DE1804019A1 - Detergents containing optical brighteners - Google Patents

Description

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Henkel & Cie GmbH Düsseldorf, 1st Austria. October 1968

Patent department Henkelstr. 67

Dr.Wa / Ml. ■■ 1804019

D 5782 -

Patent application

D 3782
"Laundry detergents containing optical brighteners"

It is well known that polyester-based textiles can only be optically brightened very imperfectly, since these are also special The types of brighteners developed for polyester are relatively difficult to attach to the fibers. · The polyester brighteners In addition, the usual detergents are added, so there is practically no lightening, since the compounds Do not get absorbed on the fibers in the detergent solution. A progressive yellowing of the polyester fiber over time can therefore not, as is the case with other types of Paser possible, can be compensated by a washing or brightening treatment.

This problem is solved by the invention explained below. The invention relates to detergents with a content of at least one optical brightener suitable for polyesters from the class of substituted benzoxazoles, benzimidazoles and coumarins as well as cyanoanthracensi-furthermore at least one organic washing raw material from the class of nonionic, anionic and zwitterionic surface- active compounds that they at least

009820/1740

a compound from the class of the aromatic esters according to contain the following formula:

in which the symbols have the following meaning: X = -H, -OH, OCH ₃ , OC ₂ H ₅ , alkyl radical C ₁ to C ^, ·

^Y - - ^C n ^H 2n- '-f " ^C n ^H 2n- >

OZ = residue of a monohydric or dihydric alcohol or Ether alcohol or a monohydric phenol with a total of not more than 12 carbon atoms, η = a number from 1 to 5.

The content of the optical brighteners suitable for polyester fibers in the detergents should be 0.01 to 1% by weight , preferably 0.02 to 0.5% by weight. amount% and to the aromatic esters contain from 1 to 50 wt .- ^, preferably 2 to 30 weight '%, based on water-free or solvent-free Geroische - of surfactants washing raw materials 1 to 50 wt .- #, preferably 10 to 40 wt.. .

009820/1740

Suitable optical brighteners have, for example, the following structural formulas:

C-CH = CH-C

- R (I)

C-CH = * CH-C "N ^ ■ N

R ¹

R (II). ■

N-

^ S 0

(in)

CH,

(IV)

C = K

(V)

where R and R ^{1 are} hydrogen or lower alkyl radicals.

009820 / 17A0

However, the invention is not limited to the structures specified above, but all of the known structures can be used brighteners absorbed on polyester fibers can be used.

The acid residues of the esters to be used according to the invention are derived, for example, from the following acids: Phenylacetic acid, pheny! Propionic acid, pheny! Butyric acid, 2-benzoyl acetic acid, ^ -Benzoylpropionic acid, 4-benzoylbutyric acid, Phloretinic acid and its methyl ethers and the derivatives of the above alkylated on the aromatic ring Acids.

The alcohol residues can be derived from the following compounds, for example:

Methanol, ethanol, n-propanol, i-propanol, the various Isomers of butanol, pentanol and hexanol, cyclohexanol, also ethylene glycol, propylene glycol, butylene glycol and the Monomethyl and Monoäthyläthembzw. Mono-, di- and triglycol ethers of the glycols mentioned, also phenol, cresol and Benzyl alcohol.

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009820/1740

The aromatic esters are said to be colorless and insoluble in water be, which is why the number of ethylene glycol ether groups optionally contained in the esters is preferred should not be more than 2. Those compounds which do not contain any free phenolic groups are particularly suitable and which do not have a strong or unpleasant odor attached.

The aromatic esters act as so-called detergents. "Carrier", i.e. they have the effect that the optical brighteners are increasingly absorbed onto the Paser, so that with the inventive Polyester-based textiles treated with detergents have a significantly better degree of whiteness than those with textiles washed with conventional detergents.

In order to also lighten mixed fabrics made of polyester fibers with cellulose or polyamide fibers, the agents advantageously contain Brighteners of the diaminostilbene disulfonic acid type according to the following formula:

009820/1740

180A019

in which X and Y have the following meanings: NH, NH-CE ₅ , NH-CH ₂ -CH ₂ OH, CH ₃ -N-CH ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH ^ ₂ , morpholines Dimethyl morpholino, NH-CgH, NH-C ^ H ^ -SO_H, OCH ₃ , Cl, where X and Y can be identical or different. Those compounds in which X is an anilino and Y is a diethanolamino or morpholino group are particularly suitable represent.'

Optical brighteners of the diarylpyrazoline type can also be used be present according to the formula below?

Ar'-C -—- CH ₀ '■

..Ar

In this formula mean

R. a hydrogen atom, an alkyl radical or aryl radical,

which may be substituted,

Ar + Ar ¹ 'Aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents «such as hydroxy»,' _ ■ · ■ · '. ¹ '. '''. -amino, carboxyl, .SuIfonsli ^ © ° - "i? l SMlf & aasaidgruppen ·. or HaIoMMM Al 74.CL,.' ■ ■

I, j5-Diary! .Pyrazolines are preferably used in which R represents a hydrogen atom.

The detergents and cleaning agents also contain at least one organic washing raw material. These include non-ionic ones Compounds, e.g. polyglycol ether derivatives of alcohols, fatty acids and alkylphenols, the 3 to JO Glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon rest included. Polyglycol ether derivatives in which the number of ethylene glycol ether groups is particularly suitable 5 to 15 and their hydrocarbon radicals differ from straight-chain, primary alcohols with 12 to 18 carbon atoms or of alkylphenols with a straight chain, 6 to 14 carbon atoms having derive. By the addition of from 5 to 15 moles of propylene oxide to the last-mentioned polyethylene glycol ethers or by transferring them to the acetals, detergents are obtained which are characterized by a particularly low vision ability.

Other low-foaming compounds are water-soluble 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Containing polyethylene oxide adducts with polypropylene glycol, ethylene diamino polypropylene glycol and alkylene-polypropylene glycol with 1 to 10 carbon atoms in the alkyl

chain in question. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

- 8-09820/1740

Examples of anionic detergent raw materials are those of the sulfonate or sulfate type / z «B. Alkylbenzenesulfonates, also olefin sulfonates, such as are obtained, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, and alkyl sulfonates, such as those obtained from n-alkanes by sulfochlorination or sulfoxidation - and subsequent hydrolysis or »neutralization or by bisulfite of olefins are available. Also suitable are ot-sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated alcohols. Further compounds of this class, which may possibly be present in the detergents, are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali salts of the monoalkyl ethers or the monofatty acid esters of glycerol monosulfuric acid ester or 1,2-dioxypropanesulfonic acid. There are also sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols! * As well as fatty acid taurides and fatty acid isethionates

-h-.ii called Masohrohsfcoffen from sulfonates and sulfate · köraaen the means also alkali elves of fatty acids ^ Äs $ = * yt-S'a wi © Alk2flb © feala @ wad Alkjlsulföbetain® wi & söJa © f © a®id, © f & m fjfp d ©? ÄPJia @ .Eisl © «ad Swlf © xii © '©

9 i & ö / I / 4 U

The anionic detergent raw materials can be in the form of sodium, potassium and ammonium salts as well as salts of organic bases, such as mono-, di- or triethanolamine. Unless the mentioned detergent compounds an aliphatic hydrocarbon radical it should preferably be straight-chain and have 8 to 22 carbon atoms. In the connections with araliphatic hydrocarbon radicals, the preferably unbranched alkyl chains contain an average of 6 to 16 Carbon atoms.

The new detergents and cleaning agents can, depending on their intended use, contain other common constituents, such as pyrophosphates, triphosphates and more highly condensed phosphates in the form of the sodium, potassium or ammonium salts. Furthermore, silicates can be present, in particular sodium silicate in which the ratio of Na ₃ O: SiO _{2 is} 1: 3.5 to 1: 1. Oxygen-releasing or active chlorine-containing bleaches such as alkali perborates, alkali percarbonates, urea perhydrate, alkali hypochlorites and chlorinated cyanuric acid or its alkali salts, stabilizers such as magnesium silicate and neutral salts such as sodium sulfate or sodium chloride can also be present as constituents of the mixture.

- 10

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Furthermore, complexing agents may be present, in particular alkali salts of aminopolycarboxylic acids and / or aminopolyphosphonic acids, such as the sodium or potassium salts of * aminotriacetic acid, ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid, triethylenetetraminohexaacetic acid, triethylenetetraminohexaacetic acid, ethylenetetraminohexaacetic acid, ethylenetetraminohexaacetic acid, ethylenetetraminohexaacetic acid, ethylenetetraminohexaacetic acid, 1-methylethylethylamino-ethylaminophosphate, 1 -Hydroxyethane »-1,1-diphosphonic acid and the higher homologues of the polyphosphonic acids mentioned» ⁵

Substances are also regulated as components of the mixture the pH value, such as bicarbonates, carbonates, hydroxides and borates of sodium or potassium, and also lactic acid and citric acidc The amount of alkaline reacting substances Including the alkali silicates and phosphates should be so dimensioned that the pH value of a usable lye 7 'to 11

The detergents according to the invention can also contain enzymes from the class of proteases * lipases and amy lases ,, dietierisefoen and vegetable origin * z. B ₀ can be obtained from digestive yeasts such as ^ Peps ^ n ^ Pancreatin ^

"■ F " "" ^! """''""ff" ■ 'Γ ·' - ■■■■ ■■■ '■''■. ■■ - · - ■ ■■ '■ "■" ■ ■■''> ■■■■ .. ■ ■ · ■ ■. <; ■■ (! Fi?!, ■ -.

Trypsin, papain and diastase. Preferably from bacterial strains or fungi, such as Bacillus subtilis and Streptomyces griseus, enzymatically obtained active ingredients are used, which have the advantage over the first-mentioned enzymes that they have the advantage over alkali, per compounds and anionic washing active substances are relatively stable and not even at temperatures between 45 ° and 70 ° are significantly inactivated.

Skin protection substances such as fatty acid mono- and dialkylolamides can also be present as components of the mixture. For use Agents used in washing machines may contain additional foam inhibitors, e.g. fatty acids or their alkali soaps with 20 to 24 carbon atoms or triazine derivatives, which by reacting 1 mole of cyanuric chloride with 2 to 5 moles of an aliphatic, straight-chain, branched or cyclic primary monoamine or by propoxylation or Butoxylation νςη melamine are available. Furthermore you can Graying inhibitors, such as sodium cellulose glycolate, disinfectants and enhancing agents, fillers, such as urea, and dyes and fragrances, may be present.

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009820/1740

The detergents and cleaning agents can be in liquid, pa-. present in rough or solid form, for example in powder or granulated form. Agents whose content of carriers, ie the esters according to the invention, exceeds 3% by weight, are expediently used as liquid or paste-like preparations. In order to achieve uniform distribution or dispersion in these agents, it is advisable to choose a weight ratio of carrier to surface-active washing substance of at least 2: 1, preferably from 1: 1 to 1: 5 contain solvents which are miscible with water for the purpose of better solubility, in particular ethanol and i-propanol and solubilizers such as the alkali salts of benzene *, toluene, xylene or ethylbenzenesulphonic acid.

In relation to anhydrous or solvent-free active ingredients) do the agents according to the invention thus * have the following composition (in percent by weight)?

01T9 8 20/174

- 50 ^ preferably 2 to 30 % carrier,

0.01-1 %, preferably 0.1-0.5 % optical

Brightener "for polyester fibers,

- 50 % preferably 10 to 40 $ of at least one compound from the class of nonionic, anionic and zwitterionic surfactants,

- 90 %, preferably 20 to 60 % inorganic

and / or organic salts,

- 50 i> preferably 1 to 30 % bleach, in particular per compounds and their mixtures with bleach activators or stabilizers,

- ·· 20 %, preferably 1 to 12 fo other detergent ingredients, • such as graying inhibitors, foam suppressants, skin protection agents, bio-silk, enzymes, optical brighteners for cellulose and polyamide fibers, solubilizers, as well as parbs and fragrances.

009820/1740

A standard detergent was used in the following examples The following composition is used (given in parts by weight) ί

Na-n-Dodecylbenesolsulfonatj,

Leyl alcohol ethoxylated (10 glycol ether groups),

Soap Ci2 "™ Cpp *

Pentanatriuratriphosphafc *

Sodium water glass j,

Magnesium silicate,

Na-ethylenediaminotetraacetate,

Perborate,

Sodium cellulose glycolate,

an optical polyester brightener of the formula III »

After adding the dissolved in ethanol or dimethylformamide. Carrier were washed samples from non-optically brightened polyester fabric in a laboratory washing machine 10 times respectively minutes at 6O ⁰ Cj, a detergent concentration of 5 g / l and a weight ratio of textile material to wash liquor of s 4 ©. The measurements of the textiles that have been photometrisoh, slad ia the following

14th Parts It Ji 45 .: It 4th ? f 1.5 Il 0.5 It 20th JI - 1.5 9t 0, .03 19th

OÄ8-20 / 1740

180A019

They show a clear increase in the white values when the aromatic esters and ethers are added.

Ex. Carrier g / i White level - No brightener, no carrier - 69> 1 - with brightener, without carrier - 85.9 1 Ethyl phenylacetate 1 9 ^, 8 2 Phenyl acetic acid phenyl ester 1 95.5 3-benzoylpropionic acid butyl 1 button 4th 3-Benzoy! Propionic acid 1 92.7 methoxypropylene ester

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009820/174

Claims (5)

Henkel & Cie GmbH - ΐβ - 180A0 19 Patent Department. D 3782 claims 1) Detergent with a content of at least one optical brightener suitable for polyester fibers from the Class of substituted benzoxazoles, benzimidazoles and coumarins as well as cyanoanthracene. furthermore at least one organic. Laundry raw material from the class of non-ionic, anionic and zwitterionic surface-active compounds, characterized in that they contain at least one Compound from the class of aromatic ethers and esters according to the following formula: ^ OZ in which the symbols have the following meaning: X = H, -OH, OCH ₃ , OC ₂ H ₅ , alkyl radical C ₁ to C ₁ ^, ^Y - - ^C n ^H 2n- '-? - ^C n ^H 2n-' OZ »residue of a monohydric or dihydric alcohol or ether alcohol or a monohydric phenol with a total of no more than 12 carbon atoms,
η = «a number from 1 to 5 · - 17 - COPY CC 98 20/1 7 /. '■ 'Patent Department
D 3782 2) Composition according to claim 1, characterized by a content arrival for polyester fibers suitable optical brighteners from 0.01 to 1 wt -.%, Of surface-active washing raw materials of 1 to 50 wt -. $> And aromatic esters of 1 to 50 weight . -%. j5) composition according to claim 1, characterized by a content of polyester fibers suitable for optical brighteners of 0.02 to 0.5 wt -.%, of surface-active detergent-based materials of 10 to 40 wt -.% and of aromatic esters of 2 to wt. -%, 4) Means according to claim 1 to 3, characterized by a. Content of aromatic esters that contain no more than 2 ethylene glycol ether groups. 5) Means according to claim 1 to J5> characterized by a Content of aromatic esters that do not contain any free phenolic groups. Henkel & C ie. GmbH. i.V. a. (Dr. Haas) (Dr. Arnold /) 009820/1740 COPt