JPH02302498A - Liquid detergent composition - Google Patents

Abstract

PURPOSE: To provide the subject novel composition containing disulfonated dibenzofuranylbiphenyl as the optical whitening agent, being capable of preventing bleaching stops from forming and having excellent whitening effect and very good storage life.

CONSTITUTION: This composition contains 0.01-2 wt.% optical whitening agent represented by the formula [wherein X is sulfonic acid, H or a 1-4C alkyl; Y and Z are each sulfonic acid, H, a 1-4C alkyl, a 1-4C alkoxyl, a halogen, CN, phenoxyl or benzyloxy (provided that any one of X, Y and Z is sulfonic acid, and neither of the remaining two groups are sulfonic acid)].

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel detergent compositions containing in particular disulfonated dibenzofuranylbiphenyl as optical brightener, a process for their production and their use.

The use of optical brighteners in liquid detergent compositions is known. During processing, optical brighteners are adsorbed onto the textile material to be washed and have the effect of eliminating yellowing and improving whiteness due to their special light absorption/emission properties.

However, this effect also affects bleach spots (bleach spots).
h 5pots). That is, when textile materials are brought into contact with such liquid detergent compositions, for example during pre-treatment, bleach spots are formed. To solve this problem, European Patent Application No. A-167205 proposes the use of monosulfonated stilbentriazolyl, stilbentriazine or distyrylbiphenyl optical brighteners in anionic liquid detergent compositions. There is.

It has now been found that the optical brightener of the following formula can also prevent the formation of bleach spots, and that a liquid detergent composition having an excellent whitening effect and very good storage properties can be obtained.

In the formula, X is a sulfonic acid group, hydrogen or C,-C,-alkyl, and Y and Z are independently a sulfonic acid group, hydrogen, C1-
C4-alkyl, Ct C4-alkoxy, halogen, CN, phenoxy or penciloxy,
Either X, Y or Z is a sulfonic acid group i
group and that the remaining substituents are not sulfonic acid groups.

Preferred halogens are fluorine, chlorine and bromine, with chlorine being particularly preferred.

Suitable C1-C-alkyl (or C,-04-alkoxy) groups are straight-chain or branched alkyl (or alkoxy) groups.

These alkyl (or alkoxy) groups can be substituted, for example, by aryl (phenyl, naphthyl), C□-C4-alkyl, C1-C,-alkoxy, OH or CN groups.

Among the dibenzofuranylbiphenyls of formula (1), preferred are those of the following formula.

or in the formula, R8 is hydrogen, C, -C, -alkyl, chlorine, C1-04
-alkoxy, phenoxy or penciloxy, R2 is hydrogen or C,-C,-alkyl, M is hydrogen and/or an equivalent non-chromogenic cation.

M means non-chromogenic cations such as alkali metals such as lithium, sodium, potassium, or ammonium, mono-, di- or tri-ethanolammonium, mono-, di- or tri-propatur ammonium or tri- or tetra-methylammonium. Substituted or unsubstituted ammonium is preferred.

Particularly preferred are compounds of the following formula.

In the formula, R3's each independently represent hydrogen, methyl or ethyl, and M is preferably sodium or potassium.

Use these optical brighteners in one of the following ways! It is possible to build A.

a) 1 mole of the compound of formula (X) in an inert organic solvent at 20°C.
to the boiling point of the solvent used with at least a chemical equivalent of the SO:ll base complex salt. In addition,
This compound (X) may be polysubstituted, the substituent R being hydrogen, C,-C,-alkyl, C□-C1-alkoxy, halogen, phenoxy or benzyloxy, and R4 being hydrogen or means C,-C,-alkyl.

b) 1 mole of a compound of formula (X) is reacted with at least a chemical equivalent of chlorosulfonic acid in an inert Ti machine agent at a temperature of 20 to 40'C.

C) Heating the compound of formula (X) with concentrated sulfuric acid or sulfuric acid/glacial acetic acid or fuming sulfuric acid/glacial acetic acid to a temperature of 40 to 140°C.

d) 1 of 4,4°-his(halogenmethyl)hyphenyl
moles of the following formula (XI) or (Xll) (The compound of the above formula can be polysubstituted with a substituent R, where R is hydrogen, Ct -C4-alkyl, C, -C,
- means alkoxy, halogen, phenoxy or benzyloxy, M means hydrogen and/or an equivalent non-chromogenic cation, R5 means phenyl or chlorophenyl) or an annealing thereof. The bisbenzyl ether of the following formula (XIII) or (XIV) produced by etherification is cyclized with a base.

The starting compounds of formulas (X), (XI), (Xll) (7) are known or can be produced by known methods. However, method (d) requires the intermediate (Xll
It is preferable to carry out the reaction without isolating l) or (XIV) using a container method (so-called one-pot method).

In particular, compounds of formula (III) and (TV) can be prepared by method (a)
) Manufactured by.

S03/base complexes are organic bases such as dioxane or preferably nitrogen bases such as triethylamine,
N-ethyldiisopropylamine, dimethylformamide (DMF), particularly preferably pyridine, is to be understood as an addition compound of SO:I. The stability of this adduct is an important factor determining the degree of sulfonation. That is, for example, compounds of formulas (III) and (V) can be prepared using 2 to 6 moles, particularly 3 to 5 moles (based on S Off ) of the S03/pyridine complex salt per mole of the compound of formula (X). be done.

SO,/It! Base complex salts are known and can be prepared by known methods [E, E, Gilbert (E, E, G11bert).

Paper by E. P. Jones, Industrial Engineering Chemistry (Ind, Engineering, Chem, ) 49. N
o.

9, part II, +55: pages 1 et seq. (1957);
Beilstein 20. II
I/IV, 22:! See 2 l.

Examples of inert organic solvents are saturated aliphatic hydrocarbons such as gasoline, petroleum ether, refloin, etc., halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, dichlorodifluoro methane, dichlorotetrafluoroethane, etc., chlorobenzenes such as mono-, di- or trichlorobenzene, and also nitrobenzenes such as nitrobenzene, nitrotoluene, and bicyclic hydrocarbons such as E and cyclohexane, methylcyclohexane or decalin.

Compounds of formula (R1) and (1v) are prepared in particular by method (c).

The etherification of process (d) is carried out by known methods at temperatures from 60 to 140° C., in particular from 100° C. to 120° C., for example by adding 1 equivalent of the base as the tertiary amine or of the base mentioned below for the subsequent cyclization. or using formula (XI) or formula (xrr) which is already the phenate form of this base.

The reaction is carried out in a polar aprotic solvent or solvent mixture. For example, dimethylformamide, N-
It is carried out in methylpyrrolidone, hexamethylphosphoric triamide, tetramethylurea or preferably dimethylsulfoxide.

The cyclization of process (d) is also carried out in a polar aprotic solvent, preferably in the same solvent used for the etherification, and at a temperature slightly higher than that used for the etherification and in the presence of a base. It will be carried out in

Bases include, for example, quaternary ammonium bases, alkaline earth metal hydroxides, alkali metal amides, alkali metal hydrides, alkali gold carbonates, or preferably alkali metal alcoholides such as potassium tert-butylade, sodium methylate, in particular Preferably, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide or lithium hydroxide are used. The basic condensing agent is used in at least stoichiometric amount, preferably in excess.

This reaction is preferably carried out in the absence of atmospheric oxygen and under an inert gas atmosphere.

By liquid detergent compositions we mean, for example, European Patent Application Section A
-167205 or US Pat. No. 450721
9 or British Patent No. 8,712,430.

The content of the optical brightener in this liquid detergent composition is 0. Ol
2% to 2%, preferably 0.01 to 1%, most preferably 0.03 to 0.3%.

These liquid detergent compositions contain, in addition to optical brighteners, inter alia 1 to 60% anionic, nonionic, zwitterionic surfactants, and if desired cationic surfactants, and 25 to 60%. Contains 65% wood, preferably 40-55% wood. More specifically, the detergent composition contains 3 to 50%, preferably 15 to 25%, of an anionic surfactant in addition to the optical brightener.

2 to 30% nonionic surfactant, preferably 4 to 1
5%, 3 to 30% of ethoxylated or non-ethoxylated C, -C, fatty acids such as capric acid, lauric acid, myristic acid, coconut oil fatty acids, palm kernel oil fatty acids or mixtures thereof; Preferably 5
1 to 20% detergent builder, preferably 1 to 25% l
1 to 10%, and if desired 1 to 10% zwitterionic surfactants, preferably 1 to 5%, and 0.5% of quaternary ammonium, amine or amine oxide surfactants.
3% preferably 0.7 to 2%, and conventional detergent additives such as enzymes, enzyme stabilizers, antioxidants, preservatives and sterilizers, fragrances, dyes, complexing or sequestering agents, solvents, etc. Contains 1 to 10%.

Surfactants suitable for use include, for example, U.S. Pat. No. 428
No. 5841, No. 3929678, No. 428453
No. 2 and British Patent No. 2,041,986. In particular, European Patent Application Section A-1672
Particular preference is given to using the surfactants which are exemplified as preferred in No. 05, but most preferably the anionic surfactants used are ethoxylated or non-ethoxylated, for example triethanol. C, -C, a-alkyl sulfates, ClO-CI5-alkylbenzenesulfonates or mixtures thereof, in the form of amine salts, and particularly preferably used nonionic surfactants are C10-C1% fat It is a condensation product of 1 mole of alcohol and 3 to 8 moles of ethylene oxide.

Suitable builders include the preferably polycarboxylated compounds described in US Pat. No. 4,321,165 and US Pat. No. 4,284,532, such as citric acid.

In particular, liquid detergent compositions containing sulfonated dibenzofuranylbiphenyl may also contain bleaching agents, such as those described in GB 8,712,430. As bleaching agent it is preferred to use perborates.

Hereinafter, the present invention will be further explained by examples. Parts and percentages in the examples are by weight. A vitiligo spotting test was conducted in the following manner.

a) Preparation of the optical brightener/detergent composition: 0.1% of the optical brightener or optical brightener mixture (100% of active substance) is dissolved in the detergent composition. 0.6 g of this optical brightener-containing detergent composition (A)
400 m1 of water at a temperature of 0°C (hardness 10@-12
Dilute with @) (washing bath B).

b) Fix a sample piece (20 g) of bleached cotton cloth to a tension frame.

C) Pre-marked circular area (
Using a pipette, evenly apply 0.6 ml of the solution of detergent composition (A) onto the sample (diameter 5 cm). After an exposure time of 30 seconds, the fabric is placed in the washing bath (B) prepared above and washed at 30° C. for 15 minutes. Afterwards, rinse with cold water and dry at 70°C.

d) The difference in whiteness between the treated circular area and the surrounding area is measured by the method of Ganz. The difference in whiteness between the two areas is a measure of the so-called tendency to develop spots (formation of bleaching spots).

This is measured by a Zeiss RFC3 photometer on single-ply fabrics.

Actual] 1 case” 2 A liquid detergent composition having the following composition was prepared.

CII-CI3-alkylbenzenesulfonate 15 parts polyethoxylated CI4-CIs-fatty alcohol (
7 moles of ethylene oxide) 14 parts soap
10 parts ethanol
9 parts triethanolamine 5 parts sodium citrate 4 parts water
43 parts Optical brightener of the following formula 0.1 part When this composition was tested for vitiligo, only very inconspicuous white spots were produced.
The whiteness of the laundry was very high.

This detergent composition was storage stable.

A liquid detergent composition was produced in exactly the same manner as in Example 1, except that a compound of the following formula (200) was blended in place of the Migoseiyu compound (100).

The properties of this liquid detergent composition were the same as those of Example 1.

A liquid detergent composition was produced in exactly the same manner as in Example 1, except that a compound of the following formula (:100) was blended in place of the branch compound Th (100).

The properties of this liquid detergent composition were the same as those of Example 1.

Enman 1A A liquid detergent composition was produced in exactly the same manner as in Example 1, except that a compound of the following formula (400) was blended instead of compound (100).

This liquid detergent composition was extremely storage stable. In the vitiligo test, almost no white spots were produced.

(i) A liquid detergent composition was produced in exactly the same manner as in Example 1, except that a compound of the following formula (5OO) was blended in place of compound Q (100).

This liquid detergent composition was extremely storage stable. In the vitiligo test, almost no vitiligo formation was observed. The whitening effect was excellent.

A liquid detergent composition having the following composition was prepared. Triethanolamine 6.5 parts NaOH 3.5 parts Ethanol 6.5 parts Propane
1,2-diol t, S part polyethoxylated C14
-C15-1? ! Fatty alcohol (7 moles of ethylene oxide) 11.5 parts Coconut fatty acid alkyl sulfate
2.5 parts Direct button Dodecylbenzenesulfonic acid 10.5 parts Oleic acid 4.0 parts Saturated CI2
CI4 acid 10.5 parts Deionized water
43.0 parts Optical brightener of the following formula
0.1 part This liquid detergent composition was opaque, homogeneous, and storage stable. When this composition was tested for white spots, only very inconspicuous white spots were observed, and the whiteness of the laundry was very high.

A liquid detergent composition was produced in exactly the same manner as in Example 7 except that a compound of the following formula (400) was blended in place of the Mitate compound (200).

The properties of this liquid detergent composition were the same as those of Example 6.

Claims (1)

[Claims] 1. Based on the weight of the liquid detergent composition, there are formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (I) (wherein, X is a sulfonic acid group, hydrogen or C_1-C_4-alkyl , Y and Z independently of each other mean a sulfonic acid group, hydrogen, C_1-C_4-alkyl, C_1-C_4-alkoxy, halogen, CN, phenoxy or benzyloxy, provided that either X or Y or Z 0.01 to 2% by weight of an optical brightener (meaning a sulfonic acid group and the remaining substituents are not sulfonic acid groups)
A liquid detergent composition containing. 2. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, R_1 is hydrogen, C_1-C_4-alkyl, chlorine, C_
1-C_4-alkoxy, phenoxy or benzyloxy, R_2 means hydrogen or C_1-C_4-alkyl, M means hydrogen and/or an equivalent non-chromogenic cation)
2. A liquid detergent composition according to claim 1, containing an optical brightener. 3. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) (In the formula, plural R_3 independently mean hydrogen, methyl or ethyl. , M is preferably sodium or potassium. 4. The liquid detergent composition according to claim 1, which contains an optical brightener having the formula ▼ (100), which includes mathematical formulas, chemical formulas, tables, etc. 5. The liquid detergent composition according to claim 1, which contains an optical brightener having the formula ▼ (includes mathematical formula, chemical formula, table, etc.) ▼ (200). 6. The liquid detergent composition according to claim 1, which contains an optical brightener having the formula ▼ (includes mathematical formula, chemical formula, table, etc.) (300). 7. The liquid detergent composition according to claim 1, which contains an optical brightener having the formula ▲ (400), which includes mathematical formulas, chemical formulas, tables, etc. 8. The liquid detergent composition according to claim 1, which contains an optical brightener having the formula ▼ (includes mathematical formula, chemical formula, table, etc.) ▼ (500). 9. A method of using a liquid detergent composition according to any one of claims 1 to 8 for washing and pre-treating textile fabrics. 10. The method for producing a liquid detergent composition according to any one of claims 1 to 8, wherein an optical brightener, a surfactant, an auxiliary agent, a builder, a bleaching system if desired, and water are mixed to obtain a homogeneous composition. A method characterized by: