JPH01172497A - Stable detergent containing fluorescent brightener - Google Patents

Abstract

PURPOSE: To provide a detergent which has strong bleaching performance, excellent storage stability and suitability for cleaning fabric materials by combining inorganic or organic peracid (or salt) with a specific stilbene fluorescent whitening agent.

CONSTITUTION: A fluorescent whitening agent expressed by formula I (A is H, -SO₃M, halogen or phenylpyrazole-1-il; B is benzofran-2-il (when A in H), B is 2-(stibene-4-oil)-oxadiazole-5-il, etc.; R₁, R₂ are H, halogen, C₁-C₄ alkyl, alkoxy; N is H, monovalent nonocoloring cation; h is 0-2) is prepared (e.g. formula II and III). The final detergent is produced by combining the fluorescent whitening gent (I) of 0.03-0.5% and inorganic peracid (salt) (e.g. sodium percarbonate) or organic peroxide (salt) comprising diperoxydodecane-2-acid of 0.5-30%.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to storage-stable detergents containing, in addition to at least one peracid or persalt, at least one specific fluorescent brightener of the stilbene type, and to these detergents. of its use in the washing of textiles.

The content of synthetic fibers and mixed fibers in currently manufactured fibers has increased, and due to the desire not to wash colored items separately and from the point of view of energy conservation, in many countries laundry is now heated to 90°C. Clothes are no longer washed at temperatures ranging from 95°C to 95°C or at the boiling point, but are now being washed at lower temperatures. For this reason, in order to obtain a satisfactory bleaching effect even at washing temperatures of 60°C to 80°C, tetraacetylethylenediamine (TAED) was used to replace perborate, which is presently contained in ordinary detergents and acts as a bleaching agent. It has become necessary to activate with auxiliary agents such as. However, at lower wash temperatures, perborate/activator systems no longer give satisfactory results.

Therefore, 5. German patent publication number 2,756°58 for detergents containing stronger bleaching agents such as peracids
3, European Patent No. 145.438, British Patent No. 2,1
No. 41.754, No. 2.141.755, US Pat. No. 4,028,263 and British Patent No. 59.272.

These new bleaching agents already show a pronounced bleaching effect even at temperatures from 20° C., but on the one hand they decompose the usual fluorescent brighteners contained in detergents.

It has now been found that certain stilbene compounds surprisingly have excellent stability in detergents containing such strong bleaching agents.

Under average storage conditions as well as under harsh conditions (temperatures above 30°C and ambient temperatures above 60%), these particular stilbene fluorescent brighteners remain in detergents for several months. It is completely stable, or even if it decomposes, it decomposes only to the extent that it does not cause any practical problems.

Therefore, the present invention provides diperoxide dodecanedioic acid (diperoxide) as 0.5 to 30% inorganic peracid or organic peracid.
oxydodecanedioic acid) or a salt thereof, or a mixture of a peracid or a salt thereof, and 0.03 to 0.5% of a fluorescent brightener of formula (I) or a mixture thereof. Information about detergents.

(In the formula, A is a hydrogen atom, -5O, M group, a halogen atom,
Phenyl group or phenylpiracyJL/-1-i)L
t group; B is a benzofuran-2-yl group when A is a hydrogen atom, and a 2-(stilben-4-yl)-oxadiazole-5-4nt group when A is a halogen atom;
When A is a phenylpyrazol-1-yl group, it is a phenylpyrazol-1-yl group, and A is -so! When it is an M group or a phenyl group, it is a benzoxazol-2-yl group, or when A is a hydrogen atom, it is a naphthoxazol-2-yl group; R9 and R2 each independently represent a hydrogen atom,
Halogen atom, CI~C# alkyl group or C1~C4
is an alkoxy group; M is a hydrogen atom or a monovalent non-chromogenic cation; n is zero to 2; (I)
Compounds of formula contain at least one -SO,M group.

M in formula (I) is for example an alkaline earth metal such as magnesium or calcium, but preferably an alkali metal such as lithium, sodium or potassium, or ammonium, mono-, di- or triethanol-ammonium. , mono-, di- or tripropatur-ammonium, or substituted or unsubstituted ammonium groups such as tri- or tetramethyl-ammonium.

In particular, the detergents of the invention contain compounds of formulas (ff) to V) as fluorescent brighteners.

(In the formula, R is a hydrogen atom or a halogen atom, and M is the same as defined above.) I2゜t (In the formula, +R1 and R1 are hydrogen or a C1 to C# alkyl group, and M is (Same as defined above.)
owM (in the formula, 1M is the same as defined above) and/or (in the formula, 1M is the same as defined above).

All of the fluorescent brighteners of formulas (I) to V) are known and can be produced by known methods.

Peracids and their salts are inorganic or organic compounds that are described in the literature or are commercially available, and
Bleach the fibers already at temperatures from °C. A suitable organic peracid is diperoxide dodecanedioic acid (DPDDA)
It is. The amount of organic peracid used is 0 based on the total weight of detergent.
．． 5 to 10%, preferably 1 to 5%. However, highly active inorganic peracids such as persulfates and/or percarbonates can also be used. is between l and 3 based on the total weight of detergent.
0%, especially 10 to 20% is preferred. Optionally and advantageously, small amounts of catalytically active divalent metal salts are also used, as described in U.S. Pat. Nos. 4,655,782 and 4,655,953. Copper and/or manganese salts are preferred as metal salts.

It is of course also possible to use mixtures of organic and/or inorganic peracids or mixtures of their salts.

The peracid is added to the detergent by dry blending, such as an automatic screw metering device and/or a fluidized bed mixer.

The detergent is a dry detergent of normal composition. Usually, in addition to the combination of peracids and fluorescent brighteners according to the invention, detergents are used, for example, anionic, nonionic, amphoteric and/or cationic surfactants, phosphates such as sodium tripolyphosphate or its substitutes. acid salts, polycarboxylic acid salts, acrylic/maleic acid copolymers, zeolites, builders such as nitrilotriacetate and ethylenediaminetetraacetic acid, soil suspending agents such as sodium carboxymethyl cellulose, alkali metals or alkaline earth metals. silicate-like p
H regulators, foam regulators such as soaps, salts for adjusting spray drying and granulation properties such as sodium sulfate, fragrances,
and, if necessary, antistatic agents and softeners, enzymes, photobleachs, pigments and/or toning agents. These components must of course be stable to the bleaching system used.

The combination of the invention provides a detergent that satisfies numerical criteria such as washing power, soil removal and refreshing appearance of the washed product even when washing is carried out at temperatures between 20°C and 60°C. can be provided. Therefore, there is an advantage that colored items and white items can be washed together regardless of the type of fiber.

The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

The percentages herein refer to % by weight.

The detergents used in the following examples are prepared in two steps in a conventional manner.

Granules A are first prepared by drying and granulating a slurry consisting of about 1 part water and 1 part of the composition described below.

Linear dodecylbenzene 84g sulfonate tallow alcohol tetradecane - 31g ethylene glycol ether (14 moles of ethylene oxide) Sodium soap (mainly behene 37g acid and C+
a ~ C2゜) Sodium tripolyphosphate 458g Sodium silicate 79g Magnesium silicate 20g Carboxymethylcellulose 12g Ethylenediaminetetraacetate
2g sodium sulfate 2
22g (II) or V) 1g
Fluorescent whitening agent (FWA) 500% of the above granules A with residual moisture reduced to 5% by drying
15 g of peracid B (DPDDA > 15 g) is uniformly mixed in a dry state.

Storage and wiping folds The following tests were conducted on the sample of detergent D (granules A, ten peracid B) obtained above.

- For the detergent sample, FWA was immediately extracted and the absorbance was measured using a spectrophotometer to analyze the FWA content, which was used as a control value at the start of storage.

(Theoretical FWA content: FWA is 1% by weight based on basic detergent A) - A detergent sample is placed in a coated cardboard bag (box) suitable for packaging commercially available powder detergents, and the sample is heated to a pre-selected temperature. It was stored for a period of time under controlled conditions with environmental humidity. Immediately after storage, each sample was measured for its FWA content. The difference between this measured value and the value at the beginning of storage, expressed as a percentage, is the FW for the corresponding bleach in the detergent powder.
Let A be a measure of stability.

The above FWA measurement method is as follows.

The detergent powder was thoroughly homogenized by polishing, 1 g of it was taken and mixed with 200 ml of a solvent consisting of 9 parts of dimethyl sulfoxide and 1 part of water, and the resulting mixture was heated for 30 min at room temperature.
Stir for a minute. This is then centrifuged for 30 minutes. A sample of the resulting clear solution is pipetted into a 1 cm quartz cell, and the absorbance of the sample solution is measured at the maximum absorption wavelength in the ultraviolet region of a standard solution of the specific FWA. This absorbance is F
Proportional to WA depth. As long as the tests are kept under exactly the same conditions, the reproducibility of the test results is approximately ±1%.

Measure the loss rate during storage of FWA under the above conditions. Store at 2o to 25°C in a sealed bag (box). The FWA loss rate after 6 months of storage is as follows.

Amount I

Claims (1)

[Scope of Claims] 1. 0.5 to 30% of diperoxide dodecanedioic acid or a salt thereof as an inorganic peracid or an organic peracid, or a mixture of peracids or salts thereof; .5% of a fluorescent brightener of formula (I) or a mixture thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A is a hydrogen atom, -SO_3M group, halogen atom, or phenylpyrazol-1-yl group; B is
When A is a hydrogen atom, it is a benzofuran-2-yl group, and when A is a halogen atom, it is a 2-(stilben-4-yl)-
Oxadiazol-5-yl group, when A is phenylpyrazol-1-yl group, phenylpyrazol-1-yl group, when A is -SO_3M group or phenyl group, benzoxazol-2-yl group, or When A is a hydrogen atom, it is a naphthoxazol-2-yl group; R_1 and R
_2 is each independently a hydrogen atom, a halogen atom, a C_1-C_4 alkyl group, or a C_1-C_4 alkoxy group; M is a hydrogen atom or a monovalent non-color-forming cation; n is zero to 2; However, the compound of formula (I) has at least one -SO_3M group. 2. Detergent according to claim 1, containing a peracid or a salt thereof which bleaches textile materials at temperatures from 20°C. 3. The detergent according to claim 1, which contains a persulfate and/or percarbonate together with a catalyst as the peracid or persalt. 4. The detergent according to claim 1, which contains a compound of formula (II) as a fluorescent whitening agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R is a hydrogen atom or a halogen atom, and M is the same as defined in claim 1.) 5. As a fluorescent whitening agent The detergent according to claim 1, which contains a compound of formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_1 and R_2 are hydrogen atoms or C_1~
It is a C_4 alkyl group, R_3 is a -SO_3M group or a ▲ group having a numerical formula, a chemical formula, a table, etc., and M is the same as defined in claim 1. 6. The detergent according to claim 1, which contains a compound of formula (IV) as a fluorescent whitening agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, M is the same as defined in claim 1.) 7. Contains a compound of formula (V) as a fluorescent brightener. The detergent according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (V) (In the formula, M is the same as defined in claim 1.) 8. A claim for washing textile materials at a temperature of 20 to 60°C. A method using the detergent according to any one of Items 1 to 7. 9. A method for producing the detergent according to any of claims 1 to 7 by dry blending using an automatic screw metering device and/or a fluidized bed mixer.