US3379493A

US3379493A - Activated inorganic bleaches

Info

Publication number: US3379493A
Application number: US379025A
Authority: US
Inventors: Dithmar Karl; Koblischek Peter
Original assignee: Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 1963-07-06
Filing date: 1964-06-29
Publication date: 1968-04-23
Anticipated expiration: 1985-04-23
Also published as: GB1059434A; DE1297065B; NL6407415A

Description

United States Patent 5 Claims. 61. 8-111) ABSTRACT OF THE DISCLOSURE Bleaching process for textile fibers employing a peroxidic bleaching bath activated with an acylated phosphonic acid ester or an acylated phosphinic acid which contains at least one organic group bound directly to the phosphorus atom through a carbon atom and solid peroxidic bleaching compositions containing such activators.

The present invention relates to an improved process for the treatment of natural and synthetic textile fibers, either as such or in the form of yarns, woven and knitted fabrics or articles produced therefrom, with aqueous baths containing peroxidic bleaching compounds and more particularly with such baths containing novel activating agents and compositions suitable for the preparation of such activated baths.

It is known that peroxidic compounds, such as hydrogen peroxide, sodium peroxide, sodium per-borate, sodium percarbonate, sodium perphosphate and the like, can be used in washing and bleaching baths for textile fibers of all types. However, in some instances certain difiiculties occur in their use as relatively high temperatures must be employed if the desired bleaching action is to be achieved. As a rule, temperatures almost up to boiling are used for such Washing or bleaching. Such high temperatures 'for the washing and bleaching baths require considerable heat energy and furthermore are not suited for the ordinary Washing machine.

For these reasons various so-called activators have been proposed which will permit the Washing and bleaching operations to be carried out at lower temperatures while still achieving the desired whitening effect and good spot removal. Examples of such activators, for example, are: tormamide, amides of unsaturated lower carboxylic acids, organic nitriles, anhydrides of diand poly-basic carboxylic acids, as well as anhydrides of unsaturated carboxylic acids.

Furthermore, according to US. Patent 3,073,666, acetylated alkyl phosphate esters are useful activators to inorganic penoxidic bleaches,

According to the invention it has now been found that acylated phosphonic acid esters or acylated phosphinic acids, that is, compounds Which contain organic groups lbou'nd directly to the phosphorus atom through a carbon atom and not through an intermediate oxygen atom, are good activators for inorganic per-oxidic bleaching agents. Illustrative examples of such acylated phosphonic acid esters or acylated phosphinic acids are as follows:

Acylated phosphonic acid esters Acylated phosphinic acids As indicated, the organic groups directly connected to the phosphorus atom through a carbon atom such as alkyl or aryl groups may carry sub-stituents.

The novel activators according to the invention, depending upon their composition, are liquid or solid and easily or difficultly soluble in water. The quantities of such activators required are relatively small and as a rule 0.1 to 1 mol of the activator per mol of active oxygen in the bleaching bath suflices.

Usual stabilizers, buffers, Wetting agents, detergents, protective agents for fibers and/or optical brighteners may also be added to the activated bleaching baths according to the invention.

The best action according to the invention is obtained in neutral, weakly acidic or weakly alkaline baths or, in other words, at a pH between about 3 and 11. The active oxygen content of such baths preferably is between 0.05 g. and 20 g. per liter.

The presence of the activators according to the invention in the bleaching baths causes a bleaching action to take place at relatively low temperatures. For example, bleaching actions which can only be achieved at temperatures between 70 and C. in the absence of activators can be attained in the presence of the activators at temperatures between 30 and 60 C.

It furthermore was found that mixtures of solid inorganic peroxidic bleaching compounds with activator compounds according to the invention which are solid as Well as with the other usual components of washing agents are stable at normal temperatures and therefore can be stored in a form ready for use in preparation of the aqueous activated bleaching baths.

The following examples will serve to illustrate the invention with reference to several embodiments thereof.

Example 1 A rayon staple fiber woven fabric 'was boiled in red wine and dried. The white content thereof when measured with a Zeiss-Elrepho-whiteness degree measurer against white standard 56-5 with filter 6 was 31%.

The strongly soiled fabric was washed 3 times for minutes at 60 C. in a Launder-O-Meter (Atlas) with an aqueous bath which per liter contained the following:

G. Lauryl sulfate 1.250 Sodium pyrophosphate 0.625 Sodium tripolyphosphate 0.625 Dry water glass 0.350 Sodium perborate 1 0.700 O-benzoyl-phenyl phosphonic acid ethyl ester 1.000

The pH of the bath was 7-8. After such wash the fabric had a 64.3% white content.

In comparison, when the soiled fabric was given a washing treatment under 'the same conditions with the same bath composition except for the omission of the O-benzoyl-phenyl phosphonic acid ethyl ester its white content was only raised to 44.5%.

Example 2 A red wine soiled cotton woven fabric with a white content of 26% was washed 3 times for 15 minutes at 60 C. as in Example 1 with an aqueous bath which per liter contained the following:

G. Lauryl sulfate 1.250 Sodium pyrophosphate 0.625 Sodium tripolyphosphate 0.625 Dry water glass 0.350 Sodium perborate 0.700

O-benzoyl-phenyl phosphonic acid phenyl ester 1.000

Example 3 A rayon staple fiber woven fabric was boiled in red wine for 1 hour and dried. The strongly soiled fabric which had a white content was washed three times for 15 minutes at 60 C. as in Example 1 with an aqueous bath which per liter contained the following:

O-benzoyl-styryl phosphonic acid phenyl ester 1.000

After such wash the fabric had a 57.2% white content. t

In comparison, when the soiled fabric was given a washing treatment under the same conditions with the same bath composition except for the omission of the O-benzoyl-styryl phosphonic acid phenyl ester its white content was only raised to 47.2%.

The increase in whiteness content caused by the presence of the activator therefore was 10.0% steps.

' Example 4 A rayon staple fiber woven fabric was boiled in red Wine for 1 hour and dried. The strongly soiled fabric which had a 28.0% white content was washed three times for 15 minutes at 60 C. as in Example 1 with an aqueous bath which per liter contained the following:

G. Lauryl sulfate 1.250 Sodium pyrophosphate 0.625 Sodium tripolyphosphate 0.625 Dry water glass 0.350 Sodium perborate 0.700 O-benzoyl-diphenyl phosphinic acid 1.000

Example 5 A rayon staple fiber woven fabric was boiled in red wine for 1 hour and dried. The strongly soiled fabric which had a 28.0% white content was washed three times for 15 minutes at 60 C. as in Example 1 with an aqueous bath which per liter contained the following:

G. Lauryl sulfate 1.250 Sodium pyrophosphate 0.625 Sodium 'tripolyphosphate 0.625 Dry water glass 0.350 Sodium perborate 0.700 O-benzoyl-di-n'butyl phosphinic acid 1.000

After such wash the fabric had a 57.8% white content.

In comparison, when the soiled fabric was given a washing treatment under the same conditions with the same bath composition except for the omission of the O-benzoyl-di-n-butyl phosphinic acid its white content was only raised to 38.6%.

The increase in whiteness content caused by the presence of the activator therefore was 19.2% steps.

We claim:

1. In a process for the treatment of fibers with an aqueous bath containing an inorganic peroxidic bleaching agent, the step which comprises incorporating a sufiicient amount of a compound selected from the group consisting of acylated phosphonic acid esters and O-benzoylphenyl phosphonic acid ethyl ester, O-benzoyl-chlorophenyl phosphonic acid ethyl ester, O-benzoyl-phenyl phosphonic acid phenyl ester, O-benzoyl-chlorophenyl phosphonic acid phenyl ester, O-benzoyl-styryl phosphonic acid phenyl ester, O-benzoyl-diphenyl phosphinic acid and O-benzoyl-di-n-butyl phosphinic acid in such bath to activate said bleaching agent.

2. The process of claim 1 in which 0.1 to 1.0 mol of said compound is incorporated in said bath per mol of active peroxidic oxygen.

3. The process of claim 1 in which the temperature of said bath is between 30 and 60 C.

4. A solid activated peroxidic bleaching composition consisting essentially of a solid inorganic peroxidic bleaching agent and 0.1 mol of a solid compound selected from the group consisting of O-benzoyl-phenyl phosphonic acid ethyl ester, O-benzoyl-chlorophenyl phos- 5 6 phonic acid ethyl ester, O-benzoyl-phenyl phosphonic References Cited acid phenyl ester, O-benzoyl-chlorophenyl phosphonic UNITED STATES PATENTS acid phenyl ester, O-benzoyl-styryl phosphonic acid phen yl ester, O-benzoyl-diphenyl phosphinic acid and O-beu- $003910 10/199 mthmar 252 99 XR zoyl-di-n-butyl phosphinic acid. i 5 3073666 1/1903 Dlthmar 8 111 3,122,417 2/1964 Blaser et a1 252186 XR 5. The solid activated perovidic bleaching composition of claim 4 in which the quantity of said solid compound is 0.1 to 1.0 mol per mol of active oxygen in said LEON ROSDOL Puma]? Examiner peroxidic bleaching agent. M. WEINBLATT, Assistant Examiner.