JP2756013B2 - Bleach and bleach detergent composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a bleaching agent and a bleaching detergent composition containing an organic peracid having a cationic group or a bleaching activator.

[Problems to be solved by conventional technology and invention]

Oxygen-based bleaches that do not have these drawbacks have recently become very popular because chlorine-based bleaches have limitations on the fibers that can be used, cannot be used on colors and patterns, and have unique odors. I'm starting.

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

However, the oxygen bleaching agent has a weaker bleaching power than the chlorine bleaching agent, and various bleaching activators are used in combination.

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

[Means for solving the problem]

The present inventors have conducted intensive studies to obtain oxygen-based bleaching agents and bleaching detergents having higher bleaching power, and as a result, have found that compounds having a specific cationic group are extremely excellent as bleaching agents or bleaching activators. We have found and completed the present invention.

 That is, the present invention provides the following general formula (I)[In the formula, Q: carbon which may have an alkyl group or a hydroxyl group
An alkylene group of numbers 2 to 12,−CH_TwoCH_Two-O-CH_TwoCH_Two-Or(M: 0 to 2, R: alkyl group having 1 to 20 carbon atoms) Y₁, Y_Two: Having an alkyl group or a hydroxyl group
C1-C12 alkylene group or -CH_TwoCH_Two−
(OCH_TwoCH_Two)_n− (N: 1-5) R₁₁, R₁₂, R₁₃, R₁₄: An alkyl group having 1 to 3 carbon atoms or
Hydroxyalkyl group R₁, R_Two: Having an alkyl group or a hydroxyl group
An alkylene group having 1 to 12 carbon atoms or(P, q: 0-2) L₁, L_Two: Organic peracid by reacting with -OOH or hydrogen peroxide
Leaving group Z₁, Z_Two: Same or different inorganic or organic anionic groups
(However, in the case of a divalent anionic group, the ionic group is one kind.
You. Also, And L₁, L_TwoIf Z forms an inner salt, Z₁ , Z_Two Without
Bleaching containing an organic peracid or an organic peracid precursor represented by the formula:
And a bleaching detergent composition.

The leaving group of L ₁ and L ₂ in the general formula (I) includes:
For example, the following are mentioned.

s and t are each _{-H, -SO 3 M, -COOM,} -COOR 1, -O
H represents a halogen atom, —OR ¹ , —R ^1, or —N (R ¹ ) ₃ .A. Here, M represents an alkali metal, an alkaline earth metal, an ammonium salt, an alkanol ammonium salt or the negative charge itself, and R ¹ is H, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a hydroxyalkyl group,-(C _{2 H 4 O)} 1~5 H
Or - it represents a _{(C 3 H 6 O) 1~5} H. A represents an inorganic or organic anion. Further, s and t may be the same or different.

An oxime having the structure:

Here, R ² and R ³ have the same meaning as R ¹ and may be the same or different at the same time, but at least one is not H.

An imidooxime represented by the formula:

Here, R ¹ has the same meaning as described above, and Y is an alkylene group having 1 to 9 carbon atoms which may have a hydroxyl group,-(C ₂ H
_{4 O) 1~5 -C 2 H 4} - or - indicates a _{(C 3 H 6 O) 1~5} -C 3 H 6.

d) alkanesulfonic acid represented by -O-Y-SO ₃ M. Here, Y and M represent the same meaning as described above.

polyglycol ester represented by _{e) -O (CH 2 COO)} k H.

 Here, k represents a number from 1 to 10.

An acid anhydride represented by

Here, R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group, or an optionally substituted phenyl group.

Or An imide represented by the formula:

Here, R ¹ and Y have the same meaning as described above.

A pyrrolidonecarboxylic acid derivative represented by the formula:

Wherein R ⁵ represents M or R ^1.

A ketone derivative represented by the formula:

Here, R ¹ has the same meaning as described above, and W is —C≡N, —NO ₂ or —SO ₂ R ^1, which may be the same or different.

An enol derivative represented by

Here, R ⁶ represents R ¹ excluding H.

The organic peracid precursor of the present invention can be synthesized, for example, by the following method.

(A) A compound selected from the following 1) and a compound selected from 2) are reacted to obtain a compound having an N, N-di-lower alkylamino group at both ends.

1) dicarboxylic acids such as succinic acid, alkenyl succinic acid, adipic acid, dodecane diacid, phthalic acid, terephthalic acid and iminodiacetic acid; diamines such as ethylene diamine, propylene diamine and bisamino diethyl ether;
Polyamines such as triethylenetetramine, diols such as ethylene glycol and hexylene glycol 2) Amino groups such as N, N-dimethylaminopropylamine, N, N-dimethylethanolamine, N, N-dimethylglycine, hydroxyl groups or carboxyls N with a group,
N-Lower alkylamino compound The following is an example of a compound obtained by the above reaction.

(B) The thus obtained compound having N, N-di-lower alkylamino groups at both terminals (X is a halogen, R is the same as R ₁ and R ₂ and L is the same as L ₁ and L ₂ ), and the amino group is quaternized to react with the organic compound of the present invention. A peracid precursor is obtained. As the compound of 3), for example, And the like.

The organic peracid of the present invention is obtained by reacting a compound having an N, N-di-lower alkylamino group at both terminals with, for example, chloropropionic acid to obtain a carboxylic acid having a quaternized amino group, Then, it is obtained by reacting it with concentrated hydrogen peroxide by a method as described in JP-A-1-153674.

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 mixing ratio of the hydrogen peroxide or the peroxide (a) that generates hydrogen peroxide in an aqueous solution and the organic peracid precursor (b) is usually (a) / (b) (molar ratio). ) = 99.9
/0.1 to 20/80 is preferred, and more preferably 99/1 to 50/50. As the peroxide, sodium percarbonate, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide adduct,
Or _{4Na 2 SO 4 · 2H 2 O} 2 · NaCl, sodium monohydrate perborate, sodium perborate tetrahydrate, sodium peroxide,
Calcium peroxide and the like are exemplified. Of these, sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferred.

In the bleaching agent and the bleaching detergent composition of the present invention, in addition to the above essential components, a bleaching agent or a known component usually added to the bleaching detergent composition can be added. For example, as the builder, sulfate, carbonate, bicarbonate, silicate, water-soluble inorganic builder such as phosphate, water-insoluble inorganic builder such as zeolite, 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 silicofluoride, magnesium oxide and magnesium hydroxide, and silicic acids such as sodium silicate. Salts can be used. If necessary, carboxymethylcellulose, polyvinylpyrrolidone, a re-staining agent such as polyethylene glycol, alkyl sulfate, alkane sulfonate, alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, higher fatty acid Anionic surfactants such as soap, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl ethers, mono- or diethanolamides of higher fatty acids, nonionic surfactants such as 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.

The bleaching agent of the present invention can be appropriately mixed with a conventionally known granular detergent for clothing to obtain a bleaching detergent composition.

〔The invention's effect〕

The bleaching (cleaning) agent of the present invention not only exhibits an excellent bleaching effect, but also provides an excellent washing effect to sebum stains and mud stains.

Further, the bleach activator used in the bleaching agent and the bleaching detergent composition of the present invention is biodegradable and has high safety to the human body.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 Synthesis of compound (1) Using a 14-neck flask equipped with a cooler, a mechanical stirrer, a thermometer, and a dropping funnel, 100 g of dehydrated and dried sodium p-phenolsulfonate (MW 196.2, 0.51 mol
l), dimethylformamide 300g, pyridine 40.3g (MW7
9.1, 0.51 mol), and chloroacetic acid chloride 5 in a water bath.
7.6 g (MW 112.9, 0.51 mol) was added dropwise over about 1 hour.
One hour after maturation, dimethylformamide was distilled off under reduced pressure, and the resulting pyridine hydrochloride was washed and removed with acetone or tetrahydrofuran to give white solid compound (1).
132.5 g was obtained.

MW272.6, purity 85%, yield 81% Reference Example 2 Synthesis of compound (2) Compound (2) was synthesized in the same manner as in Reference Example 1, except that 71.9 g (MW 140.9, 0.51 mol) of chlorobutyric acid chloride was used instead of chloroacetic acid chloride.
I got

Yield: 147.8 g, MW: 300.6, purity: 83%, yield: 80% Reference Example 3 Synthesis of compound (3) Using a 14-necked flask equipped with a cooler, a mechanical stirrer, a thermometer, and a Dean Stark trap, 200 g of N, N-dimethylaminopropylamine (MW102.
2,1.96 mol) and 57.9 g (MW 118.1, 0.49 mol) of succinic acid were mixed and heated to 150 ° C. The reaction was carried out for about 10 hours while distilling off water generated by the reaction from the dehydration tube. 1 / 10N KOH
The reaction mixture was titrated with an aqueous solution (indicator: phenolphthalein), and after confirming that no unreacted carboxylic acid remained, this was distilled to obtain 121.8 g of a compound (3).

MW286.5, purity 98%, yield 85% Reference Example 4 Synthesis of compound (4) In a 14-neck flask equipped with a cooler, a mechanical stirrer, a thermometer, and a Dean-Stark trap, 200 g of diethyl adipate (MW 202.3, 0.99 mol), 352.8 g of N, N-dimethylethanolamine (MW 89.1, 3.96 mol) ) Was mixed and heated to 100 ° C. Then sodium ethylate
5.5 g was added, and the mixture was reacted for about 1 hour while distilling off ethanol produced by the reaction. Thereafter, excess N, N-dimethylethanolamine was distilled off under reduced pressure, and the residue was distilled to obtain 267.8 g of compound (4).

MW288.5, purity 96%, yield 90% Reference Example 5 Synthesis of compound (5) Octylamine 10 was placed in a 14-necked flask equipped with a cooler, mechanical stirrer, thermometer, and dropping funnel.
0 g (MW 129.2, 0.77 mol), sodium chloroacetate 198.4 g
(MW 116.5, 1.70 mol) and 300 g of ion-exchanged water
Heated to ° C. Thereafter, 226.7 g (1.70 mol) of a 30% aqueous solution of sodium hydroxide was added dropwise from the dropping funnel over about 2 hours, and aging was performed for 4 hours. After cooling, the reaction mixture was adjusted to pH 4 with a 35% hydrochloric acid aqueous solution, and water was distilled off using an evaporator. The residue was dissolved in ethanol, the precipitated sodium chloride was separated by filtration, and ethanol was distilled off under reduced pressure to obtain 178.3 g of compound (5).

MW 245.2, purity 90%, yield 85% Reference Example 6 Synthesis of compound (6) In Reference Example 3, compound (5) 13 was used instead of succinic acid.
Synthesis was carried out in exactly the same manner except that 3.5 g (MW 245.2, 0.49 mol) was used.

Yield 150.2 g, MW 413.6, purity 85%, yield 63% Reference Example 7 Synthesis of Compound (7) Using a 14-neck flask equipped with a cooler, mechanical stirrer, thermometer, and dropping funnel, chloroform
200 g and 50 g (MW100, 0.5 mol) of succinic anhydride were mixed and dissolved. Thereafter, the mixture was heated so that chloroform was slowly refluxed, and 51.1 g (MW 102.2, 0.5 mol) of dimethylaminopropylamine was dropped from the dropping funnel over about 2 hours. After cooling to room temperature, 71.4 g of thionyl chloride (MW1
19,0.6 mol) from the dropping funnel over about 1 hour.
After confirming that acid chromatography was generated by R, chloroform and excess thionyl chloride were distilled off under reduced pressure by an evaporator. Next, 200 g of fresh chloroform was added, and 44.6 g (MW 89.1, 0.5 mol) of N, N-dimethylethanolamine was added dropwise from the dropping funnel over about 1 hour while cooling in a water bath, followed by aging for 2 hours. Thereafter, 83.3 g of a 48% aqueous sodium hydroxide solution was added dropwise to neutralize the amine hydrochloride formed, and chloroform was distilled off under reduced pressure. The precipitated sodium chloride was separated by filtration. Next, the filtrate was washed several times with an aqueous sodium chloride solution, and the oil layer was distilled to obtain 61.9 g of a compound (7).

MW273.3, purity 95%, yield 43% Reference Example 8 Synthesis of compound (8) Compound (8) was obtained in the same manner as in Reference Example 4, except that diethyl adipate was replaced by dodecanedioic acid.

MW372, purity 94%, yield 91% Synthesis Example 1 Synthesis of Compound (Ia) In a 13-neck flask equipped with a condenser, a mechanical stirrer, and a thermometer, 200 g of dimethylformamide, 50 g of compound (2) (MW 300.6, 83% purity, 0.14 mol) and 20 g of compound (3) (MW 286.5, 0.07 mol) were mixed and heated to 120 ° C. After the reaction for about 10 hours, after confirming that the compound (2) had disappeared by TLC, dimethylformamide was distilled off under reduced pressure, and 200 g of acetone was added to precipitate white crystals. The crystals were collected by filtration and recrystallized several times with methanol to give Compound (Ia) 28.3.
g obtained.

MW770.7, purity 99.3%, yield 52% Synthesis Example 2 Synthesis of Compound (Ib) In a 13-neck flask equipped with a cooler, a mechanical stirrer, and a thermometer, 200 g of acetonitrile, 50 g of compound (1) (MW 272.6, 0.16 mol), and 23.4 g of compound (4) (MW2
88.5, 0.08 mol) were mixed and heated so that acetonitrile was slowly refluxed. After reacting for about 10 hours, TL
After confirming that compound (1) has disappeared by C,
Acetonitrile was distilled off under reduced pressure, and the obtained solid was recrystallized from methanol to obtain 71.1 g of a compound (Ib).

MW716.7, purity 98.4%, yield 61% Synthesis Examples 3 to 5 Compounds (6) to (8) and (2) were reacted in the same manner as in Synthesis Example 1 to give the following compound (Ic). ),
(Id) and (Ie) were obtained.

Examples Compounds (Ia) to (I-) obtained in Synthesis Examples 1 to 5
The following bleaching test was performed using e).

<Bleaching test> Measurement of bleaching effect Sodium percarbonate was dissolved in 300 ml of water at 20 ° C so that the available oxygen became 0.05%, and 1/16 of the hydrogen peroxide in this solution was dissolved.
The compounds (Ia) to (Ie) and tetraacetylethylenediamine (TAED) for comparison were added at the ratios shown in Table 1 so as to be equivalent to each other, and a black tea-contaminated cloth prepared by the following method ^* Perform immersion bleaching for 30 minutes using 5 pieces,
After washing with water and drying, the bleaching ratio was determined by the following equation.

Bleaching rate of black tea cloth: The reflectance was measured with NDR-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter. The higher the value, the higher the bleaching rate.

* Tea-contaminated cloth: 80 g of Nitto black tea (yellow package) is boiled with 3 liters of ion-exchanged water for about 15 minutes. Strained with desalted cotton,
Dip a cotton cloth # 2003 in this solution and boil for about 15 minutes.
It was lowered from the heat as it was, left to stand for about 2 hours, allowed to dry naturally, washed with water until the washing liquid did not color, dehydrated, pressed, and then used as an 8 cm × 8 cm test piece, which was subjected to the experiment.

 Table 1 shows the results of the bleaching test.

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I)[In the formula, Q: the number of carbon atoms which may have an alkyl group or a hydroxyl group
2 to 12 alkylene groups,−CH_TwoCH_Two-O-CH_TwoCH_Two-Or(M: 0 to 2, R: alkyl group having 1 to 20 carbon atoms)Y₁, Y_Two: Having an alkyl group or a hydroxyl group
C1-C12 alkylene group or -CH_TwoCH_Two− (O
CH_TwoCH_Two)_n− (N: 1-5) R₁₁, R₁₂, R₁₃, R₁₄: An alkyl group having 1 to 3 carbon atoms or ar
Droxyalkyl group R₁, R_Two: Having an alkyl group or a hydroxyl group
An alkylene group having 1 to 12 carbon atoms or(P, q: 0-2) L₁, L_Two: Reacts with -OOH or hydrogen peroxide to produce organic peracid
Leaving group Z formed₁, Z_Two: Same or different inorganic or organic anionic group (however
In the case of a divalent anionic group, the ionic group is one type.
Also, And L₁, L_TwoIf Z forms an inner salt, Z₁ , Z_Two Without
Bleaching containing an organic peracid or an organic peracid precursor represented by the formula:
And bleaching detergent compositions.