DE1812166A1 - White detergent - Google Patents

Description

D 3751
"White detergent"

It is known detergents and cleaning agents, in particular those that contain bleaching agents containing active oxygen, complexing aminopolycarboxylic acids or their alkali salts, such as nitrilotriacetic acid (CTA), ethylenediaminotetraacetic acid (EDTA) and diethylenetriamonopentaacetic acid (DTPA) add to the stability of the bleach to increase or the optical brighteners contained in the detergents against the attack of the oxidizing agent to protect. However, certain agents adhere to these agents, especially the two most widely used compounds, NTA and EDTA Disadvantages. NTA can only inadequately protect the optical brighteners against oxidative attack, while EDTA is not completely resistant to oxidizing agents and can be oxidized to inactive compounds. Another The disadvantage is that NTA, EDTA and DTPA cause the foaming of machine detergents, behenic acid or its alkali salts contain as foam suppressants, promote in an undesirable manner, presumably for this reason, v / eil the alkaline earth metal ions are largely bound in a complex manner, so that the formation is prevented by foam-suppressing lime soaps. The above The complexing agents that get into the rivers and lakes can also greatly reduce the calcium content of the vase and thus impair the growth of the fish.

The applicant has shared the task of making detergents to develop, which can also be identified by the good resistance of the optical brighteners contained therein, without them the above-mentioned night J.f. own.

009825/1903

The invention relates to V; aschmitt /? L, containing ' surface-active substances, builder salts UAd Bleach, marked by ·. a content of

a) 0.1 to 50 percent by weight, based on the amount of an anhydrous substance, an alkali metal, Ammonium or organic ammonium salt of a Poly (N "ß-propionoic acid) ethylene: Lmins of the middle Molecular weight 500 to 200,000 and

b) 0.01 to 1.5 percent by weight of at least one optical brightener from the class of bis- (triazinyl) -4, '-'-diaminostilbene disulfonic acid derivatives and the 1,4-diaryipyrazoline derivatives.

The preparation of the polymeric N-β ~ propionic acid ethylenimines or their salts takes place according to known processes, for example by adding salts of acrylic acid, acrylic acid ester, acrylamide or acrylonitrile onto polyethyleneimines with a corresponding degree of polymerization and saponifying the compounds obtained. The polyethyleneimines can also be reacted with β-halopropionic acid or its derivatives in an alkaline medium. The compounds obtained in the manner indicated are, according to the structure of the polyethyleneimines, more or less strongly branched and, depending on the degree of alkylation, can also contain unsubstituted primary or secondary amino groups or, in the case of a reaction with S-halopropionic acid derivatives, also contain quaternary ammonium . Among the Umsetzungsproduk- * th of polyethyleneimine such products are suitable in which the vorhanden3n in Au.sgangsmaterial primary and secondary /'.minof-r-"uppen 50 to 100 '- are substituted by one ß-Garboxyäthylrest..

Linear polymers can be produced by polymerizing M- (ß-propionic acid ; er) aziridine, N- (ß-iVcpJorsäureamid) aziridine or N- (ß-propionitrile) aziridine in opposition to L ^ VJIS-

009825/1 903 _ 3 _

BAD LOCAL

Acids, such as carbon trifluoride or neutral sulfuric acid uni Tiochlietfonde Ver ^ oifunr; of the polymers with watery A Uralion was obtained. Through treatment with ion exchangers, the alkali metal salts obtained can into the iYeien Säuro.u or through the following Neutralization with ammonia or organic ammonium bases, such as mono-, di- or triethanolamine, morpholine and N-methylmorpholine, into the corresponding AT.nionium salts Be transferred.

Since the polymers with increasing molecular weight also Develop cleaning properties, preference is given to using those which have a medium molecular weight of at least 1,000, for example 1,000 to 150,000.

Suitable optical brighteners are the bis (triazinyl) -4, V-diamino-tilbene disulphonic acid derivatives suitable for lightening cellulose fibers and the 1,4-niaryipyrazoline derivatives suitable for lightening polyamide fibers. In addition, Welst3ner suitable for brightening up other types of color may be present, for example those of the type of the Kaphthotriazolstilhonsulfrnate, Xthylen-bisbenzimidaüole, Ithylon-biü-benzoxazole, Thiophene-binbenzoxazole, Dialkylaminocurnrino urd 'es Cyano ^ nthracena. These brighteners bzv /. their mixtures li-i:; on in the. shake in quantities of 0.01 Μσ 1.5 Oev; .- Ji, before un Λ zv.ar, so: «it is ur. : -υ1Γοηε "ν --nippen onthaltorje Verl ir. boys acts, in Vum ihr-'r /•lkalirr.-jV.ailr-al?:^, insh ^ nondore der iiatri'iTda.lze.

n: 9i? 25/1 903

Suitable optical brighteners of the Bi3 ~ (triazinyl) -4, V-diaminostilbene disulfonic acid type are those of the form

in which X and Y have the following meanings: NHp * NH-CI-L, NH-CH ₂ -CH ₂ OH, CH ₃ -N-CH ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH) ₂₁ morpholino , Whore thy Imorpholino, NH-C ₆ H ₅ , NH -CgH ^ -SO ₅ H, OCH ₅ , Cl,. where X and Y can be the same or different. Those compounds in which X represent an aniline and Y represent a diethanolamine or morpholino group are particularly suitable

The optical brighteners of the Diarylpyrazoilne type have the formula below

Ar "

In this formula, Ar and Ar 'mean aryl radicals, such as phenyl ,, Diphenyl or haphthyl, which can carry further substituents, like hydroxy, alkoxy, hydroxyalkyl, amino, alkyl » amino, acylamino, carboxyl, sulfonic acid and sulfonic acid groups or halogen atoms. Preferred * id.rd a 1 ^ 3-diarylpyrazoline derivative used, in which the radical Ar is a p-sulfonamidophenyl group and the radical Ar 'a p-chlorine », phenyl group represents.

009825/1903

The agents according to the invention also contain at least one further compound from the class of nonionic, anionic and zwitterionic washing active substances.

As surface-active washing active substances come in the Cases in which little foam development is important, primarily non-ionic compounds in question, including, for example, the polyglycol ether derivatives of alcohols, Fatty acids and alkylphenols count from JJ to JO Glycol ether groups and 8 to 20 carbon atoms in the Contain hydrocarbon residue. 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 having 6 to 14 carbon atoms Derive alkyl chain. By adding 3 to 15 moles of propylene oxide to the latter polyethylene glycol ethers or by converting them into the acetals, detergents are obtained which are characterized by a particularly low foaming power distinguish.

Other suitable nonionic detergent raw materials are the water-soluble, 20 to 250 ethylene glycol ether groups and Polyethylene oxide adducts containing 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to carbon atoms in the alkyl chain. The mentioned connections usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Also non-ionic compounds of the amine oxide type, and sulfoxides, which can optionally also be ethoxylated, can be used.

- 6 -009825/1903

The detergents and cleaning agents can also be anionic

Contain washing raw materials of the sulfonate or sulfate type. Primarily alkylbenzenesulfonates, for example n-dodecylbenzenesulfonate, come into consideration, furthermore olefin sulfonates, such as, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis are obtained, as well as alkyl sulfonates, as they are obtained from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. "C & -Sulf © fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols. Further Compounds of this class, possibly in the Maschmittel may be present, are the higher molecular weight sulfated Partial ethers and partial esters of polyhydric alcohols, like dlo alkali salts of monoalkyl ethers tosw. the monofatty acid ester of glycerol monosulfuric acid ester or 1,2-dihydroxypropanesulfonic acid. Sulphates also come from ethoxylated or * propoxylated petfcsaureamiden and Alkylphenols as well as fatty acid taurides and fatty acid isethionates are possible.

Other suitable anionic washing raw materials are alkali soaps of fatty acids of natural or synthetic origin, E.g. the sodium soaps made from coconut, palm kernel or tallow fatty acids. As zwitterionic washing raw materials come alkyl betaines and especially AIky! sulfobetaines in question, e.g. J5- (N, N-dimethyl-N-aIky! ammonium) -propane-1-sulfonate and 5- (N, N-dimethyl-K-alkylammonium) -2-hydroxypropane-1-sulf onat.

009825/1903

181

The anionic detergent raw materials can be in the form of the sodium, potassium and ammonium salts as well as organic salts Bases such as mono-, di- or triethanolamine are present. Provided that the washing-active nonionic, anionic ones mentioned and zwitterionic compounds have a long-chain aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In connections with araliphatic hydrocarbon radicals contain the preferably unbranched alkyl chains with an average of 6 to 16 carbon atoms.

Suitable components of the mixture are also inorganic synthesis salts, in particular condensed phosphates, such as pyrophosphates, triphosphates, tetraphosphates, trimetaphosphates, tetrametaphosphates and more highly condensed phosphates in the form of the neutral or acidic sodium, potassium or ammonium salts. Alkali metal triphosphates and their mixtures with pyrophosphates are preferably used. Furthermore, silicates are possible, in particular sodium silicate in which the ratio of Na ₃ OtSiO ₂ 1 s 3 # 5 is to 1: 1. The condensed phosphates can also be wholly or partly replaced by phosphorus-containing organic builder salts. These include the alkali or ammonium salts of aminopolyphosphonic acids, in particular aminotri (methylenephosphonic acid), ethylenediamine tetra * (methylenephosphonic acid), 1-hydroxyethane-l, 1-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and the higher homologues of the polyphosphonic acid mentioned. If necessary, low molecular weight aminopolycarboxylic acids such as NTA and EDTA or the alkali metal salts can also be present in a minor amount.

- 8 009825/1903

■■ '■; mm !!! il'ii »!!.;. '» nnpnpi ι ¹ », ¹

NeutraIsalas, such as sodium sulfate and sodium chloride, as well as substances for Regulation of the pH value into consideration, such as bicarbonates, carbonates, borates and hydroxides of sodium or potassium, also acids such as lactic acid and citric acid. The amount of alkaline reacting substances including the Alkali silicates and phosphates should be dimensioned in such a way that the pH value of a usable lye for coarse washing 9 to 12 and for delicates 6 to 9.

Through a suitable combination of different surface active " In many cases, various detergent raw materials or building salts with one another can have an effect, for example improved detergency or reduced foam «can be achieved. Such improvements are for example possible by combining anionic with nonionic and / or zwjtterionic compounds, by combining different anionic compounds with one another, by combining different non-ionic compounds shear connections with each other or by mixtures of detergent raw materials of the same type, which differ with regard to the number of carbon atoms or the number and position from double bonds or chain branches in hydrocarbon. Likewise, they can be synergistic active mixtures of inorganic and organic synthesis salts used or with the mixtures mentioned above be combined.

Depending on their intended use, the agents can contain oxygen-releasing or active chlorine-containing bleaching agents, such as alkali perborates, alkali percarbonates, alkali perphosphates, urea perhydrate, alkali hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid or their alkali metal salts, as well as their mixtures with bleach activators and stabilizers . 009825/1903.

Other suitable mixture components are graying inhibitors, e.g. sodium cellulose glyolate, as well as the water-soluble alkali salts of synthetic polymers, which contain free carboxyl groups. These include the polyesters or polyamides made from tricarboxylic and tetracarboxylic acids and dihydric alcohols or diamines, also polymeric acrylic, methacrylic, maleic, fumaric, itaconic, citracon and aconitic acid and the copolymers of the unsaturated carboxylic acids mentioned or their copolymers with olefins and vinyl ethers.

Agents which are intended for use in drum washing machines suitably contain known foam-suppressing agents Agents such as saturated fatty acids or their alkali soaps with 20 to 24 carbon atoms or triazine derivatives, by reacting 1 mole of cyanuric chloride with 2 to 5 moles of an aliphatic, straight-chain, branched or cyclic primary monoamines or by propoxylation or butoxylation of melamine.

To further improve the dirt-releasing properties of the agents according to the invention, these can also contain enzymes the class of proteases, lipases and amylases. The enzymes can be of animal or vegetable origin, e.g. obtained from digestive enzymes or yeasts, such as Pepsin, pancreatin, trypsin, papain, catalase and diastase. Preferably from bacterial strains or fungi, such as Bacillus subtilis and Streptomyces griceus, obtained enzymatic Active ingredients used that are relative to alkali, percompounds and anionic washing active substances are stable and also at temperatures between 45 ° and 70 ° C cannot yet be inactivated to any significant extent.

- 10 009825/190 3

IO

181

The detergents and cleaning agents can be liquid, pasty * or solid j for example powdery , granulated or lumpy Porjii Torliegea »Liquid preparations can contain solvents that are miscible with mass *, in particular ethanol and i-propanol, as well as solubilizers, such as the alkali algae represent benzene» * Contains toluene, xylene or stfayltoenzenesulphonic acid o To increase the visual acuity and to improve skin tolerance, alkylolamides ^ "" ie fatty acid mono- and aiäiiianolaniide, sugssstsfc are also used, the mixtures of coloring and fragrances, bactericidal active ingredients, advising against Active substances and fillers _5, for example, urea, urea, hold _e

Ϊ Lu HiTH l Jl «tlf l3 ^ 'I * ^f * t ^fl r L» * Λ * i "I

Li ¹⁴ Ms. r Wt U « ^Q I 'F <" ii £ "·, C ^ ni ^{1 1} ^ r" ^J ig

erf IfLJD * SüL> i »i En ^ jiii til ϊ -> η ι j is missing

L ° b 'lit · "- ^1" K nf · »'."> ^Uf "i'tQ and possibly"

i'tif t η! ^rT > * · 's ί °. “ One kri ™

* ι i «ijj. i * ■ " ¹ I ^ si * dlisper-

I k "ii uiil Ij« «j Vi. T ^ ir" - τ n ^ iub it j all rest

^r <cbt ^ i audit lic ¹ -nir'r, Hc "-" I 2 ^Λ ϊι j ⁴ Hr> n the enzymes «Lc den Ubrlfu L« t / a '"« ι. * ^τ ι v ^a i ; 1 , ^ ' ₉ ^ n generally the mixtures do not tend to form dust or to separate.

The poly (β-pionic acid) ethylenimine can be added to the remaining ingredients in the form of salts or free acids, in which case in the ^{latter case 1} the agent used to reduce alkaline reacting amounts to binding fertilizers in sufficient quantities Content of soda when dissolving the detergent: -.?: In water, the neutralization of free acid groups takes place. "

0 0 3 8 2 5/13 ff 3

The mixtures can thus have the following composition have, the quantities in percent by weight based on anhydrous substance:

0.1 - 50 £, preferably 0.2 to 25 % poly (NB propionic acid ) ethyleneimine or its salts »

- 50 % t preferably 2 to 50 % of at least one compound from the class of non- ionic, anionic and zwitterionic veneids «

- 80 %, preferably 20 to 60 # inorganic

and / or organic salts, - 40 %, preferably 10 to JO % bleach,

In particular per compounds and their devices with bleach activators or stabilizers *

0.01 - 1.5 % » preferably 0. x to 1 % optical brighteners,

0.1 to 20 _β Ji, preferably 0.5 to 10% of other detergent ingredients such as antiredeposition agents, skin protective agents, biocides, enzymes, solution promoters, and dyes and fragrances.

- 5 % $ preferably 0.1 to 3 % foam-suppressing

Preparations from the class of the saturated fatty acids and their alkali salts and the reaction products of cyanuric chloride and monoamines.

In the following , some detergent compositions are listed that have proven particularly effective in practice.

- 12 -

009825/1903

1 »Powdered ₃ low-foaming detergent t

- 15 # sulfonate ^{detergent raw material from the class of 9} alkyl taenzenesulfonates, »olefin sulfonates and n-alkanesulfonates,

0.5 - 5 $ AlkyXpoXygXycoXäther (Cjg-Cg-AXfcyl) or AlkyXphenolpolyglycoXäther (Cg-C. ^ - Alkyl) with 5 to 10 EthylenglycoXäthergruppön, 5 % soap Cg-Cg,

0.2 - 5 $ foam suppressants from the class of trialkyl melaraine and saturated fatty acids or their alkali soaps with 20 »24" carbon atoms,
- $ 50 of a condensed alkali metal phosphate

the class of pyro- or tripoXyphosphates,

0.1 - 25 # poly (N-ß-propionic acid) -äthylenirain or «· its AlkaXisaXze,
Sodium silicate,
Sodium perborate tetrahydrate, enzyme,

at least one optical brightening agent from the class of the diaminostilbendllsulfosic acid or ", Diarylpyrasollnderiyate,

0.1 - 30 % of an inorganic salt from the class

der carbonates., bicarbonates, borates, sulphates and chlorides of alkali metals, 4 % magnesium silicates

0.5 - 3 % Sodium CelXulosegXycolate

1 - 5 10 - 35 0 - 5 0 . 05 - 1

- 13 -

009825 / 1S03

2. Powdered, foaming detergent:

- 30 # sulfonate detergent raw material

0.5 - 10 % alkyl polyglycol ether sulfate (Cg-C ^ 1-5 ethylene glycol ether groups, - 20 % alkyl polyglycol ether (C ₁₀ -C ₁ Q-AIlCyI) or

Alkylphenol polyglycol ether (Cg-C _{12 -alkyl) with}

5-12 ethylene glycol ether groups, 0.2 - 25 5 ^ poly (N-ß-propionic acid) ethyleneimine or its

Alkali salts,

- 5 % fatty acid ethanolamide or diethanolamide, - 20 % alkali metal tripolyphosphate,
0.05-1 % of a brightener from the class of the diaryl

pyrazoline derivatives and their mixtures with polyester brighteners,
- 70 % sodium sulfate.

3.Liquid detergent:

0.5 - 10 % sulfonate detergent raw material

- 10 % alkyl polyglycol ether sulfate (Cg-C ^ -alkyl,

1-5 ethylene glycol ether groups), 0.2-25 % poly (N-fl-propionic acid) -ethyleneimine or its

Alkali salts
0.1-5% fatty acid amide glycol ether condensate

(CjQ-CjQ-alkyl, 1-10 ethylene glycol ether groups),

- 10 % solubilizer from the alkali class

salts of benzene, toluene or xylenesulphonic acid *

- 30 % neutral or acidic potassium pyrophosphate, - 10 % organic solvents from the class of Cp-C, alcohols and ether alcohols, - 1 % optical brighteners from the class of diamine <> stilbene disulfonic acid and diarylpyrazoline; father.

Remaining water, fragrances, colorings, preservatives

009825/1903 " ^l4 "

812166

A detergent of the following composition was used

(Data in percent by weight)?

8 % Na-n-Dodecylbenzenesulfonate

5 % sodium soap of fatty acids C, «- Cp ₂

3 % Oley3.alcohol polyglycol ether (10 ethylene glycol

groups)

40 % pentasodium triphosphate

5 % sodium silicate (Na ₃ O, 3 * 3 SIO ₉ )

2 fj magnesium silicate

1 % sodium cellulose glycolate

$ Sodium Perborate Tetrahydrate

8 % water

0.8 % pyrazoline-type whitening agent

0.2 % Diarainostilben type whitening agent

The lightening agents had the following structure;

Cl-

- C - CH,

(I I '

N CH,

• SO ^ NH ^

Pyrazoline type

Diaminostilbene type

009825Λ1803

15 -

2% of the sodium salts of poly (N-β-propionic acid) ethyleneimines used in Examples 1 to 3 and 2% Na nitrilotriacetate (NTA) and Na ethylenediaminotetraacetate (EDTA) were added to this agent.

By these means were washed textiles made of polyamide fiber (Perlon ^) in a laboratory washing machine, said wash liquor is heated over 15 minutes from 20 ⁰ C to 6O ⁰ C and another 15 minutes, left at this temperature. The detergent concentration was 5 g / l and the weight ratio of textile to washing liquor was 1:30. The water used had a hardness of 16 ° dH and a content of 10 ^J mol. Per liter of copper ions. The whiteness of the laundry, rinsed four times and then dried, was determined photometrically. The results are compiled in the table below. They show the superiority of the invention. according to compounds to be used.

Ex. Poly (N-ß-propionic acid) -ethy-
lenlmln (sodium salt) Whiteness after
1 wash 5 washes 1
2
4th
5 Molecular weight 1,050
"2,400
"5,000
"8,300
"14o 000 103 112
104 112
105 II ¹ *
105 115
106 114 - MTA
EDTA 100 104
103 HO

009825/1903

- 16 -

Example 6

In a household washing machine with a horizontally positioned drum, lightly soiled laundry (cotton) Washed with the detergent used in the previous examples using soft water (5 ° dH). as Addition was

a) 2 % of the poly (N-ß-propionic acid) used in Example 1> ethyleneimine with a molecular weight of 1 0.50, as the sodium salt,

b) 2 % EDTA as sodium salt

used.

The detergent concentration was 5 g / l, the Gewiohtsverhältnis of textile material to wash liquor 1: 10. The detergent solution prepared by using the composition of the invention (test a) showed no tendency to foam over, while in the comparative test (b) above 8O ⁰ C such a 'strong Foam began to develop so that foam or detergent solution flowed out of the machine.

- 17 -

009825/1903

Claims (6)

Claims 1. Detergents containing surface-active detergent. substances, building salts and bleaching agents by a content of a) 0.1 to 50 percent by weight, based on the amount of anhydrous substance, of an alkali metal, ammonium or organic ammonium salt of a poly (N-ß-propion ~ V acid) -ethylenimines with an average molecular weight of 500 to 200,000 and b) 0.01 to 1.5 percent by weight of at least one optical brightener from the class of bis (triazinyl) -4,4'-diaminostilbene disulfonic acid derivatives and the 1,4-diarylpyrazoline derivatives. 2. Means according to claim Ii, characterized in that 50 to 100 % of the amino groups present in the polyethyleneimine are substituted by a ß-carboxyethyl radical. 3. Means according to claim 1 and 2, characterized by a content of poly (N-ß-propionic acid) -ethylenimines or their salts with a molecular weight of 1000 to 150,000. 4. Means according to claim 1 to 3 «characterized by a Content of 0.2 to 25 percent by weight of salts of poly (N-ß-propionic acid) -ethylenimine. 5. A composition according to claim 1 to 3, characterized duroh a related to anhydrous substance containing 0.1 - 50 wt% ~ PQly- (Nd-propionaäure) -äthylenimin or its salts -1 -.. 50 wt »£ least a compound from the, class of nonionic, ahloni ^ chen and zwitterionisoheii Tenaide, j 10 - 8Ö 0EW »£ anorganiaghe Aufbausalae au · 4p. j
Class dfr alkali polymer phosphates, alkali silicates, alkali 009825 / 1B03 - 18 - " -18- 1812188 carbonates and alkali borates, 5- ^ 0% by weight of per compounds and their mixtures with bleach activators or Stabilizers, 0.01-1.5 wt.% Optical brighteners, 0.1-20 wt. 6. Means according to claim 1 to 3 * characterized by a content based on anhydrous substance of 0.2 to 25 wt. - $ least one Ver · bond from the class of nonionic, anionic and zwitterionic surfactants, 20 to 60 wt .- # inorganic builder salts from the class of alkali metal polymer phosphates, alkali metal silicates, alkali metal carbonates and alkali metal borates, from 10 to 30 wt -.% per compounds and their mixtures with bleach activators or stabilizers, 0.1 to 1 wt .- ^ optical brighteners, 1 to 12 wt .- ^ detergent ingredients from the class of graying inhibitors, skin care substances, bio-silk, enzymes, solubilizers and parbohydrates and fragrances as well as 0.1 up to 3 wt .- ^ foam suppressants from the class of saturated fatty acids and their alkali salts and the reaction products of cyanuric chloride and monoamines, Handle 4 Ci β. GmbH. i.V. (Dr. Haas) - (Dr. Hagel) t 009825/1903