DE2656384B2 - Process for cleaning textiles in organic solvent baths - Google Patents

Description

2. The method according to claim 1, characterized in that the solvent is perchlorethylene. Trichlorethylene, 1,1,1-trichloroethane, monofluorotri- _ ■ - ■ chloromethane, Trifluortrichloräthax can be used.

3. The method according to claim 1, characterized in that that the solvent bath 0.1 to 3% based on the textile to be cleaned of water is added.

4. The method according to claim 1 or 2, characterized in that the solvent with the Required amount of fluorosurfactant impregnated fiber fleece is fed.

5. The method according to claim 1 or 2, characterized in that the solvent is the required Amount of fluorosurfactant is supplied in the form of tablets.

6. The method according to claim I or 2, characterized in that for cleaning textiles a solvent bath containing fluorosurfactant after contact with the items to be cleaned via a filter and the dirt dissolved in the solvent bath is separated off by distillation, whereupon the purified solvent is used again.

The invention relates to a method for cleaning of textiles in organic solvent baths Use of solvents soluble or emulsifiable Fluorosurfactants.

To improve the removal of polar soiling that is not soluble in the solvent from the to Cleansing substrate are added to the cleaning baths, cleaning enhancers (RV).

According to the established definition (DIN 5.1180), RV surface-active products that enhance the cleaning effect Increase (strengthen) organic solvents and expand them by incorporating them Water in the organic medium increases the cleaning effect of the system even on hydrophilic soiling expand.

RV are usually used in concentrations of J to 7 g / l solvent and consist of:

30-50 wt% Tcpsidcn;

5-15% by weight of solubilizers (/ .. IJ. Alcohols), 5-15% by weight of water.
30-50 Gcw. ⁿ / o thickening agent (e.g. mineral oil)

(Lindner: Tenside. Textilhilfsmittcl. Wavchrohstoffc, page 1332 ff. Scientific publishing company, Sdittgar, 2nd edition, 1964).

In the context of the above-mentioned basic formulation, additives, e.g. mineral oil, are referred to as thickening agents, which serve to bring the cleaning booster into a liquid, easy-to-use state bring. Adjusting agents are used for the cleaning process itself Frcmdstoffc. because they are regarding the Heini effect indifferent.

When cleaning textiles in solvents (Chemical cleaning) will comply with the KV Baths passed through a filter to put in the solvent to deposit insoluble pigment dirt. After a single use, the solvent bath is turned into a Given the distillation device to remove the solvent (preferably perchlorethylene) by distillation impurities not separated by filtration to be freed.

The dirt removed from the substrate stays together with the residues of the cleaning enhancers and filter aids used (kieselguhr) in the distillation residue.

Based on work by Marcou (Teintex 17: page 627. 1952), Hess (Revue Chcm. Rein. 1: page 6. 1958) and Sure (Färberzcilung 18: page 412. 1965) are at the chemical cleaning extracted an average of 14 g of dirt from 1 kg of textiles

60% pigment dirt.
Oil 10%. Fats and
30% water-soluble substances

consists.

In commercially available cleaning machines with a liquor ratio (kg of textiles per I liquor) of I: 3 to I: 5 work and add the amount of liquor per batch to the distillation, an average is calculated Distillation load per kg of textile material of

14.0 g loosened dirt,
7.5 g filter powder (kieselguhr).
20.0 g cleaning booster
41.5 g.

This means that approx. 48% of the distillation backlog consist of KV and dal! with a Mincralölgchalt of e.g. 50% in the KV 24% of the residue is mineral oil.

2 (1

As described, the cleaning enhancers remain in the distillation residue and have disadvantageous Effects on the distillation behavior, namely

1. At higher concentrations in the solvent, mineral oil and surfactants cause a boiling point ' increase, so that a complete expulsion of solvent residues from the distillation residue is only possible by introducing steam (carrier steam distillation);

2. In the steam distillation of dry cleaning liquors, relatively volatile ones also go Components of manure dirt (e.g. low molecular weight fatty acid fractions from body excretions) with over that contaminate the distillate and unpleasant smell of the distill- '' cause lats, which is transferred to the cleaned textile goods and reduces the success of the cleaning process;

3. The high percentage of mineral oil in the distillation residue makes waste disposal difficult, taking into account ecological aspects:

4. The RV content of 40 to 5 (T ¹ O in the distillation residue consumes unnecessary energy for heating the distillation;

5. The consistency of the residues from textile cleaning is liquid as a result of the RV share. "'If these shares weren't available, you would get a residue of powdery, dry consistency.

From the point of view of environmental protection, the waste jn elimination and energy costs, the RV share in the distillation residue is the main problem carrier.

The disadvantageous effects of cleaning enhancers on the distillation behavior can be avoided if their application concentration r, in the organic solvent baths is reduced from usually 3-7 g / l to 0.01 to 0.2 g / l. This requires the properties necessary for cleaning textiles

Dirt removal, "'

Dirty be able to

Avoidance of electrostatic charges

at an application concentration of less than 0.2 g / l to the extent that it is achieved with known 4-, Cleaning boosters are given at 3–7 g / l.

According to the state of the art, this has so far not been possible.

It is known that in aqueous solution, at much lower concentrations, fluorocnidene limits the limit -, n In many cases lower the surface tension even more than conventional surfactants.

It is also known (DE-AS 21 10 767) that fluorosurfactants also have surface-active properties in organic solvents. In DE-OS -> 21 27 232 it is described that it is necessary to use higher proportions of commercially available emulsifiers for the production of stable emulsions of water in fluorocarbons, but their proportion can then be kept significantly lower if _w > 0.1% = fg / l of a perfluorocarboxamide amide indenate is added: vgi. Ie example 6.

Fis is also known to use fluorosurfactants in a concentration of about 0.02 to 1% = 0.2 to 10 g / l in anhydrous carbonated hydrocarbons to detach liquid, organic films from solids (US-F ¹ S 50 09 061) .

Simply from the fact that a substance is surface-active and that it may also have good emulsifying properties, that this is surface-active Substance is sufficiently soluble in organic solvents and that it is still at Concentrations of 0.02% is effective, no teaching can be derived that this substance also n! S Detergent booster is suitable for cleaning textiles in organic solvents

Fluorosurfactants that are to be used as cleaning enhancers must also have the property both water-soluble dirt and pigment dirt from all textile fibers if possible detachable equally well, to disperse this detached dirt sufficiently to allow dirt redeposition (Graying) and to prevent electrostatic charging of the textile items to be cleaned.

The perfluorinated carboxamide amine derivatives described in DE-OS 21 27 232 meet these requirements Requirement not.

It has now been found that "an improvement in the Desililation behavior of the solvent baths and a Improvement of the consistency and a reduction in the amount of distillation residues in the Dry cleaning when using fluorosurfactants can be brought about on '/ att conventional surfactants can. Few of the large number of known fluorosurfactants are suitable for one application concentration from 0.01 to 0.2 g / l as a cleaning booster for cleaning textiles in organic solvent baths to be used by, in addition to the ability to reduce and emulsify the interfacial tension, the properties necessary for textile cleaning

Dirt removal,

Dirty be able to

Avoidance of electrostatic charges

to the extent that they have known detergent boosters at application concentrations of 3–7 g / l are given.

The fluorosurfactants used in accordance with this invention can be anionic, cationic or nonionic or be ampholytic in nature. They come with an application concentration of 0.01-0.2 g / l preferably 0.05 - 0.1 g / l in the solvent bath for use.

Details of the groups of fluorosurfactants which can be used in accordance with this invention are given below made.

I. Anionic fluorosurfactants of the general formula 1.1 Perfluoroalkylalkylenecarboxylic acids and their salts

C "l ^; ,,, i (CI '..) "COOM
here mean:

M is hydrogen or a monovalent metal ion, preferably an alkali metal, or NH ₄ *. RiNH ', NR ₄ ',
where R cine alkyl uc'er alkylol group with 1 to! Represents carbon atoms. η is an integer from 6 to 12 and

m cwc gan. '. c number from I to 4.

Connections of this type are described in DF-PS 19 16 669.

1.2 Perfluoroalkylethercarbonsüiiren and their salts

V (Cl \>"(CH-)," - () C ¹ I!, Cl I. ((X) M

here mean:

Y Il or F.

M hydrogen or a monovalent metal

ion or NH ₁ ', R ₁ NFf '. NRr,
or Nile, '. R ₁ NH ·. NR ₁ -.
wherein R represents an alkyl or alkiol group having I to J carbon atoms.

/; an integer from b to 12.

into a whole / aiii from I to 4.

Compounds of this type are described in I) S-PS Jl 4 ^r ) 222.

Ij rV * i riiioi i

visuifuiisiiin en ιπκί ucreii Suize

here mean:

M hydrogen or a monovalent metal

ion or NIIj-. RiNH \ NRr,
wherein R represents an alkyl or alkylol group with I bi <3 carbon atoms.

/; an integer from 6 to 12.

Connections di
DH-AS 10 29 822.

Kind are described in

1.4 Tetrafluorethylene oligomer of oxyphynylcncarbopic acid or -silfonsaure and their salts

here mean:

X COOM or SO ₁ M.

wherein M is hydrogen or a monovalent metal ion or NH ₄ '. RiNH ". NR ₄ - is.

wherein R is an alkyl or alkylol group with I to J represents carbon atoms.

η is an integer from 6 to 12.

Compounds of this type are described in DE-OS 17 93 714

2, Cationic fluorosurfactants of the general formula 2.1 Perfluoroalkylalkyleneammonium salts

j [i CF = CH-CH-NR ¹ RR] A

here mean:

R ¹ . R-. R3 is hydrogen or alkyl or alkylol groups with 1 to 3 carbon atoms or, instead of R ¹ + R ² -t- R ^3, the radical of a cyclic ring compound in which N is incorporated as a hetero atom.

A is an inorganic acid residue.

η is an integer from ö to 12.

Compounds of this type are described in US Pat. No. 3,535,381.

2.2 Perfluora I ky! Groups
amidamine

containing carboxylic acid

₁ K ₁₁₁₁ (ClI-VC N (CH-LN'RR ¹ U ' ¹ A

ii ι:

j OR ¹

here mean:

R ^{1 is} hydrogen or cine alkyl or alkyl

lol group with 1 to 3 carbon atoms.

R ¹ , Κ ·. R ^{1 is} hydrogen or alkyl or alkylol groups with 1 to 3 carbon atoms or R - '+ R' + R ^{1 is} the radical of a cyclic ring compound in which N is incorporated as a heteroatom.

A is an inorganic acid residue.

η is an integer from b to 12.

into an integer from I to 4.

/ 'is an integer from I to 4.

Connections of this type are described in DF-AS 10 Ob 42h and DH-OS 14 4 '> 630

3. Non-organic fluorosurfactants of the general formulas

3.1 Oxalkylenetc l'erfluoroalkyl groups containing Alcohols

K ₁ (CIhUXO (MI,), ll

here mean:

Rr the telomer remainder C-F.,.,. : or H (CF;)

η is an integer \ on 6 to 12.

into an integer \ on 0 - 4.

ρ is an integer from 5 - 25.

Compounds of this type are described in US Pat. No. 2,723,999 and DH-OS 22 hl 681.

3.2 Perfluoroalkyl alcoholic acid esters with polyethylene glycol

R ₁ CH, CO (OClI, »... Oll

here mean:

Ri the remainder of telomer C., F _: · .. ι or H (CF :)

η is an integer from 6 to 12.

ρ is an integer from 5 to 25.

produced by esterification of the corresponding carboxylic acids or carboxylic acid chlorides with polyethylene glycol in the equivalent of dehydrating or acid-binding agents.

4. Ampholytic fluorosurfactants of the general formulas 4.1 Amine oxides containing perfluoroalkyl groups

CFV ₁ Y, - (CH -) ... NR ^: R ^;

here mean:

R ^! an alkyl group with! up to 4 coals

atoms or hydrogen.

K-. K ¹ alkyl groups with I to 10 carbon atoms,

Y - C- N- or SO ₂ -N-

R ¹ R ¹

η is an integer from 6 to 12.

;;) an integer from 1 to 4,

/ j 0 or I.

Compounds of this type are described in DE-OS 20 08 531.

4.2 Addition products of amines sewing on perfluoroalkyl groups with cyclic phosphites

Cl,., (CI ^ C HUCIL) N WW - (Q) OP

l \

Il O

here mean:

Q -CH, - or -CH-CM.- or

-CH.C HR- or -01, CRR ¹ -.
wherein

R is an alkylresl with 1 or 2 carbon atoms,

R ^{1 is} hydrogen, an alkyl radical with 1 or 2 carbon atoms or cm phenyl radical,

R- '. R 'is hydrogen or an alkyl or alkylol group with I to 4 carbon atoms, / i is an integer from 6 to 12.

/ ;; O or 1.

t is an integer from 1 to 4.

produced by reacting amines of the formula:

CF-, .., (CF-CH |, "~ (CII;), -NRR ¹
with cyclic phosphites of the formula:

O O

Q V

O H

at temperatures between +20 and + 140''C in substance or in a polar solvent.

As has been found, it is possible to practice the method of the invention in such a way that mixtures the aforementioned fluorosurfactants can be used. Such mixtures can consist of

a) anionic and / or nonionic and / or ampholytic Fluorosurfactants.

b) cationic and / or nonionic and / or ampholytic fluorosurfactants.

As a solvent in the process of the invention all solvents suitable for cleaning textiles are used. In particular, are too name: Perchlorethylene, Trichlorethylene, I.I.I-Trichlorälhan, Monofluorotrichloromethane, trifluorotrichloroethane.

It i:, t also possible to use the method of the invention in in such a way that the cleaning bath 0.1 to 3 wt .-%, based on the textile material, of water is added to the detachment of water-soluble or emulsifiable dirt.

A particular advantage associated with the invention is that the solvent can be recycled by the solvent bath containing fluorinated surfactants intended for cleaning textiles after contact with the items to be cleaned is passed through a filter and after separation of the detached ones feslen pigment dirt particles the dirt dissolved in the solvent bath by distillation of the Solvent is separated, whereupon the purified solvent is reused.

Solvent bath with an addition of 0.01 to 0.2 g / l fluorosurfactants produce equally good or better cleaning results than solvent baths an addition of 3 to 7 g / l of conventional detergent booster.

As a result of the 97.5 to 99.5% lower application concentrations and the freedom from setting agents of the fluorosurfactants is the volume of the distillation residues decreased by approx. 50%. The distillation residues from chemical cleaning machines are free of Mineral oil, can be freed from oil residues without steam distillation! be and lie in simple powdery consistency to be handled. The effort required to dispose of waste is significantly reduced. The smaller amount of distillation residue saves energy. As a result of the nichl required With steam distillation, the distillate is pure and free of foreign odors.

When cleaning metal, the last rinse is not an option necessary.

As a result of the low use concentration of the fluorosurfactants of the method of the invention are advantageous Dosing possibilities given. During the RV additive measured volumetrically with conventional cleaning methods and via an addition trough ter must be fed to the machine. In the process of the invention, the fluorosurfactants can be used as a tablet or a section of one impregnated with fluorosurfactants Fiber fleece can be put directly into the machine with the items to be cleaned. A separate dosing process is therefore not required.

To prove that fluorosurfactants are already included in extremely low application concentration, the interfacial tension between organic solutions The interfacial tension of perchlorethylene / water was used to reduce the concentration of agents and water more strongly than a conventional cleaning booster in the optimum concentration measured.

A du Noiiy Tensiomcter served as the device (Lindner. P. 3028). The force that is required is measured. around a platinum-iridium ring with 20 mm To push diameter through the interface water / perchlorethylene.

Different surfactant solutions were used for the measurement made in perchlorethylene. 30 ml of these solutions were in a glass vessel with a 6 mm high water layer.

12th

The interfacial tension between water and perchlorethylene was compared of perchlorethylene solutions of a conventional cleaning intensifier (reference substance) with that of various fluorosurfactants. A commercially available cleaning booster is used as a comparative substance ordering from:

18% dodecylbcholsulflonate (KSaIz) 5% dodecyl sulfonate (Na-SaI /)

Siihsl.in/

Perehloriithvlen pure

. JlI ι ', ι, ι 1 1 /: \

Substance A

CJtSO ₁ NH ₁
Cl ₁ -CIh-CII-COONa
CJVC HC H-OC HC H-COO K

R ₁₁ -O- <T y COOK

C Jt SO, N (CH, ICO (OC-IIj) ₁₁₁ OCn., O

R ₁ . CH-CII-OP-ONa

\
ONa

R ₁ C IhC0 (0C-II ₁ K., OClI,
R _1. -CH-CO (OC.II.,) ,,, OH

H% 2- A thy I hex a ml- phosphoric acid ester Na-Sal / kon / L'nlr; itinii (.Iren / - (Mixture of monoester disodium salt / and 11, κ licii- Diest e rmonor. atrium salt) (μ / lt (ilMi / iin » 8th' Nonylphenol polyglycol ether (3 mol 40 Ethylene oxide) 4% Isopropanol 10% water 49% mineral oil 100.0% Substance A

C, l, -CH-CO (OC-H ₁ KdI,

0.1 D.1 0.1 0.1 0.1

I) .1 0.1

0.1 0.1

o.i

0.1

0.1

27

24 IO

14th

IS

1')

| CJ vC H-CONIl (C H,), N IKCH.). | CI

CJrCH-CH, N

SOVCH,

0.1 0.1

I 1 12

IR, Cl - ■■ C II - C HN (C II ₁ IC II-C I IO I UCI

CJ _n Cl ^ -CH CH., N <(\ ll.) .- C !! .. C <CII,) - C! L · - OP = O

CI - ',, CONIhCIh) ₁ N (ClI ₁ ) -> O

K] ₁ Oliiziimcrongciiiisch dos lclnilluiinith> Ions, lclnimcr bis lievmicr K ₁ , Iclonicrrcst C '"l ·' - ,,. _s : n h - 12 K | lcliimcrrcst C ',, 1'- ,. ι: H ~ 5 - II

These results show that fluorosurfactants at an application concentration which is only 2% that for conventional Cleaning booster, a higher 0.1

0.1

(1.1

Reduction of the interfacial tension water / perchlorethylene effect than conventional RV in the optimum concentration.

The lowering of the interfacial tension perchlorethylene / water gihl a clue for that Surface activity vi.n surfactants t> ci determined Use concentrations. From this canr. but only conditionally on their usability as cleaning enhancers getting closed.

Criteria for assessing the usability of surfactants for the production of cleaning agents core are:

Solubility in organic solvents.
Effectiveness in organic solvents.

Should the cleaning boosters be used for cleaning \ un Textiles that are used in organic solvents (dry cleaning) must also be used die Schnnit / rcdeposiiion (graying) and clcktrou; itisrhr Prevent the Trxlilipn from charging

The cooling effect can be determined by chillingly soiled cloth fabrics (soiling: iron oxide. Soot. Starch, oil) from Testfabrics Inc., Middlesex. III .. USA. Made of cotton. Wool. Polyamide. Polyester !.. N and polyacrylonitrile are cleaned in a so-called mechanical washing unit 54024 on the basis of D ¹ · Di cleaning effect is calculated as% of the whitening .I Forme ^1:

I 10 (1

Il

H ,;

Ho = remission of the unsoiled original tissue

Η ·: = remission of the soiled tissue
Hj = remession of the soiled fabric after cleaning

The graying of the treated, not soiled The original tissue is determined according to the formula:

Γ - 100

Uo- H r
Ho

Remission of the unsoiled original tissue
Wv = remission of the cleaned sample

The antistatic effects are determined by the half-life of the voltage drop of a voltage of 100 mV. which is applied to a! Ocm long, 5 mm wide test strip, the lower the Half-life is, the higher the conductivity of the treated sample? and the less the danger the occurrence of electrostatic charges.

A half-temperature of 20 seconds in a standard climate (20'C. b'V '/ i relative humidity) is sufficient to avoid sticking around lenses to the items to be cleaned during the drying process.

To prove that fluoride surfactants are used for cleaning Solid substances are suitable, were cleaning effect (Lightening of soiled test fabrics) and V ^ r graying examined in the laboratory using the methods described above.

Ak surface-active substances became substance A (conventional cleaning booster) or one anion-active each. cation-active and non-ionic fluorocside:

Substance H: C, l _r C ILCILCOONa

Substance C: | C _S I _P CILCONIKC ILhNH (CH,) ..] CT Substance I) CM ₁ -C 11, CO (OC ILC IL) "-.Ol I

(Ti ¹ I different application concentrations:

5 g / l. I g 1.0.1 g / |

used.

Prepare the test tissues

Samples of both the artificially soiled and the pure white test fabrics were used 5x5 cm cut. For a comparable water content In the cleaning trials, the samples became 90% relative for 24 hours Air humidity and 20 "C conditioned.

Implementation of laboratory cleaning

The remission of 4 series of artificially soiled and pure white samples of the test fabrics made of cotton (CO). Wool (WO). Polyamide (I ¹ A). Polyester (PE) and polyacrylonitrile (PAC) were measured, and treatment was then carried out in a 400 ml liquor for 10 minutes at 30 ° C. in a nu ^ har see washing device based on DIN 54 024. After the treatment, the liquor and samples were separated from one another and a second series of identical, untreated test bottles were treated in the same way in the same liquor. The liquor was used to clean 4 series of tissue samples in order to be able to determine the effects of increasing smear load on the liquors on the graying of the pure white tissue samples. The results recorded in the table are mean values from cleaning series 1 to 4.

substance 5 g / l Lightening (A) 1.6 WHERE V Graying (V) V PE V PAC V 5 g / l CO 3.4 \ °: a 0.5 PA 2.5 A% 0.2 A% 0.9 5 g / l A% V 9.9 8.0 1.0 A ⁰ Zo 4.0 7.0 8.9 7.1 2.1 A. 5 g / l 5.0 14.7 10.7 8.3 8.8 3.4 6.8 6.2 13.8 8.9 B. 1 g / l 5.2 -> ι 8.1 4.8 9.2 7.1 3.1 10.9 6.4 7.2 C. lg / 1 1.2 3.5 9.3 2.8 6.0 5.6 6.4 7 2 5.9 3.9 D. lg / 1 10.2 8.3 5.4 0.2 5.9 4.0 3 1 10.1 4.6 2.0 lg / 1 2.3 10.9 10.3 5.1 3.9 3.0 7.0 5.9 13.9 9.6 B. 4.6 7.2 1.7 9.0 5.5 3.0 7.8 6.8 5.7 C. 0.9 8.8 6.1 6.1 5.2 D. 7.4 5.8

horisctZLinu Stop position (A) WHERE V Forg ruuung (V) PK V PAC V substance CO A ¹ Vn 5.2 PA A "/.ι 11.4 A% 10.7 A% V 2.7 O.i V 0.9 10.6 2.1 1.8 0.8 8.4 10.3 3.4 1.8 7.9 7.2 5.8 ny 9.2 A 0.1 g / l 4.2 3.9 7.5 0.6 8.7 4.4 2.8 3.5 6.9 3.0 B 0.1 g / l 0.7 7.6 8.0 5.8 1.9 '.0 5.0 C 0.1 g / l 6.0 6.3 5.8 2.0 D 0.1 g / l

These results show, surprisingly, that the fluorosurfactants used here, with decreasing application concentration from 5 g / l to 0.1 g / l only an extremely small decrease in the cleaning effect with partial show a clear reduction in the tendency to graying, while the conventional cleaning enhancer (substance A) shows a significant loss of effectiveness learns. The result is particularly surprising that individual fluorleiisides in certain test points at an application concentration of 0.1 g / l show a better effect than the conventional cleaning booster at the usual application concentration of 5 g / l.

LJm to show which fluorosurfactants at an application concentration 0.1 g / l are particularly preferred for cleaning textiles, a large number of them became various substances used after preselection and cleaning effect (lightening of soiled Test tissue) and graying in the laboratory according to the methods described above and tested with the compared to conventional RV (substance A).

I. Anionic fluorosurfactants

Substance FA 1: C ₈ F ₁₇ SO ₃ K

Substance FA 2: C ₈ F ₁₇ CH ₂ CH ₂ COOLi

Substance FA 3: R ₁ -O

COOK

Substance FA 4: CjF ₁₇ SO ₁ NH ₄

Substance FA 5: C ₈ F ₁₇ CH ₃ CO (OC ₇ IU) ₁ OSO ₃ NiI

Substance FA 6: C, F _{| 7} CH, CH, OCH _: CH ₂ COOK

R ₁ = oligomeric genic of tetrafluoride. telramer to hcxamcr.

substance Lightening (A) V WHERE V Graying (V) PE V PAC V CO 10.3 A% 3.7 PA A% 8.1 A% 7.2 (g / l) A ° / o 3.8 8.9 0.0 A% V 0.6 10.5 7.5 1.6 FA 1 0.1 0.3 4.8 10.2 1.2 5.0 3.8 7.3 3.1 12.7 3.1 ΓΑ 2 0.1 4.4 1.9 7.2 0.0 9.0 4.1 6.4 9.9 6.3 1.8 FA 3 0.1 5.0 6.2 1i.4 2.0 7.0 2.6 2.6 7.3 4.2 3.6 FA 4 0.1 4.5 3.2 8.8 0.9 6.1 0.0 4.0 8.7 4.3 2.0 FA 5 0.1 1.0 12.4 5.5 1.1 5.8 8.1 FA 6 0.1 2.0 1.6 0.5 7.9 3.1 0.2 0.9 Substance A 8.0 7.0 7.1 5.0 5.0 8.8 2.5

According to this test, the substances FA 2. FA 3. FA 4 are particularly advantageous.

2. Nonionic lluortcnside

Substance. FN 1: C ₈ F ₁₇ CH ₂ CO (OCjH ₄ V ₇ OH

Substance F-'N 2: CJ ₁ , CH ₂ CO (OC, ΙΙΛ,., ΟΓ, Ι '.,

Suhsiiin / IN .VC, I, -CH _; CO (OC; H,) "., OH

Substance IN 4: CI ₁₁ CH ₁ CO (OCjH ₁ Ii ₁ OH

Substance FN 5: R ₁ C 11., COIOC; !!,),., OH

Substance FN <>: C, F _r CH, CO (OC, ll ₄ ) ". * () Ll

Substance IN 7: C ₅ ! , -C 11, CO (OC, H ₁ ) ,,., OCOC H ₂ CI, -

030 HB / 27?

Substance FN 8: R _f CH ₃ CO (OC ₃ H ₄ ) _4S OH

Substance FN 9: C _s F ₁₇ SO ₃ N (CHj) CO (OC ₃ H ₄ ) _l4 (OC ₃ H ₆ ), ₄ OC ₄ H,

Substance FN 10: C ₈ F ₁₇ CH ₃ CH ₃ O (C ₃ H ₄ OV ₈ H

R _f = C "F,"_H;/; = 6-12.

substance Lightening (A) V WHERE V Graying (V) PE V PAC V CO 9.4 A% 2.9 PA A% 4.7 A% U (g'i) A% 6.5 7.9 2.1 A ⁰ A V 5.0 6.3 6.6 0.8 FN 1 0.1 0.3 6.3 8.5 0.6 3.2 3.2 2.5 3.5 6.0 3.0 FN 2 0.1 1.5 10.3 8.0 2.2 3.8 3.0 6.0 4.0 5.0 7.8 FN 3 0.1 6.0 4.4 8.2 0.4 5.8 2.0 3.8 1.9 43 2.0 FN 4 0.1 0.6 10.4 10.3 3.3 3.0 2.7 7.9 5.7 5.2 7.0 FN 5 0.1 7.2 8.2 7.1 2.8 6.2 1.7 4.7 5.7 5.6 1.0 FN 6 0.1 0.4 10.2 8.8 4.1 3.8 2.0 3.0 7.2 6.3 8.9 FN 7 0.1 1.8 13.7 11.3 3.8 63 1.5 6.2 10.1 6.6 5.2 FN 8 0.1 5.4 3.9 6.7 1.4 5.8 3.9 0.1 3.4 16.0 3.3 FN 9 0.1 0.1 12.7 2.5 5.2 6.0 53 FN IO 0.1 4.6 1.6 0.5 7.1 3.0 0.2 0.9 Substance A 8.0 7.0 7.1 5.0 5.0 8.8 2.5

Particularly advantageous results in comparison / u a conventional cleaning enhancer (substance A), used with 5 g / l, deliver the fluorosurfactants FN 3 and FN at an application concentration of 0.1 g / l

3. Canonical I luortcnsidc

Substance IK I: [C „! , ₇ CH ₃ CONH (CH ₃ hNH (C ₃ H ₄ OII) j | CT SubsUin / IK 2: [CF.jCHjCONIKCH ^ NIKC · ll,), | Cr 'Substance IK 3:

Suhsiiin / IK 4:

IK 5:

C ₇ F ₁₅ CI = C H-CH ₃ NH ₃ CH:

SO ₁ Na

Cl "

CI ₁₇ C ₃ II ₄ N

SO ₄ CH,

., ι., uz IK h: | R, Cl = CII —CHjN (CH,) ₃ CH, CII, OII | CI

K 7: IR ₁₁ Ct = CH —CH ₃ N (CH,), CH, C 11.011 ISO ₁ CII,

I ' (I. . ".,:" ''12. WHERE V V t ■ r μ mining (V) in the: V PAC V K. ( .1 . ,: »5 II. Λ ¹ Vn 3.4 I ¹ A Λ% 6.6 Λ% 6.6 ',' lh ·. 1, Ml / Lightening (Λ) HI i.4 A 'Vn V 4.4 5.8 2.9 9.2 'O 7Λ 4.0 i.7 2.6 2.8 6.9 6.9 7.6 (μ / Ι) Λ '«. V 4.3 ).H 1.9 ^Γ ), 8 2.6 I K I 0.1 1.1 7.1 !. () 6.4 I K 2 0.1 0.7 7.6 I K ) 0.1 0. ^Γ ) 10.9

19 20

yy-y continuation

Substance lightening (A) amusement (V)

CO WO PA PE PAC

(g / l) A% VA% VA ^ü / "VA% VA%

FK 4 0.1 2.7 12.2 5.3 9.5 2.0 9.6 3.0 5.8 2.0 '3.6

FK 5 0.1 03 6.3 7.0 1.3 7.5 0.0 2.5 7.2 2.5 7.5

FK 6 0.1 4.5 1.9 14.2 1.2 9.2 2.1 7.5 0.1 10.2 1.8

FK 7 0.1 5.2 2.4 19.1 1.0 12.4 1.8 6.9 0.7 14.0 3.1

Substance A

5 5.0 1.6 8.0 0.5 8.8 2.5 7.0 0.2 7.1 0.9

The substances FK 6 and FK 7 with an application concentration of 0.1 g / l are the conventional RV (Substance A), used at 5 g / l, clearly superior.

4. Amnholytic fluorosurfactants

O '

* I

Substance EB 1: C ₇ F ₁₅ CF = CM-CH ₂ N (C ₁ IlShCH ₂ C (CHJhCH ₁ OP = O

Substance FB 2: R _r CI- = CM —CH ₂ N (C, H,). CHjC (CH,). CH, —OP-O "

Il ο

R, C ₁₁ F ₂ ,,,; «= Left 5

Substance FB 3: C, l ^; "CONfl (CII.), N <CH,>, -> ()

Substance lightening (A) \ crgr; iiiiing (V)

CO WO | 'Λ PC PAC

(g / l) A% V Λ% V A% V A% V A% V

FB 1 0.1 4.3 6.7 14.8 1.9 10.1 3.4 6.1 0.1 16.0 3.4

FB 2 0.1 6.9 1.4 20.8 0.6 9.7 2.4 8.8 OJ 14.3 0.5

FB 3 0.1 2.4 6.1 6.3 3.7 5.4 4.8 6.7 1.3 6.4 2.8
Substance A

5 5.0 1.6 8.0 0.5 8.8 2.5 7.0 0.2 7.1 0.9

Substances FB 1 and FB 2 have particularly advantageous cleaning results.

5. Chemical combinations

When using Fluoricnsjdgeniischcn and with normal climates were air-conditioned. After that, the

synergistic L ^; ffektstiegingen demonstrated. Conductivity of a sample ^{strip of 1} Sx 100mm in

In addition to cleaning and graying, measured by a static voltmeter.

Test results were also determined in the following experiments. The reverberation rating was determined. This is the / hurry.

the antistatic properties bcsiimmi. Hicr / ti was a voltage given at a pole of

the samples of a washed, unequipped _h , 100 mV drops over the sample to the outside to 50 mV.

Wollgcwcbcs in a Perchloriithylenfloitc with a- | e kür / er the llalbwcrt / cit. the better the conductivity

rope 5 g / l of substance A and on the other hand 0.1 g / l of a strength and the lower the tendency to build up stan

Mixture of fluids impregnated. dried shear charges.

The untreated sample has a half-life of greater than 300 sec.

Substance FF 1:
30.0 FA!
30.0 FA 3
20.0 FN 4
20.0 FB 2
100.0

Substance FF 2:
80.0 FK 6
20.0 FA 2
100.0

Subsiance FF 3:
20.0 FA 2
30.0 FA 3
20.0 FN 5
30.0 FB 2
100.0

Substance FF 4:

30.0 FB 2

50.0 FK 7

20.0 FN 5

100.0

All values are to be understood as parts by weight.

substance

Lightening (A)

CO

A% V

WHERE

A%

Graying (V)

PA

A% V

PE

A%

PAC

A%

Antistatic

2
(sec)

FF 1 0.1
FF 2 0.1
FF 3 0.1
FF 4 0.1
Substance A
5

6.8
4.1
7.6
9.0

5.0

1.4
5.3
1.8
1.9

1.6

19.6
143
24.7
17.2

8.0

0.4
2.9
0.2
0.8

0.5

17.3

9.6

16.7

15.1

8.8

9.0

3.7

9.0

11.1

7.0

0.4
5.8
4.3
0.0

0.2

8.8

6.2

8.6

18.3

7.1

0.6
3.3
0.8
1.2

0.9

12th

? 4

16

Surprisingly, these surfactant combinations show an application concentration of OJ g / l are not only clearly superior to the conventional substance A, used at 5 g / l, but the results are also better than that. which are achieved with the individual components of the respective surfactant mixtures. An exception is the substance FF 2, in which the cationic FK 6 is combined with the anionic FA 2 became.

example 1

In a commercially available cleaning machine with a loading weight of 12 kg, 10 batches were made Normally soiled textiles cleaned with the addition of 5 g / l substance A. During each batch there was a Bath with 401 cleaning liquor (solvent bath in the cleaning drum) given for distillation. To of the 10th batch, the filter content was used for filter regeneration added to the distillation and distilled out. About the residual amounts of perchlorethylene from the distillation residue to drive off was a steam distillation of at the end of normal distillation 15 min required.

Distillation residue:

5.4 kg of black, oily mass

Mineral oil content 1.2 kg

Surfactants 0.9 kg

Filter powder l.iikg

Perchlorethylene 0.2 kg

Clothes dirt 1.6 kg

Perchlorethylene distillate
Appearance
Water content
Spe / weight
Refractive index nD
odor

slightly cloudy, colorless

0.43 g / l

l.bi g / ml (20'C)

1.5030

weak foreign odor

the substance FF 4 to be used according to the invention was added with 0.1 g / l perchlorethylene. To the end the distillation was a live steam supply to drive off perchlorethylene residues from the distillation residue not mandatory.

Distillation residue:

3.2 kg dry, gray powder

Mineral oil content 0.0

Traces of surfactants

Filter powder 1.5 kg

Perchlorethylene traces

Clothes dirt 1.7 kg

Perchlorethylene distillate
Appearance
Water content
Spec. Weight
Refractive index nD
odor

clear, colorless

1.62 g / ml (2O ⁰ C)

1.5055

typically perchlorethylene

In comparison, 10 batches of the same textile type were purified under the same conditions, the total volume of the distillation residue in the process of the invention being only 59%. based on the obtained amount ümmlichen using the manufacturers' ■ A substance.

The perchlorethylene distillate is anhydrous and free from foreign odors. in density and refraction. · index unaffected and can be used again immediately. This also applies to other solvents. With the conventional one Processes, on the other hand, have clearly negative effects on the quality of the distillate.

Example 2

/ to determine the ineffectiveness of the fluorosurfactants in the method of the invention were compared to / um Einsät / conventional detergent enhancers Test fabric used. For determining the removal of pigment dirt and graying were used in test fabrics from Testfabrics Inc. The determination of the distance of water-soluble and water-swellable

Soil was measured by measuring the lightening of cotton fabrics, the

a) with a blue, water-soluble chromium complex color (Hohenstein Research Institute, Bönnigheim / Württ.), and

b) have been impregnated with milk cocoa (EMPA, St. Gallen).

24

The test Gewfbc were; m one of the to be cleaned Garments attached. In order to avoid different influences from the items to be cleaned (type of soiling, Fiber composition, color fastness) to exclude the test fabric as much as possible, the machine was loaded with 10 kg military uniforms. 3 batches were cleaned for each experiment and the results evaluated as mean values.

Test fabric CO Noun A IA 2 IN ■> IK 7 IB 2 Fl 1 CO 5 g / l 0.1 g / l 0.1 g / 1 0.1 g / l 0.1 g / l 0.1 g / l 11 ΙΓ \ (%) (%) ("/») (o / o) (0/0) (%) A. TT KJ 15.7 13.8 13.5 16.2 19.9 19.5 V Where 4.5 5.4 4.6 4.8 3.8 3.6 Λ PE CC 1 Cl i CC -7 CC Λ cc -ι ΓΛ PE \ J t , 1 J \ J, I UJ ₁ -T w, r t) f, £ V PAC 0.9 0.4 0.6 1.2 0.8 0.4 A. PAC 56.1 56.9 64.0 55.8 61.0 68.1 V Colored CO 1.0 3.9 0.7 2.4 0.9 0.7 A. CO impregnated 46.0 42.1 40.5 52.5 53.6 49.5 V with cocoa 3.3 4.4 2.5 4.1 4.8 2.1 A. 23.0 19.7 20.5 25.8 23.9 26.1 A. 12.8 12.9 13.2 14.0 13.1 14.2

A-lightening (cleaning effect).
V = graying (dirt redeposition).

The results indicate that the cleansing effect in the method of the invention is equivalent to significantly better compared to the conventional method is.

Example 3

To show the extent to which the secondary requirements for cleaning enhancers, such as

Filtration behavior. Distillation behavior, antistatic Properties, smell of goods, separation of water / solvent in the water separator

be met by the method of the invention 5 batches of normal textile goods each with 5 g / l of conventional substance A or 0.1 g / l of substance FA 2. FN 5, FK 7, FB 1, FF 4 cleaned and filter pressure, distillation speed, antistatic effects. Warning smell and the condition of the water separator after distillation is determined.

Noun A FA 2 FN 5 FK 7 FB 1 FF 4 Filter pressure (at) 1.1 0.8 1.0 0.7 1.1 0.8 Distillation time (min) 23 18th 18th 17th 18th 18th Antistatic Well no no Well middle Well Goods genjch clear neutral neutral neutral neutral neutral Phases in the water separator: water milky clear clear clear clear clear Perchlorethylene cloudy clear clear clear clear clear

It should be particularly emphasized that the addition of 4 g of fluorosurfactant product per batch in the process of the invention is much easier to carry out than the addition of 200 g of cleaning enhancer per batch in the conventional process. This is especially true then. if the fluorosurfactants are dosed as tablets (1 g each) or if a section of a ^{fiber fleece impregnated with 5 g fluorosurfactant product per dm 2 is placed} in the machine together with the items to be cleaned.

Claims (1)

26 56
ι 384 A. C ₁₁ F ₂ ,, I.
I.
2 [ A ^{! Li} here mean: Hydrogen or an alkyl or R ₁ (CII ₃ Iol groups with I to 3 carbon ι the Tclomer radical C ₁₁ F ₃ ,, -1 or c "i ^; >, the Telomcrrest CF ₃ ,, ₁ 1 or ulcn: η of R ¹ + R ¹ + R ³ the remainder of one! Ri Alkylol group with 1 to 3 carbons atoms or R ² + R ¹ + R ⁴ the remainder H (CF ₃ ) ,,, H (CF.) ,, Patent claims: cyclic ring compound into which | material atoms, a cyclic ring compound,; an integer from 6 to 12, '' icriii heal a j:; inze number from 6 to 12. N 'is incorporated as a hetero atom,? R-. Ri, R ⁴ hydrogen or alkyl or alky- '_ bound into the N as a heteroatom an integer from 0 to 4. an integer from 5 to 25; 1. Process for cleaning textiles in orga an inorganic acid residue, is. ι an integer from 5 to 25; niche solvent baths thereby i an integer from 6 to 12; , ^: an inorganic acid residue, 0 (OCjII ₁ VOII identifies as a cleaning enhancer an integer from 6 to 12, here mean: Υ ,, ίίΊΙ.Ι, Ν — K- ¹ K '
I. N or SO., - N - Fluorosurfactants of the following general form an integer from I to 4, Ri I.
O meln in an application concentration of 0.01 η mCCHi ^ C-N (CH ₂ ), "N * R ² R ³ R ⁴ a gan / c number from 1 to 4; ^: K 'R ¹ to 0.2 g / l, preferably from 0.05 to 0! g / l, individually A. /) or several can be used in OR ¹ η ! ,,, 0 (OCjII ₄ MI P. Hydrogen or an alkyl ^ 'sips. ¹ ; i) CFj ₁₁ H (CHjI ₁₁₁ COOM m with I to 4 carbon atoms. here mean: P. here mean: Alkyl groups with 1 to 10 carbon M is hydrogen or a monovalent r, R, ', toffiitomen. Metal ion, preferably an alkali a nan / .e number from 6 to 12. limetalles. or NH ₄ ⁺ , R ₁ NH ⁺ , η a pan / c number from 1 to 4. NR ₄ -, 111 I) or 1: where R is an alkyl or alkylol P. group with 1 to 3 carbon atoms: <i R ₁ CIIjC men represents. η is an integer from 6 to 12 and m is an integer from 1 to 4; () \}
Μ b) Y (CFJ) ₁₁ (CHJ) ₁₁₁ OCIIjCHjCOOM Il YC here mean: Y H or F M is hydrogen or a monovalent one Metal ion or NH ₄ ⁺ , R ₁ NH \ m Ri NR ₄ ⁺ , where R is an alkyl or alkylol R ² . R ¹ gruppc with 1 to 3 carbon atoms men represents. ti η is an integer from 6 to 12 and;> m ni is an integer from 1 to 4; η D CJ-J ,,, ι SO., M H) here mean: n. M is hydrogen or a monovalent one Mclallion or NH ₄ *. R ₁ NH *. NR ₄ *. where R cine alkyl or alkylol gruppc with I to 3 carbon atoms · ,, men represents. π a gan / c number from 6 to 12: i) «1» C "I,", O - <^> X here mean: X COOM or SOiM. wherein M is hydrogen or a little metal ion or NHr. ,, R ₁ NH *. Represents NR _4. where R cine alkyl or alkylol gruppc with 1 to 3 carbon atoms men means. η is an integer from 6 to 12: _w > O [K ₁ CI- (II CIIjN ¹¹¹ K ¹ KK ¹ IA here mean: R. CJ - ',,, .. _h , R ¹ . RK R ι hydrogen or Alkyl or alkylol groups with I to 3 carbon atoms oiler instead he k) l \ H here mean: η
m
t -CH.- or -CH ₅ -CH ₁ - or CH ₂ CHR- or -CH ₂ CRR'-,
wherein R is an alkyl radical having 1 or 2 carbon atoms
R ^{1 is} hydrogen, an alkyl radical with 1 or 2 carbon atoms or a phenyl radical, R- ', R ¹ hydrogen or an alkyl or alkylol group with 1 to 4 carbon atoms,
an integer from 6 to 12,
• "or 1,
an integer from 1 to 4.