DE2166778B2 - EMULSIFIER MIXTURE FOR CHEMICAL CLEANING AND SOLVENT ROLLING - Google Patents

Description

In general, surface-active, anionic bodies, such as alkylsulfonates, alkylarylsulfones and alkylsulfals, and surface-active, nonionic preparations, such as those produced by condensation of alkylene oxides with aliphatic alcohols, are used as emulsifiers (cleaning boosters) in chemical cleaning. Alkylphenols!) And amines. used either alone or in admixture with one another. Also acidic phosphoric acid esters of ethoxylated. higher alcohols and phenols and their salts are known alone or in a mixture with the abovementioned anionic or nonionic products as emulsifiers for the stated purpose. The same products can also be used alone or in a mixture with one another as emulsifiers in what is known as dry whale.

The disadvantage of these known emulsifiers is mainly their low water removal capacity, see above that the emulsion stability especially when used as emulsifiers in fulling in organic Solvent is not sufficient to achieve optimal Lgalitäl. Besides, the cleaner and that Dirt carrying capacity of these known emulsifiers is too low for today's requirements. Next to it will Textiles made from synthetic fibers, in particular from polyester and polyamide fibers when using the only a limited antistatic effect imparted to known emulsifiers as cleaning enhancers. A Another disadvantage of these known emulsifiers or emulsifier mixtures is that, if one Re-impregnation of the cleaned textiles is necessary, an unacceptably high impregnation influence caused by residues of these emulsifiers on the fabric.

From DT-AS 12 89 598 a method / ur dry cleaning of textiles is also known, where as Detergent booster monoesters and / or their alkali and alkylolamine salts from 1 to 2 mol on the one hand Maleic and / or phthalic anhydride and, on the other hand, 1 mol of fatty acid alkyloiamide are used will. The production of the known cleaning enhancers is cumbersome. The water-binding capacity the same is inadequate. Also with regard to the anti-static properties imparted during dry cleaning Effect, the known products are inferior to the emulsifier mixtures of the present application.

Weilerhin are from CiB-PS 10 43 488 lubricant compositions known from a predominant amount of lubricating oil (1) and a subordinate Amount of a reaction product of ethoxylated phosphoric acid esters and imidazoline compounds (2) By adding small amounts of compounds (2), the corrosion properties are increased of the lubricant improved. The use of these compounds (2) as emulsifiers for chemical cleaning and solvent mill cannot be found in the citation. Also could one such use from the prior art due to the compulsory use of large amounts cannot be derived from lubricating oil.

In the DT-OS 2161602 the use of certain products for dry cleaning and

described for the l.ösungsmitielwalke, which by reacting 1 mole of a saturated or unsaturated, Fatty acid optionally substituted by OH groups and having at least 12 carbon atoms I to 1.2 mol of a compound of the general formula

H ₂ NC ₂ H ₄

(I)

in which Λ is 2 or J and X is the group -NIIj, -Oll or a radical of the general formula

- (NH-C "H ..") z -Y

wherein / is I or 2 and Y is the group —Nil., or -Oll is, mean, at up to / ii 260 "C with cleavage of at least 1.4 mol of water and subsequent further reaction of the condensation products obtained with compounds of the general formulas

IK) OM

and or or

, (- () --- C, H., RV-O

O (H)

OH

R, (- 0 - C ₂ H ₁ RV-O O (III)

in which \ equals O to 12, the group Ri is an alkyl radical with 2 to 7 carbon atoms (with ν = O), an alkyl radical with 4 to 18 carbon atoms (with v = 1 to 12) or an alkylphenyl radical with an alkyl radical of at least 3 carbon atoms and the radical R ^{1 represents} a hydrogen atom or a methyl radical.

Particularly useful are emulsifiers which are obtained by the condensation products obtained before the further reaction with the compounds of the formula (II) and or or (IM) or with Urea and optionally lower polyamines or alkanolamines are further condensed.

These emulsifiers combine to an unexpectedly high degree in themselves high water emulsifying power, which plays a decisive role, especially in the alloying of the water in the liquor, and good Filter wedge. When used as a cleaning booster, the high cleaning power and to emphasize the good dirt-carrying capacity. Due to the antistatic effect that comes with using this Emulsifiers is achieved, above all, the build-up of lint on the cleaned wardrobe be reduced or prevented entirely. The low impregnation effect is also with the use these emulsifiers are particularly noteworthy as cleaning enhancers. Both when using as a cleaning booster as well as when used as an aid for the solvent whale is an advantage mention that the use of these emulsifiers improves the feel of the cleaned or tumbled goods is much softer, so that, especially when flexing, the use of an additional Plasticizer unnecessary.

The production of the condensation products by

It is known to heat the fatty acids mentioned with compounds of the formula (I) in an approximately molar ratio (see, for example, US Pat. No. 2,267,965). The details s ^! nd can be found in DT-OS 21 61 602. Any further condensation with urea and possibly lower amines or alkanolamines and the subsequent reaction with the acidic phosphoric acid esters is also described in DT-OS 2161 602. The emulsifiers obtained thereafter are adjusted to a Cichalt of 30 to 80% detergent substance.

It has surprisingly been found that the properties of the emulsifiers according to the DT-OS 2161 602 can still be improved if the same 2 to 20 percent by weight, based on the washing-active substance, of non-ionic, washing-active substances Substances are added.

The present invention thus relates to an emulsifier mixture for dry cleaning and Solvent whale consisting of a saturated or unsaturated, Fatty acids optionally substituted with OH groups and having at least 12 carbon atoms with I to 1.2 Moles of a compound of the general formula

H ₂ NC ₂ H ₄ -NH-CH ₂₁₁ -X

in FIG. 6 equals 2 or 3 and X is the group -NH), -OH or a radical of the general formula

- (NH-C /, Η.'λΛ-Υ

in the if equals 1 or 2 and Y is the group -NHj or -OH is, mean at up to 260 ° C with cleavage of at least 1.4 mol of water, optionally additional condensation of 0.25 to 1 mol I larnsloff and optionally also 0.2 to 0.5 mol of polyamine of the general formula

H ₂ NC ₁₁ H ₂₁₁ -X

(IV)

wherein ./equals 2 or 3 and X is the group -NH ₂ . -OH, or a group of the formula -NHCzFl ₂ Z-NH ₂ or - NHCH ₁ ) Z-OH, in which / is 2 or 3, mean, per mole of the fatty acid used as the starting substance, and subsequent further conversion of the condensation product obtained, with compounds of the general formulas

HO OH

/ \ R, (- O —C ₂ HjR ') _t —OO (II)

and or or

R, (- O - C ₂ H, R ') _t - O OH

R, (- O -C ₂ HjR '). _v -OO (III)

in which χ equals O to 12, the group R, an alkyl radical with 2 to 7 carbon atoms (when χ = O), an alkyl radical with 4 to 18 carbon atoms (when x = 1 to 12) or an alkylphenyl radical with an alkyl radical of at least 3 Carbon atoms and the radical R 'denotes a hydrogen atom or a methyl radical, product produced in combination with 2 to 20

Percentage by weight, based on detergent substance, of non-ionogenic detergent compounds.

The mixture according to the invention preferably contains Fmulgalor but 5 to 15 percent by weight, based on the active washing substance, of non-ionic washing active substances Links.

Surprisingly, the addition of the nonionic, washing-active substances increases the solubility in water and the water emulsifying ability of the Hmulgaioren of DT-OS 21 61 602 even further improved.

Such nonionic surfactants are the polyglycol ethers of fatty acids, fatty alcohols and Fctlsäureamid; n with a saturated or unsaturated alkyl radical with at least 12, preferably 14 to 20 Carbon atoms and the polyglycol ethers of alkyl or Dialkyiphonolcn with an alkyl radical of at least 4, preferably 8 to 12 carbon atoms, where the Polyglykolätherresl contains 4 to 20 ethylene oxide, in Question. Examples of such compounds are: nonyl or dinonylphcriol polyglycol ethers with 9 ethylene oxide, Hxyl- or Dihcxylphcnolpolyglykoläther with 15 ethylene oxide and decyl or Dideeylphenolpolyglykoläthcr with 4 or 18 ethylene oxide, the polyglycol ethers of Laiirin-. Palmitic, stearic, oleic and bchic acid or their amides with 5. 10 or 15 ethylene oxide and l.auryl, cetyl, oleyl and Stearyl alcohol polyglycol ether with 10 or 15 ethylene oxide.

Since a certain impregnation fluid cannot be avoided when using these polyglycol ethers. the corresponding polypropylene glycol ethers of fatty acids, fatty alcohols are particularly preferred and Fcttsäureamidinn with a saturated or unsaturated alkyl base of at least 12, preferably 14 to 20 carbon atoms and of alkyl or dialkyl phenols with an alkyl residue of at least 4, preferably 8 to 12 carbon atoms, also used, since in this case the water soluble and the Water emulsification can be increased in the same way, but one caused by this addition Impregnation influence is not observed. Hey the Polypropylcnglykoliilliern especially those are used which contain 4 to 10 propylene oxide.

Phosphoric acid esters of the general formula are also non-ionogenic, washing-active substances

R (-O-CM1, R ') _V -O

R (-0-

,-O

0- (C ₂ H ₁ R'-O -),. R

in which R is a saturated or unsaturated alkyl radical having 7 to 22 carbon atoms, R ' is hydrogen or a methyl radical and ι are identical or different numbers from 3 to 15, can be used. Examples of such compounds include: phosphoric acid esters of alkoxylated 2-ethyl-alcohol. Lauryl alcohol. Oleyl alcohol or stearyl alcohol with a total of 15, 25 or 35 propoxy or ethoxy groups on average. Here, too, the phosphoric acid esters of propoxylic alcohols are preferably used, since in this case, too, an impregnation effect caused by the addition of these compounds cannot be determined.

The Erl'indiingsgemäik'ii I .mulgalor mixtures will be both as a cleaning booster for dry cleaning of all kinds of textiles. as well as Emulsifiers in the first solution milled wool and articles containing wool. Λ !. Solvents are those mentioned in Dl-OS 21 61 602; in I-rage.

Dry cleaning of textiles includes pre-spotting. the normal automatic cleaning process and the Naehdelachur. the mixtures according to the invention being particularly advantageous for pre-molding can be used in the steam spray process. Carrying out the entire dry cleaning takes place in the manner indicated in Dl-OS 21 61 602.

liei use of the crl'induiigsgcmiiUcn Fnuilgaloi · Mixtures as cleaning enhancers are those already mentioned in DT-OS 21 61 602 for the fertilizers Benefits on. In addition, a particularly outstanding feature of these mixtures is their considerable water solubility and to mention the enormously high water-binding capacity.

liei the dry fulling, el. h.cler fulling in organic Solvent, pure wool particles, as well as mixed fabrics made of wool and polyamide. Polyester, polyacrylonitrile and rayon in the solvent, especially Tetrachlorethylene, with the addition of the invention Emulsifier mixtures and drummed a measured amount of water. The solvent whale is thereby carried out as described in more detail in DT-OS 2161 602.

The advantages of the infiltration loops according to the invention for the solvents are above all that the extremely high water-binding capacity ensures that the water is uniformly distributed in Walkflotic , that is to say that the emulsion is highly stable and that optimum flux is achieved will.

The following examples are intended to illustrate the invention explain:

example 1

K) Og of the emulsifier A of Example 1 of the DT-OS 21 61 602 graze with 6.5 g dinoiivlphcnolpropoxylal (4 l'iopoxygiuppcn) and 5 g of Alylgls kol.

Dm the technical progress of the Fmulgalor mixture compared to the state of the art, a number of comparative insurance policies will be shown:

Attempt a
(We sse rhi ndc abilities)

1 I cleaning liquor (tetiacliloroethylene). which contains 2 g of the above-described Rciniguii {^ reinforcing mixture (detergent substance approx. 80%) is mixed with water in a ratio of 1: 1 to 1:20 (based on the detergent substance) and the resistance of the resulting emulsion is assessed . In the same way, the water binding capacity of a chemical agent (RV) consisting of dodecylbenzenesulphonate, l.aurylpol), is determined with 7 ethoxy groups and nonylphenol glycol with 4 ethy groups (but with a ratio of about 6: 2: 1) this cleaning booster has only about 40 ¹ Vn detergent substance (remainder of usual solvents), 4 g / l can be used.

Water-binding capacity of 1 l of cleaning fluid, consisting from tetrachlorethylene and 2 g / l of the Fmulgatoi mixture or 4 g / l of the Fmulgalors RV (additional water based on a detergent substance of the additives):

Claims (2)

l \ itenians |) row: 1. Enlargement for cleaning and solvent wholesaling, consisting of a fatty acid with at least 12 carbon atoms with 1 to 1.2 mol of a compound of the general formula, which is substituted by a saturated oiler unsaturated, optionally with OH '"• sips H ₂ NC ₂ H ₄ - NH - C _h \\ _2h X (I) in which b is 2 or \ and X is the group -NH ... -OH or a radical of the general formula in the /. equals 1 or 2 and Y is the group - Nil. » oiler -Oll, mean at up to / u 260 "C" with elimination of at least 1.4 mol of water, optionally / usii /liche.s condensation of 0.25 to 1 mol of I larnstolT and optionally 0.2 to 0.5 Mol l'olyamine of the general formula HN -C ₁₁ II ,,, -X (IV) in which, · / is 2 or 3 and X is the group - Nil ·, - Oll, or a group of the formula -NHC I lv-NH .. or - NIICJ 1 -, - OH, in the /. 2 or 3, denotes, per mole of the fatty acids used as starting substance / and subsequent further mixture of the condensation product thus obtained, with compounds of the general formulas HO OH / \ (ID and or or R, (- _{O-C 2} H ₁ R ¹ ), -O OH R, (- O - C, H ₍ R ') _A -O (HD in which ν equals O to 12, the group Ri is one An alkyl radical with 2 to 7 carbon atoms (with v = 0), an alkyl radical with 4 to 18 carbon atoms (with ν = I to 12) oiler an alkylphenyl radical with a Alkyl radical of at least J carbon atoms and the radical R 'is a hydrogen atom or a Methyl radical means, based on the product produced in combination with 2 to 20 percent by weight on washing-active substance, on non-ionogenic, washing-active compounds. 2. Emulgalor mixture according to claim 1, characterized in that it is used as a nonionic, detergent Compounds of phosphoric acid esters of the general formula R (- O-C, H, RVO O R (OC ₂ H ₁ RVO 0 (C ₂ H ₁ RO) ₁ R in which R is a saturated or unsaturated alkyl radical with 7 to 22 carbon atoms, R 'is hydrogen or a methyl radical and y is identical or different numbers from 3 to 15, contains.