JPH0253962A - Cleaning method and product for upgrading bleaching capacity in cleaning - Google Patents

Abstract

PURPOSE: To obtain a product excellent in bleaching power and suitable for washing a fabric by blending a hydrogen peroxide generating source and a specified bleach activator compound. CONSTITUTION: (A) A hydrogen peroxide generating source such as a perborate or percarbonate and (B) a bleach activator compound of formula I [where R is 7-22C; A is CO or the like; R1 is H or lower alkyl; Q is R2 SO2 OM (R2 is hydroxy-containing 1-6C alkylene; and M is H, an alkali metal or the like); (n) is 0 or 1; (x) is 2 or 3; (y) is 0-4; and B is H or Q] or formula II are blended preferably in a weight ratio B:A of 1:2 to 4:1 to obtain the objective product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cleaning methods using certain sulfonated compounds as bleach activators and to products containing the compounds and a hydrogen peroxide source.

Bleach is used in cleaning to enhance the whiteness of items to be washed. Perborates are the most common bleaching agents, and perborates break down in the cleaning solution to hydrogen peroxide, which actually has a bleaching effect. The bleaching effect of hydrogen peroxide begins at about 60°C and reaches full effect at about 90°C. Washing at this temperature consumes high energy and causes unnecessary wear on the item being washed. As a result of this, so-called bleach activators have recently been developed. Bleach activators are compounds that further react with hydrogen peroxide during the cleaning process to form peroxycarbonate, which enables bleaching at low temperatures. One example of such a bleach activator is the commercial product TAED (
tetraacetylethylenediamine), which is about 6
Provides good bleaching effect at 0°C.

According to the present invention, certain sulfonated compounds characterized by containing sulfonic groups, -8(O)2-0-nitrogen and long chain hydrocarbon groups are used as bleach activators to It turns out that bleaching blades can be strengthened. These compounds are advantageous in that they react with hydrogen peroxide to yield decomposition products that are surface-active amphoteric compounds. The bleaching effect of the sulfonated compound is expressed at about 40°C,
Very good at temperatures of about 60°C.

The invention thus relates to a method for enhancing the bleaching effect during cleaning, which consists in carrying out the cleaning in a cleaning solution containing a hydrogen peroxide source and a compound characterized by the following general formula: R3 or R-( A) -N-Q (n) [wherein,
R is a hydrocarbon group having 7 to 22 carbon atoms; A is (C(O
)) group or (OCH2CH2) group; n is O or 1; R1 is hydrogen or a lower alkyl group, and in the compound of formula (■) at least one R1 group is a lower alkyl group; or 3: y is an integer from O to 4; Q is a -R2-8(O)20-M group (R2
is an alkylene group having 1 to 6 carbon atoms that may contain a hydroxy group, M is hydrogen; an alkali metal, an alkaline earth metal,
ions from ammonium or substituted ammonium groups or -C(O)R3 groups (R3 is an alkyl group)
and -B is hydrogen or a Q group as defined above.

As a source of hydrogen peroxide, known such compounds can be used, for example perborates or percarbonates. Preferably, the hydrogen peroxide releasing compound is sodium perborate monohydrate or tetrahydrate.

By combining the hydrogen peroxide source and the sulfonated compounds according to the above formulas (1) and (2) used in the process of the present invention, the latter compound can be converted into 1402-
Upon reaction with the ions, a bersulfonic acid derivative with a bleaching edge will be formed in situ in the cleaning solution. Corresponding amphoteric compounds are obtained as decomposition products after the bleaching reaction, and since these compounds are surface active, they contribute effectively to the improvement of detergency.

In the compounds of the above formulas, R is a hydrocarbon group having 7 to 22 carbon atoms, preferably 12 to 20 carbon atoms. The hydrocarbon group R can be straight-chain or branched, saturated or unsaturated, and has a small number of alkyl or alkenyl groups (cycloalkylalkyl, arylalkyl or arylalkenyl groups, both of which have 6 carbon atoms). It is preferable that R is an alkyl group or an alkenyl group.

Compounds in which A is a carbonyl group and compounds in which n is O are more preferred than compounds in which A is an (OCH2CI2) group. R4 is hydrogen or suitably a lower alkyl group having 1 to 6 carbon atoms, preferably hydrogen or a methyl group, X is 2 or 3, and y is suitably 1°2 or 3. The R2 group is suitably an ethylene, propylene, 2-hydroxypropylene or butylene group. M is hydrogen, an ion as defined above (substituted ammonium thereby is to be understood as a 7- or trihydroxyalkylammonium, such as mono- or trihydroxyethylammonium) or -C
(O)R, is a group. M is preferably hydrogen, sodium or magnesium or a -C(O)R3 group (R3 is an alkyl group having 1 to 18 carbon atoms, suitably 1 to 10 carbon atoms). R3 preferably has 1 to 5 carbon atoms, and is most preferably a methyl group.

The most preferred compound is where n is O, R is hydrogen, X is 3,
Compounds of formula I in which y is 1 or 2, preferably 1, and all B groups are Q groups. R2 in the Q group is preferably a butylene group, and M is a sodium ion or -
Preferably, it is a C(O)R3 group (R3 is a lower alkyl group, preferably a methyl group). The hydrocarbon group R in these compounds is most preferably a CI2-CI8 alkyl or alkenyl group or a mixture thereof.

Compounds according to formula (1), when in the form of acids or salts, are sulfobetaines which are known per se and are used for surface activity. The derivative of sulfobetaine in which M is a -C(O)R3 group is a new compound, and the derivative of sulfobetaine and -C
It may be prepared by reaction with an acid anhydride, such as acetic anhydride, resulting in the (O)R3 group.

Most of the compounds of formula I are also new compounds, which are monomers of the general formula % [wherein R, A, R, , n% or suitably prepared starting from polyamines.

The preparation of compounds with R25(O)20-M groups (R2 being a methylene group) is carried out by reaction of said amine with chloromethanesulfonic acid, while compounds in which R2 is an ethylene group are prepared by reaction of said amine with e.g. It can be prepared by reaction with dichloroethane or dibromoethane and subsequent reaction with a sulfite reagent. Compounds in which R2 is an alkylene group having 3 or more carbon atoms are preferred, and most preferably R2 is a propylene or butylene group, and these compounds are produced by reaction of the amine with the corresponding alkyl sultone. In this case, this reaction is
Suitably carried out in water at a temperature of about 609C to about 90C for a period of up to about 24 hours. It is appropriate to use a 1 molar excess of up to about 10% of the sultone based on the amine. Next, the above compound is salted or -C
(O)R3 group-containing compounds can be converted by reaction with preferred acid anhydrides.

Cleaning with the bleach-enhancing and cleaning effect-enhancing compositions of the invention is carried out in a customary manner, selecting the temperature with respect to the material of the fabric to be washed; a good bleaching effect is already obtained at temperatures of about 40°C. It will be done. The I)H of the cleaning solution should suitably be 8 or higher. Since the bleach-activating compounds provide a surface-active effect, it is possible to use relatively large amounts of the compounds.

The weight ratio of said compound used as a bleach activator according to the invention to the hydrogen peroxide source is suitably in the range from 1:2 to 4=1, preferably from 1:1 to 3:1. most preferably from 2:1 to 3:1
It should be within the range. "Washing"
g) Although the term J is used in this case primarily for cleaning or cleaning textiles, other industrial or domestic applications are naturally conceivable in which the bleaching effect during cleaning according to the invention is useful.

The present invention also provides at least one hydrogen peroxide source and the above formula 1. and at least one bleach activator characterized by II and having the definitions given in these formulas. The bleaching system of the present invention is
Sources of hydrogen peroxide include known such agents. The hydrogen peroxide source is suitably a perborate or percarbonate, preferably sodium perborate monohydrate or tetrahydrate. The weight ratio of bleach activator:hydrogen peroxide source in said combination is suitably within the range 1:2 to 4=1, preferably within the range 11 to 3=1, most preferably 2 It should be within the range of :1 to 3:1.

The bleaching composition of the invention can be used in powdered detergent compositions known per se. Such compositions include surface-active compounds such as nonionic, anionic, amphoteric and cationic surfactants, builders such as polyphosphates, zeolites and NTA, optical brighteners, Foam control agents, fragrances, coloring agents, etc. can be included. Other bleach activators and/or bleaches can of course also be included. The bleaching system of the invention is suitably used in an amount of 10 to 40% by weight, preferably 20 to 35% by weight, based on the dry detergent composition.

The present invention will be illustrated in detail by the following examples, which are not intended to limit the invention. Parts and percentages refer to parts and percentages by weight, unless otherwise indicated.

[Example] The bleaching effect of the following compounds was investigated; 1. In the formula (1), R is an alkyl residue derived from coconut oil fatty acid, that is, having a hydrocarbon chain length distribution of essentially CI2/CI4, and each A sulfobetaine according to formula (1), wherein the R1 group is a methyl group and R2 is a butylene group.

2. In the following formula, R is an alkyl residue from a coconut oil fatty acid, i.e. with a hydrocarbon chain length distribution essentially of CI2/CI4, and each Q group is -(CH2)5(O
) 20H group, the formula R-NQ-(CH2) 3-NQ
A compound represented by 2. This compound was prepared as follows: the corresponding diamine was reacted with butane sultone. 20.0g (84.5mmole) of the diamine
), 1,4-butanesultone 34.5g (253,5
80 mmol'e) and water were charged to a 250 d20 flask equipped with a reflux condenser and a thermometer. The reaction was allowed to proceed for 21 hours under a nitrogen atmosphere. During this process, the initially cloudy emulsion became clear. + product
It was recrystallized three times by dissolving in decanol at 70°C to +90°C and then precipitated with petroleum ether at low temperature. 27.6 g of product was obtained, which is 51%
This corresponds to a yield of

The product was analyzed by IR, 1195-1170 cm
-s (o) at -' and 104104O' respectively
Two peaks characteristic of 2- and one peak characteristic of -8-0- at 605 cm-' are obtained, which is in complete agreement with data described in the literature.

The products are also surfactants and this is demonstrated by their surface tension. The surface tension of the product is
Du No. 0.1% solution at 25°C.
4117 was determined by the ring of Uf). The surface tension of Compound 1 was measured to be 40 mNm-' and the surface tension of Compound 2 was measured to be 48 mNm-'. These values are compared to the surface tension of water (72 mNm') and the surface tension of lauryl alkyl sulfonate, a well-known surfactant (37 mNm').
-') can be compared.

The bleaching effect of compounds 1 and 2 in combination with hydrogen peroxide sources was investigated as follows: 0.5 g of tannin, 5 g of sodium bicarbonate and sodium metaborate (NaBO2” 41 (20) A solution containing 1.68 g was prepared. The pH of said solution was adjusted to about 105 with thorium hydroxide. For each test, 100 ml of this solution was used, to which 50 mg of sodium perborate monohydrate was added. and in solution 1 compound 1 6
3 mg and 1 g of compound 2113y in solution 2 were added, respectively. The bleach blades were evaluated by tracking the degree of decolorization of the solution by UV spectrophotometry. +60 for each exam
It was carried out at °C and the wavelength was 450 nm. Results are expressed as UV absorbance after the stated times and as the difference between the starting and ending values. For comparison, the above base solution 1
．． Solution 3 in which only 50 mg of sodium perborate hydrate was added to ODmR, 50 mg of sodium perborate in 100 g of the base solution, and a commercially available bleach activator T A
The results are shown for Solution 4 to which 20 mg of ED was added.

UV absorbance after a certain time (minutes) of solution 1. ．． 368],,],06
1.029 0.947 0.8882 1
．． 274 0.9B9 0.822 0.771. 0
．． 7433 (Reference') 1.3L41. ], 101.
Olo 0.9640.9164 (reference) 1.33 [
i 0.9990.8540.7720.721δ 0.480 0.531 0.398 0.615

Claims (1)

[Claims] 1. Hydrogen peroxide generating source and general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R is a hydrocarbon group having 7 to 22 carbon atoms; A is a (C(O)) group or a (OCH_2CH_2) group; n is O or 1; R_1 is hydrogen or a lower alkyl group, with the formula In compounds of II, at least one R
_1 group is a lower alkyl group; It is an alkylene group having 1 to 6 carbon atoms, and M
is hydrogen; an ion from an alkali metal, alkaline earth metal, ammonium or substituted ammonium group; or -
C(O)R_3 group, where R_3 is an alkyl group; B is hydrogen or a Q group as defined above] A method for enhancing the bleaching effect during washing, characterized by: 2. The bleach activator is such that n is O or A is (C(O
)) group, R is an alkyl group or alkenyl group having 7 to 22 carbon atoms, R_1 is hydrogen or a methyl group, and y is 1, 2 or 3. The method described in 1. 3. The method according to claim 1 or 2, wherein the bleach activator is a compound in which R_2 is an ethylene, propylene, hydroxypropylene or butylene group. 4. Claim 1, wherein the bleach activator is a compound in which M is hydrogen, sodium, magnesium, or -C(O)R_3 group (R_3 is an alkyl group having 1 to 5 carbon atoms). , 2 or 3. 5. Any one of claims 1 to 4, characterized in that the bleach activator is a compound of formula I in which all B groups are -R_2-S(O)_2-O-M groups. Method described. 6. The method according to any one of claims 1 to 5, wherein the hydrogen peroxide generating source is a perborate. 7. Bleach activator has a general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R is a carbon number of 7 to 22 is a hydrocarbon group; A is a (C(O)) group or an (OCH_2CH_2) group; n is 0 or 1; R_1 is hydrogen or a lower alkyl group, and in compounds of formula II at least one R
_1 group is a lower alkyl group; It is an alkylene group having 1 to 6 carbon atoms, and M
is hydrogen; an ion from an alkali metal, alkaline earth metal, ammonium or substituted ammonium group; or -
C(O)R_3 group (R_3 is an alkyl group); B is hydrogen or a Q group as defined above]. A bleaching system containing an agent activator. 8. The bleach activator has n equal to O or A equal to (C(O
)) group, R is an alkyl group or alkenyl group having 7 to 22 carbon atoms, R_1 is hydrogen or a methyl group, y is 1, 2 or 3, and R_2 is ethylene, propylene, hydroxypropylene or 8. A bleaching system according to claim 7, characterized in that the compound is a butylene group. 9. The bleaching system according to claim 7 or 8, wherein the hydrogen peroxide generating source is a perborate. 10. A bleaching system according to claim 7, 8 or 9, characterized in that the weight ratio of the bleach activator to the hydrogen peroxide source is in the range from 1:2 to 4:1.