JPS63101498A - Bleaching detergent composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bleach cleaning composition containing a bleach activator, and more specifically, to an oxygen bleaching composition that is safe even for one-color patterned clothing and that is superior to bleaching blades. The present invention relates to a cleaning composition.

Bleaching agents or laundry detergents containing bleach have become popular in recent years because they can remove sebum stains from clothing and stains from tea, coffee, fruit juice, blood, etc. .

There are two types of bleach: oxidized and reduced. Oxidized bleach is commonly used because of its superior bleaching effect. Oxidizing bleaches are further divided into chlorine-based and oxygen-based bleaches, but the former cannot be used on colored and patterned items because they cause discoloration and fading of the items being washed.

It has drawbacks such as a characteristic unpleasant odor. On the other hand, oxygen bleaches are superior to chlorine bleaches in that they can be used in a wider range of applications and do not have unpleasant odors like chlorine bleaches, and are therefore suitable as household bleaches.

However, oxygen bleaches generally have inferior bleaching blades compared to chlorine bleaches, and have the drawback of requiring a considerably long treatment time to obtain a sufficient bleaching effect.

For this reason, bleaching agents based on peroxides such as percarbonates and perborates have traditionally been used in bleaching agents such as tetraacetylethylenediamine (TAEI) and tetraacetylglycoluril (TAEI).
Bleach activators such as AGU) and pentaacetylglucose (PAG) are used in combination to enhance the bleaching effect. However, these activators react with percarbonates and perborates to produce peracid, which is a relatively strong bleaching agent. The color may change or fade.

An object of the present invention is to provide a bleaching detergent composition that has an excellent bleaching effect and is safe for colored and patterned clothing.

The bleaching detergent composition of the present invention is characterized by containing the following components (a), (b), and (c), or further, component (d).

(a) 0.5 peroxide releasing hydrogen peroxide in aqueous solution
~30% by weight.

(b) 0.1 to 30% by weight of a nitrogen-containing heteroalicyclic compound in which the hydrogen atom of the secondary amino group in the heterocycle is substituted with a halogen atom.

(c) 0.001-2% inorganic cobalt salt.

Weight) Nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-
Hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid or their alkali metal salts 0.1
~10% by weight.

Peroxides that produce hydrogen peroxide in an aqueous solution of component (a) include percarbonate, perborate monohydrate and tetrahydrate, as well as pyrophosphate, citrate, sodium sulfate, and urea. and hydrogen peroxide adducts of sodium silicate are preferred.

From the viewpoint of bleach activation effect, the nitrogen-containing heteroalicyclic compound as the component (b) is contained in the bleach cleaning composition singly or in combination of 0.1 to 30% by weight, preferably 0.1 to 30% by weight. 5-1
0% by weight is added. As the halogen bonded to the nitrogen atom of the nitrogen-containing heteroalicyclic compound, any of chlorine, bromine, and iodine can be used, but chlorine is particularly desirable from the viewpoint of cost. Specific examples of these compounds include the following.

(i) 1-Chloro-piperidine derivative 1-chloro-piperidine: I2 1-chloro-2-methyl 1-chloro-3,5-1piperidine: Dimethyl-piperidine:
(Margins below) (Margins below) ○H (ii) Morihorn derivative 1-chloromorpholine: ■ Q (C) Component inorganic cobalt salts include halides,
These include sulfates, nitrates, carbonates, oxides, etc., and specific examples include cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt oxide, and cobalt ammonium chloride.

The amount of component (c) added is 0.00000000000000000000000000000000000000000000000000000.
001 to 2% by weight, preferably 0.001 to 0.001% by weight.
It is 5% by weight.

In the bleach cleaning composition of the present invention, the bleach activation effect, especially from the point of achieving the desired effect in a short processing time, (
The following specific amino acid-based chelating agents can be blended as component d).

(e) Chelating agent: at least one selected from nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, or salts thereof.

(e) The chelating agent is present in the bleaching detergent composition at 0.1 to 1
It is desirable to add 0% by weight, especially 0.5 to 5% by weight. Even if more than 10% by weight is added, no improvement in effectiveness can be expected under normal bleaching conditions).

The bleaching detergent composition of the present invention can be used as is or with conventional ingredients,
For example, the (a) component (
Component b) is powder blended, and components (C) and (d) are blended into the detergent slurry before spray drying, or (a) and (b)
) It can be suitably used by powder blending in the same way as the component. As the granular detergent, those used as normal laundry detergents can be used, and for example, they can contain the components listed in (1) to (7) below, which can be selected as appropriate depending on the intended use. be done. The granular detergent is made of a slurry containing each component as shown below, for example, with a particle size of 200 to 500 pm and an apparent specific gravity of 0.1.5 to 0.
It can be obtained by spray drying to a weight of 40 g/mQ, and desired detergent components can also be powder-blended to the spray-dried product obtained.

(1) Surfactant 1) Straight-chain or branched alkylbenzene sulfonate having an average carbon number of 10-16 alkyl group 2) Having a straight-chain or branched-chain alkyl group or alkenyl group having an average carbon number of 10-20 On average, 0.
5 to 8 moles of ethylene oxide, propylene oxide or butylene oxide or ethylene oxide/propylene oxide, = 0.1/9.9 to 9.9
Alkyl or alkenyl ether sulfates added in a ratio of 10.1 or in a ratio of ethylene oxide/butylene oxide = 0.1/9.9 to 9.910.1 3) Alkyl groups having an average carbon number of 10 to 20 or an alkyl or alkenyl sulfate having an alkenyl group 4) an olefin sulfonate having an average of 10 to 20 carbon atoms 5) an alkanesulfonate having an average of 10 to 20 carbon atoms 6) a saturated or unsaturated fatty acid having an average of 10 to 24 carbon atoms Salt 7) Having an alkyl group or alkenyl group with an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, or butylene oxide in one molecule, or ethylene oxide/propylene oxide = 0° 1/ At a ratio of 9.9 to 9.910.1 or ethylene oxide/butylene oxide = 0.1/9.
Alkyl or alkenyl ether carboxylic acid salt added at a ratio of 9 to 9.910.1 8) α-Sulfo fatty acid salt or ester represented by the following general formula (A) 03Z (wherein Y is a carbon number of 1 to 3 an alkyl group or a counterion of
Z is a counterion. R1 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ) Here, examples of the counter ion include alkali metal ions such as sodium and potassium.

9) Polyoxyethylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and added with 1 to 20 moles of ethylene oxide 10) Having an alkyl group having an average carbon number of 6 to 12, 1-2
Polyoxyethylene alkylphenyl ether to which 0 mol of ethylene oxide has been added 11) Polyoxypropylene alkyl or alkenyl ether having an average carbon number of 10 to 20 alkyl or alkenyl groups and to which 1 to 20 mol of propylene oxide has been added 12 ) An alkyl group or alkenyl group having an average carbon number of 10 to 20? Polyoxybutylene alkyl or alkenyl ether with 1 to 20 moles of butylene oxide added 13) An alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and a total of 1 to 30 moles of ethylene oxide and propylene oxide or A nonionic surfactant containing ethylene oxide and butylene oxide. The ratio of ethylene oxide to propylene oxide or butylene oxide is suitably 0.1/9.9 to 9.910.1.

14) Sucrose fatty acid ester consisting of a fatty acid with an average carbon number of 10 to 20 and sucrose 15) Fatty acid glycerin monoester consisting of a fatty acid with an average carbon number of 10 to 20 and glycerin 16) Alkyl represented by the following general formula (B) Amine oxide star R2-N→0 (B) (in the formula, R2
is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R3 and R' are an alkyl group having 1 to 3 carbon atoms.

) 17) Cationic surfactants represented by the following general formulas (C) to (E) (hereinafter referred to as blank spaces) (wherein, at least one of R5, R', R', and R' has a carbon number of 8 to 24 represents an alkyl or alkenyl group; others represent an alkyl group having 1 to 5 carbon atoms; ) (wherein R', R', R7 and X are as described above.

) (wherein Rs, R', and or as previously described.

R" is an alkylene group having 2 to 3 carbon atoms, and n is an integer of 1 to 20.) (2) Divalent metal ion scavenger 1) Orisophosphate, pyrophosphate, tripolyphosphate, hexametaphosphate, Phosphates such as phytate.

2) Ethane-1,1 diphosphonic acid, ethane-1,1,2
-triphosphonic acid, ethane-1-hydroxy-1,1-
Diphosphonic acid and its derivatives, ethanehydroxy-1
, 1°2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid and the like.

3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-
Phosphonocarboxylic acid salts such as phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid.

4) Amino acid salts such as glycine, aspartic acid, and glutamic acid.

As mentioned above, alkali metal salts are suitable as the salts 1) to 4).

5) Polyacrylic acid, polyfumaric acid, polymaleic acid,
Polyelectrolytes such as poly-α-hydroxyacrylic acid.

6) Organic acid salts such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, and carboxymethyltartaric acid. As the salt, an alkali metal salt is suitable.

7) Aluminosilicate general formula % formula %) () (In the formula, M' is an alkali metal, M' is an alkaline earth metal exchangeable with calcium, and X13' and W represent the number of moles of each component. , generally X is 0.7 to 1
．． 5°y is 1 to 3, and W is an arbitrary number. ) or amorphous aluminosilicate or a mixture thereof.

(3) Alkaline agents or inorganic electrolytes silicates, carbonates, sulfates. Alkali metals are preferred as salts.

(4) Anti-redeposition agents polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose.

(5) Enzymes Protease, lipase, amylase, cellulase.

(6) Fluorescent dye 4.4'-bis-(2-sulfostyryl)-biphenyl salt + 4.4'-bis-(4-chloro-3-sulfostyryl)-biphenyl salt, 2-(stylphenyl)naphtho Thiazole derivative, 4,4'-bis(triazole-2
-yl) stilbene derivatives, bis(triazinylamino)stilbene disulfonic acid derivatives.

(7) Fragrance 1 Pigment 2" arc button According to the present invention, discoloration and fading are prevented by using a bleach activator system that uses a specific nitrogen-containing heteroalicyclic compound and an inorganic cobalt salt in combination. As a result, an oxygen-based bleaching detergent composition that is safe for colored and patterned items and has an excellent bleaching effect can be obtained.

Further, by further blending a specific amino acid-based chelating agent as component (d), the time required to obtain the above effects can be significantly shortened, and the processing time can be shortened.

EXAMPLES In each of the following Examples, the bleaching effect and color change of each bleaching detergent was evaluated according to the following criteria. ) for 15 minutes at 50°C in a washing machine at a bath ratio of 30 times, and then dehydrated for 5 minutes.

Wash and dehydrate using the same procedure again. Next, overflow rinsing is performed for 15 minutes, followed by dehydration for 5 minutes. The overflow rinsing and dehydration operations are repeated a total of 5 times, and then air-dried to obtain a pretreated cloth.

Next, a 0.5% black tea solution was boiled for 5 minutes, and the pretreated fabric was immersed in it at a bath ratio of 30 times, boiled for 30 minutes, left at 40°C for 30 minutes, and then air-dried. (Tea cloth)
shall be.

Then, a bleaching power test is conducted using method A or method B shown below.

[Method A] Bleach cleaning agent is added to water with a hardness of 3°DH at 25°C to a concentration of 0.
．． Add the tea cloth to 8% and soak a black tea cloth in the solution at 50 times the bath ratio and leave it for 30 minutes. Then, add a cotton knitted clean cloth and water at 25°C and a hardness of 3'DH to adjust the detergent concentration to 30 times the bath ratio and 0.15%.
ter (U, S, manufactured by Testing) at a rotation speed of 1.
Wash for 10 minutes at 20 rpm. The thus treated test cloth was sequentially dehydrated for 1 minute, overflow rinsed for 1 minute, and dehydrated for 1 minute in a washing machine, and then dried by ironing to obtain a bleached cloth.

The reflectance of the pretreated cloth, black tea cloth, and bleached cloth was measured using a photoelectric reflectance photometer (Ei, REP). Carl Za
(manufactured by ISS Inc.), and the bleaching effect was determined using the following formula.

Bleaching effect: Dark wading place fox cloth 9 reflective duvet roof tile,! ) 11 Keigari 0
Reflectance of 0 pre-treated cloth - Reflectance of black tea cloth [Method B] A bleaching detergent was added to water with a hardness of 3° DI at 25°C to a concentration of 0.
Add it to make it 15%, and put black tea cloth (5an
Add 10 pieces of X 5an) and a cotton knitted clean cloth to make a bath ratio of 30 medium.

Terg-0-Tometer (IJ, S, Testi
(manufactured by NG Co., Ltd.) at a rotational speed of 12 or ρm for 10 minutes. The thus treated test cloth was sequentially dehydrated for 1 minute, overflow rinsed for 1 minute, and dehydrated for 1 minute in a washing machine, and then ironed to obtain a bleached cloth.

Then, similarly to [Method A], the reflectance of the bleached cloth is measured, and the bleaching effect is calculated.

Mouth (elephant) Specified pigment (C, 1, Reactive Red 21)
Cut the dyed cloth into 7 x 7 cm+ pieces and fix the four corners of this contaminated cloth to the frame using pins. Sprinkle 10 g of the bleaching detergent of the example and comparative example on this cloth, and
After spraying with water 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 was significantly discolored and discolored, and many spots were 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 has slightly discolored and faded, and a few spots are observed.

0 point: The area that came into contact with the bleach cleaning agent does not change color or fade at all, and no spots are observed.

Example 1 Granular detergent having the composition shown in Table 1 below, sodium percarbonate or sodium perborate monohydrate as the peroxide which releases hydrogen peroxide in aqueous solution and 1- as the activator.
Powder blend of chloronitrogen-containing alicyclic compound and inorganic cobalt salt.

The bleaching detergent compositions shown in Table 2 were prepared, and the bleaching test (A
method) and discoloration and fading tests were conducted. The obtained results are shown in the second
Shown in the table.

(Leaving space below) No.'Yo and Kasa Rin's sandals - Ikkita's father's plan (% by weight) LAS Na111 7AOS
-Na” 17 Zeolite 1~
(Type 4A) 15 Sodium silicate 1° Sodium carbonate 1° Chinopal CB S
-X*30.2 Enzyme (Alcalase 2.0T) W2O, 4 water
5 soda
Part *1) Sodium linear alkylbenzene sulfonate whose alkyl group has 12 carbon atoms *2) C□4~. 8 Sodium α-olefin sulfonate *3) Fluorescent brightener (manufactured by Ciba Geigy) x4) Enzyme:
Powder blend was applied to the spray shaft and explosion contact.

(Left below) Example 2 To the granular detergent shown in Table 1, sodium percarbonate or sodium perborate monohydrate, a 1-chloro nitrogen-containing alicyclic compound and an inorganic cobalt salt as an activator, and an aminoacetic acid-based A bleaching detergent composition shown in Table 3 was prepared by blending a chelating agent into powder, and a bleaching test (Method B) and a discoloration/fading test were conducted. The results obtained are shown in Table 3.

(Margin below)

Claims (1)

[Claims] 1. (a) Peroxide that releases hydrogen peroxide in an aqueous solution 0
．． 5 to 30% by weight, (b) 0.1 to 30% by weight of a nitrogen-containing heteroalicyclic compound in which the hydrogen atom of the secondary amino group in the heterocycle is substituted with a halogen atom, and (c) 0.1 to 30% by weight of an inorganic cobalt salt. A bleaching detergent composition characterized by containing 0.001 to 2% by weight. 2. (a) Peroxide 0 that releases hydrogen peroxide in aqueous solution
．． 5 to 30% by weight, (b) 0.1 to 30% by weight of a nitrogen-containing heteroalicyclic compound in which the hydrogen atom of the secondary amino group in the heterocycle is substituted with a halogen atom, (c) Inorganic cobalt salt 0.001 (d) nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, or an alkali metal salt thereof, or an alkali metal salt thereof. agent composition.