examples include adducts, urea/hydrogen peroxide adducts, or 4NazSO1'' 2H 0 - NaC1.Also, sodium perborate hydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide, etc. There are inorganic peroxides such as

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

In the present invention, the peroxide and the organic peracid precursor are peroxide/organic peracid precursor = 99.910.1 to 20/80,
Preferably, it is used in a molar ratio of 9,515 to 50,150.

In addition to the above-mentioned essential components, the bleach composition of the present invention may contain known components that are commonly added to bleach compositions.

For example, as bilgu, sulfates, carbonates, bicarbonates,
In addition to water-soluble inorganic building blocks such as silicates and phosphates, organic building blocks such as ethylenediaminetetraacetate, tartrate, and citrate can be used. Also, magnesium sulfate, which is known as a stabilizer for peroxide or hydrogen peroxide adducts,
Magnesium salts such as magnesium silicate, magnesium chloride, magnesium fluorosilicide, magnesium oxide, magnesium hydroxide, and silicates such as sodium silicate can be used. Furthermore, if necessary, recontamination preventive agents such as carboxymethylcellulose, polyvinylpyrrolidone, and polyethylene glycol, and other ingredients such as various surfactants, enzymes, fluorescent brighteners, dyes, pigments, and fragrances are added. I can do things.

〔Effect of the invention〕

The activators according to the present invention, including organic peracids, have made it possible to achieve strong bleaching that cannot be achieved with conventional oxygen bleaching rules.

〔Example〕

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

(I) Preparation of activator ■↓ Synthesis] Ethyl bromobutyrate 78.
0 g (0.4 mol) dissolved in 300 mj of ethanol was charged, and trimethylamine (molecule i1
About 0.44 mol of 59.1) was injected under pressure. After the preparation was completed, the mixture was cooled to ambient temperature and reacted at about 20° C. for 3 hours. After the reaction is completed, the autoclave is taken out, ethanol is distilled off, and the formula (n
100.7 g (0.4 mol) of the quaternary salt of -a) were obtained. Yield 99.1%.

C1, (molecular weight 254.2) Next, in 145 g of water in which 11.5 g of KO3 was dissolved (■a
) 50.8 g (0.2 mol) was added to perform hydrolysis.

It was confirmed by +1PLc (high performance liquid chromatography) that the quaternary salt of the raw material was gone, and the mixture was neutralized with 20% sulfuric acid. After water is distilled off under reduced pressure and salt is formed, a filtration operation is performed to obtain 28.9 g (0,2
mole) was obtained. Yield 99.5%.

CHi (molecular weight 145.2)5
15.8 g (0,1
1 mol) of (I[I-a) was suspended in 250 m7 of dichloromethane, and after dropwise addition of 65 g of thionyl chloride (1119 molecules, 0.55 mol) was reacted under reflux for 1 hour. When the solvent and excess thionyl chloride were distilled off, 21.7 g (0.11 mol) of the compound of the following formula (rV-a) was obtained as a yellow crystalline substance. Yield 99
．． 6%.

CH3 (molecular weight 200.1) using a 200I117 four-day flask (rV-a
) 10.2g (0.05 mol) in 100-dichloromethane? After the mixture was dissolved, 7.2 g of sodium benzoate (11144.1.0.05 mol) was added at room temperature, and the mixture was reacted for 1 hour. When the solvent was distilled off under reduced pressure, 17.3 g of a mixture of the compound of formula (I-a) and NaCl was obtained. Further, recrystallize with acetonitrile to obtain the desired (I-a)8
．． 8g was obtained. Yield 62.1% IR (KBr:cm-'
) 1806, 1716.1602.14B5.1455.
0257.1038°1017.774,711 Reference Example 2 The following compound (I-b) was prepared eight times in the same manner as in Reference Example 1.

CH:l C1h (
I-b) Reference Example 3 The following compound (I-c) was prepared in the same manner as in Reference Example 1.

The following compound (I-d) was prepared in the same manner as in Reference Example 1.

CtHs (I-d)
No. 11Σ The following compound (I-e) was prepared in the same manner as in Reference Example 1.

C84 (Ie) Bleach compositions shown in Table 1 were prepared using activators 1-a to Ie obtained by the above preparation method, and the bleaching effect was evaluated using the method below. It is shown in Table 1 and Table 2.

[Bleaching effect of immersion bleaching (Table 1)] Dissolve sodium percarbonate in water 3001111 at 20°C so that the effective oxygen content is 0.05%, and dissolve it so that the amount of effective oxygen is equimolar to the hydrogen peroxide in this solution. After adding an activator and using black tea-stained cloth (8 x 8 CIII!, 5 sheets) prepared in the following manner, immersion bleaching was performed for 30 minutes, washed with water, and dried.
The bleaching rate was determined using the following formula.

Comparative products, magnesium monoperphthalate hexahydrate, have an effective oxygen content of 0.05%, and sodium hypochlorite has an effective chlorine content of 0.05%.
It was evaluated at 0.6%.

Bleaching rate of black tea contaminated cloth: Reflectance is N0R-101 manufactured by Nippon Heavy Industries Ltd. [IP is 46
Measured using a Qnm filter.

Black tea contaminated cloth: Boil 80 g of Nitto black tea (yellow package) in 31 ion-exchanged water for about 15 minutes, strain it through desized dry cotton cloth, soak cotton training camp #2003 cloth in this liquid, and boil it 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 no color remained in the washing solution, dehydrated, and pressed to form a 10 cm x 10 cm test piece for use in experiments.

No. table note) 1) Tetraacetylethylenediamine manufactured by Hoechst 2) Manufactured by Interox 3) Evaluation using a solution with effective oxygen concentration of 0.05%.

4) Evaluation using a solution with an effective chlorine concentration of 0.06%.

Abbreviation for balance amount to make the entire book B 100.

[When used in combination with detergent (Table 2)] 0.133% commercially available heavy agent, product 1 of the present invention listed in Table 1
~5. Turbotome was applied to a cleaning solution containing the bleach composition of Comparative Product 6.7.9 so that the effective oxygen concentration was 0.0033% using black tea-stained cloth (5 pieces of 8 x 8 cm) prepared by the above method. -After washing at 20℃ for 10 minutes,
After washing with water and drying, the bleaching rate was determined by the above method. Comparative product 8 was added to the detergent having the above concentration to give an effective chlorine concentration of 0.014%, and the same treatment was performed to determine the bleaching rate.

No. table Evaluated at effective oxygen concentration of 0.0033%.

Effective chlorine concentration 0.014 Evaluation in %.

Claims (1)

[Claims] 1. A bleach composition comprising a peroxide and a compound represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. whose alkyl group has 1 to 24 carbon atoms) and C_4 to C_6 heterocycles in which two R groups are N, S
or is independently selected from the group consisting of those bonded to P, and R_3 is an optionally substituted straight chain or branched chain C_1 to C_3_0 alkyl and alkenyl group, arylalkyl group (where the alkyl group is 1-16
-(C_2H_4O)_mH (having m of 1 to 20
), where R is an optionally substituted linear or branched chain having 1 to 1 carbon atoms;
22 alkyl or alkenyl group, or an optionally substituted phenyl group, n is an integer of 1 to 10, and X represents halogen. ] 2. In formula (I), R_1 is an alkyl group or hydroxyalkyl group having 1 to 22 carbon atoms, R_2 and R_3 are alkyl groups having 1 to 3 carbon atoms, and A is a ▲numeric formula, chemical formula, table, etc.▼, The bleach composition according to claim 1, wherein n is an integer of 3 to 10, and R is a phenyl group or an alkyl group having 8 to 20 carbon atoms. 3. The bleach composition according to claim 1 or 2, wherein the peroxide is hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution.