JPS6310700A - Bleaching composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a bleach composition suitably used for bleaching textiles, clothing, etc., particularly for washing and bleaching textile products.

[Conventional technology]

Conventionally, various compounds have been used as bleaching agents, such as hypochlorite, white powder, hydrogen peroxide, hydrogen peroxide adducts such as sodium percarbonate, persulfates, incyanurates, and organic peroxides. ing. Among these compounds, hydrogen peroxide and hydrogen peroxide adducts are less likely to cause discoloration or fading of colored or patterned items, so they can be used as bleaching agents for clothing, meaning they can bleach stains and dark spots caused by tea, fruit juice, cosmetics, etc. on clothing. Widely used for removal. However, these compounds generally have a problem in that their bleaching effect is low at low temperatures.

Therefore, in order to solve the above problems, various methods have been proposed in which various activators are added to carry out effective bleaching at low temperatures.

For example, activation names include a method of promoting the decomposition of hydrogen peroxide using a complex of heavy metals such as iron, manganese, and cobalt and EDTA (US Pat. No. 315,664), 23 o 2401),
A method is known in which a compound that reacts with hydrogen oxide to produce peracetic acid in a bleaching bath, such as J-Acylation (Japanese Patent Publication No. 38-10i65), is used. However, the activation effect is low in the method using heavy metal complexes, and it is impossible to achieve a sufficient low-temperature bleaching effect.Also, in the method using a peracetic acid-forming compound, although the activation effect is poor,
When trying to remove stains such as tea or fruit juice, the oxygen activity of Bath Lth is too high, so it simultaneously oxidizes the dyes and pigments present on colored clothing, resulting in discoloration and fading. It has the disadvantage of causing problems.

On the other hand, it is known that para-toluenesulfochlorosodium amide, which is one of the N-halosulfonamide transparent conductors, is used for desizing and bleaching and refining of fibers (Japanese Unexamined Patent Application Publication No. 4-118)
No. 9-110979). Furthermore, a method for stabilizing a halogen ion generating compound added to a detergent composition, specifically a hypochlorite salt, a halogenated isocyanate salt, etc. using the sulfonamide derivative (JP-A-61'L No. 4299) has been proposed. However, even if these techniques are used, it is not possible to provide a bleaching agent that has an excellent bleaching effect at low temperatures and does not cause discoloration or fading of colored fabrics.

[Problems to be Solved by the Invention] Accordingly, the present invention provides a bleaching agent composition that exhibits an excellent bleaching effect at low temperatures and that causes very little discoloration or fading on colored and patterned materials. The purpose is to provide

[Means for resolving the first point] Active oxygen species that are released from peroxygen compounds and exhibit a bleaching effect include hydroxyl radicals (・OH), -doublet oxygen (
l○2) is known. Of these, the inventors
It was discovered that H has too high an oxidizing effect and shows a high bleaching effect on both stain pigments and dye pigments, causing discoloration of colored and patterned clothing, which is problematic from a consumer science perspective. On the other hand, it was also found that the oxidation effect of '02 is milder than that of .OH, and the bleaching effect on dye pigments is low, but the bleaching effect on staining pigments is sufficiently high. Further studies were conducted based on the above knowledge, and it was discovered that -heavyt oxygen is effectively generated when hydrogen peroxide or its adduct is combined with a specific activator. Thus, the present invention was completed.

That is, the present invention provides hydrogen peroxide and/or a hydrogen peroxide adduct;
- at least one activator selected from the group of halosulfonamide compounds and N-halosulfonimide compounds.

The component hydrogen peroxide adduct used in the present invention is a compound that releases hydrogen peroxide in a water bath, and includes percarbonate, perborate, persitate, and urea hydrogen peroxide adduct. Illustrated. Incidentally, examples of the above-mentioned salts include sodium salts, potassium salts, lithium salts, calcium salts, and the like. Among these, in the present invention, it is preferable to use sodium percarbonate and sodium perborate.

The present invention is directed to the activation of a component (2) in which at least one halogen atom is bonded to the nitrogen atom of a sulfonamide or sulfonimide in one or more mixtures of hydrogen peroxide adducts and/or hydrogen peroxide. It is characterized in that it is combined with an agent.

Here, the N-halosulfonamide compound of component 0 is an aromatic halosulfonamide represented by the following general formula (I) or an aliphatic halosulfonamide represented by [■], and the N-halosulfonimide compound is Orthosulfobenzimide halides represented by the following general formula (III) are exemplified.

In the formula, R, and R2 are -H, -OH, and -F, respectively.

-○, -Or, -1, -NH2, -Noz, -CO
OH, OC, H*-, +, n are integers from 1 to 12.

R is -〇H, -0-C,) (,, Yai- N H-
C-C, H, or 1, -Cn H2Rh+.

X represents halogen.

y is Na, LiS K, -H, -0H1-F.

-α, -Br, -1, NH2, -NO2, -Coo)
I, -0CIIHt-41, n is an integer of 1-12.

, specifically as a compound represented by the above general formula, N
-Haloparadruenesulfonamide, ToI-Halobenzenesulfonamide, N-halosulfonamide, N-cycloalkyl-N-halosulfonamide, N,N-dihalo-sulfamoylbenzoic acid, N,N-'; Halopara Examples include toluenesulfonamide and N,N-dihalobenzenesulfonamide, in which the halogen is chlorine or bromine, and N-halosaccharin, which is a halosulfonimide compound.

In the present invention, among the compounds represented by the above general formula, a compound represented by the formula CI"l, R1, R
Both of 2 are -H or either R1 or R2 is -
Preferably, H1 is -CHs and y is Na5KSL+ or -H.

A particularly preferred compound is sodium N-chloroparatoluenesulfonamide (chloramine T).

The amount of the activator used as component (B) is 0.05 to 1.5 mol, preferably 0.05 mol, per 1 mol of hydrogen peroxide produced from the hydrogen peroxide or hydrogen peroxide adduct used. 1
It is desirable to use it so that it becomes 0.7 mol.

The bleaching agent composition of the present invention can be used as a bleaching agent as it is or by adding conventional ingredients. At this time, if 1 to 5% of a surfactant such as polyoxyethylene nonylphenyl ether (average oxyethylene chain length -p"-5 to 30) is added, the bleaching ingredients can penetrate into the clothing in water. This is preferable because it can promote the cleaning process and also improve the stain removal effect.The bleach composition of the present invention can also be added to powdery detergents as a bleaching effect imparting component.

The bleaching operation consists of dissolving or dispersing the composition in water and immersing the textile fabric therein. The amount of bleaching agent used at this time can be appropriately selected depending on the desired degree of bleaching. Further, a bleaching temperature of 20 to 40°C is sufficient, but it may of course be higher.

Although the details of the mechanism of action by which the bleach composition of the present invention exhibits excellent effects are unknown, it is presumed to be based on the following reasons.

That is, the activator of the present invention causes hydrolysis in water as shown in the following formula, and releases hypohalite ions (OX-).

Next, OX- reacts with hydrogen peroxide coexisting in the water as shown in the following formula to release 102.

OX-+11202X-+! -120+'O□---
・---・C2) The 102 released in the knee has a short lifespan of several microseconds in water, and is deactivated by triplet oxygen <302), which has a small bleaching activity. 9
Time for the reaction of formula (2) to bleach the stain: 02 It is necessary for the reaction of formula (1) to occur in an orderly manner and to release '02 at an appropriate rate. It is necessary to keep the hydrolysis equilibrium constant of the organic chlorine compound that undergoes hydrolysis expressed by When a chlorine compound such as nochloroin cyanurate is used, too much 102 is deposited, and most of the released 102 is deactivated, resulting in no effective bleaching effect.

By reacting an organic chlorine compound with an appropriate hydrolysis equilibrium constant with hydrogen peroxide, it is possible to release IO2 at an appropriate rate, which has a high fading effect on stain pigments and a low fading effect on dye pigments. However, it is presumed that the combination of the ingredients of the present invention and (2) meets this condition. In addition, as the component (2) used in the present invention, the hydrolysis equilibrium constant K is, for example, 4.9X10-9 (25°C) for talolamine T.
Particularly suitable results are obtained by using compounds of 5.times.10@-6, preferably 10@-9 to 10@-6.

[Effects of the Invention] According to the present invention, it is possible to obtain an excellent bleaching effect at relatively low temperatures, and at the same time, it does not cause discoloration or fading of colored patterned objects unlike when conventional activators are used. Therefore, it is extremely suitable for washing at home. Moreover, according to the present invention, not only does color and patterned fabrics not change color or fade, but also reef fibers, valves! ! Since bleaching can be performed while reducing the embrittlement of fibers, it is also suitable for bleaching industrial yarns and textiles and for bleaching in paper manufacturing processes.Therefore, the bleach composition of the present invention can of course be used in a wide range of applications. In particular, it is suitably used as a bleaching agent for clothing. Furthermore, it is useful as an additive for various detergents.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

〔Example〕

Each contaminated cloth carried out in the examples and comparative examples of the present invention,
The method for preparing the dyed cloth, the method for measuring the bleaching effect and the degree of discoloration and fading are shown below.

Preparation of contaminated cloth Add 20g of black tea to 1β of water and boil for 5 minutes. Add black tea pigment to the liquid. Add 10 sheets of purified cotton broad cloth (pretreated cloth, 20 x 30 cm) to the liquid and boil for 30 minutes to dye. Ta. Next, wring out this contaminated cloth and air dry it for 5 minutes.
It was cut to a size of 5 cm x 5 cm and subjected to a bleaching test.

Creating dyed cloth Add dye (C, 1, No, Roactive) to 450 tablespoons of water.
Red-21) 0°75gr and anhydrous sodium sulfate 13
．． A cotton broad cloth (20
After 20 minutes of holding at 60°C, 9g of sodium carbonate was added and the mixture was further held at 60°C for 60 minutes. Then washed with water, washed with 0.1% acetic acid aqueous solution,
Further, it was boiled for 5 minutes in a 0.2% anionic surfactant aqueous solution, washed with water, dried, cut into pieces of 5 x 5 cm, and subjected to a discoloration/fading test.

Bleach Test Method (i) For Bleach Compositions Hydrogen peroxide or a hydrogen peroxide adduct and an activator were dissolved in 200 ffl'l of water at 25°C.

Next, five pieces of tea-stained cloth were added to this bath, bleached for 30 minutes, washed with water, and dried to obtain bleached cloth.

The reflectance of the pretreated cloth, tea-stained cloth, and bleached cloth was measured using a photoelectric reflectance monitor (manufactured by BLREPHOCART Zeiss), and the bleaching rate (%) was determined using the following formula (3). .

01) In the case of a bleaching detergent composition, the bleaching detergent is added to water with a hardness of 3°DH at 25°C to a concentration of 0.
．． A black tea-contaminated cloth was immersed in the solution at a concentration of 8% and left for 30 minutes.

After that, use a clean cotton knitted cloth at 25℃, hardness 3゜OH.
of water to adjust the detergent concentration to 30 times the bath ratio and 0.15%.
Terg-0-Tometer (u, S, Te5t
ing) for 10 minutes at a rotational speed of 12 orpm. The test cloth treated in this manner was subjected to 7 steps of dehydration for 1 minute, overflow rinsing for 1 minute, and dehydration for 2 minutes in a washing machine, and then ironed.
It was called Rinpaku Evil Cloth.

The reflectivity of pre-treated cloth, tea-stained cloth) and bleached cloth is measured using a rechargeable reflective needle (εLREP) 10 arl Zeiss
The bleaching rate was determined using the following formula [3].

In this test, when the bleaching rate increases by 5%, the improvement in white discoloration can be visually determined, and an improvement in the bleaching effect is recognized in practical terms.

Discoloration and fading test method (i) For bleach compositions Prepare a bleach bath similar to the bleach test, add two pieces of dyed fabric to this bath, bleach for 30 minutes, wash with water, air dry, and then check the brightness of the dyed fabric. , hue using a color difference meter (iCtsuM manufactured by Nippon Denshoku Nigyo)
＼i D 5114 D E type), and the following formula (
4), the degree of color change ΔE was determined.

However, ΔL: Change in brightness of dyed cloth before and after drifting Δa, Δb
: 〃 Hue For I<a, the larger the number, the stronger the red, and the smaller the value, the stronger the green.b: Large numbers and direct numbers: Very yellowish (strong (・[X smaller, the stronger the blue) Changed in this test When the chromaticity ΔE is 5 or more, it can be visually determined that discoloration and fading have occurred, and it is recognized that the discoloration and fading are large in practical terms.

(11) In the case of a bleaching detergent composition Fix the four corners of the dyed cloth to a frame using screws. Sprinkle two 0.5g of each of the bleaching detergents of Examples and Comparative Examples on this cloth, and add water. After spraying and leaving for 15 minutes, wash with water and air dry. The condition of the cloth after drying was evaluated according to the following criteria, and the degree of discoloration and fading was examined.

3 points: The area that came into contact with the bleaching detergent has significantly changed color and faded.
Many spots are observed.

2 points: The area that came into contact with the bleaching detergent has discolored and faded, and spots are clearly visible.

1 point: The area that came into contact with the bleaching detergent slightly discolored and faded, with a few spots visible.

0 points: The area that came into contact with the bleaching detergent did not change color or fade at all.
No spots are observed at all.

Example 1 A bleaching test and a discoloration test were conducted using various N-halosulfonamide compounds as hydrogen peroxide adducts using sodium percarbonate as an activator, according to the method described above. The total concentration of hydrogen peroxide produced from sodium percarbonate and the activator was set to 3.7XI Q-'' mol/1, and the ratio of these amounts was set as shown in Table 1.The results are summarized in Table 1. -1.The halozone in the table is N,N-dichloro-p-sulfamoylbenzoic acid.

As is clear from Table 1, when no activator was used as a comparative example (Nal), and when dichloroisocyanuric acid Na salt, which is an organic chlorine compound with a large water decomposition equilibrium constant, was used as an activator ( Nα13) When tetraacetyl glycoluril (TAGU), a peracetic acid generating compound, is used as an activator (Nα14), excellent performance cannot be obtained in both respects due to low bleaching rate and large discoloration and fading. I understand that. On the other hand, it can be seen that the product of the present invention has a high bleaching rate but little discoloration or fading of the dye.

Example 2 A granular detergent having the following composition (Table 2), sodium perborate l hydrate as a hydrogen peroxide adduct, and various N-halosulfonamide compounds as an activating agent were mixed in powder form, Bleaching detergent compositions of samples Nα1 to Nα4 shown in Table 3 were prepared and subjected to a bleaching test and a discoloration/fading test. The obtained results are summarized in Table-3.

Table-2 (wt%) LAS-NaII 10AS
-Na"" 2AO
3-Na” 10 Zeolite (4A type) 1, 16 Sodium silicate 10 Sodium carbonate
10 Chino Pearl CB'S-X*40
．． 2 Enzyme (Aracalase 2.OT)” 0.4
water
5 Sodium sulfate
Remaining portion *1) Sodium linear alkylbenzene sulfonate with alkyl group having 12 carbon atoms *2) Sodium alkyl sulfate with C1O to 16 *3) C
14-18 α-olefins) kJt sodium chloride *4) Distylbiphenyl type fluorescent brightener *5) Enzyme was powdered after spray drying.

Example 3 N-chloro-sulfonamide Nam as an activator
, N-cyclohexyl-N-chloro-sulfonamide.
A bleaching detergent composition similar to that in Example 2 was prepared, except that Na salt or p-(N,N-dichlorosulfamoyl)benzoic acid (halosine) was used, and a bleaching test and a discoloration/fading test were conducted. As a result, excellent effects similar to those of Example 2 were obtained for each activator.

Example 4 A bleaching detergent composition was prepared in the same manner as in Example 3 except that IJum was used as the hydrogen peroxide adduct, and a bleaching test and discoloration/fading test were conducted. Excellent effects were obtained with the drug.

Claims (2)

[Claims] (1) (A) hydrogen peroxide and/or hydrogen peroxide adduct; and (B) at least one activator selected from the group of N-halosulfonamide compounds and N-halosulfonimide compounds; A bleach composition comprising: (2) The activator of component (B) is N-haloparatoluenesulfonamide, N-halobenzenesulfonamide, N
, N-dihaloparatoluenesulfonamide and N,N-
The bleach composition according to claim 1, which is one or a mixture of two or more selected from the group of dihalobenzenesulfonamides.