DE1907767B2 - PROCESS FOR IMPRAEGNATING LEATHER OR LEATHER REPLACEMENT MATERIALS - Google Patents

Description

(R ₂ NH) _n , -H

wherein R _{1 is} a hydrocarbon radical with 9 to 20 carbon atoms, R _{2 is} an alkylene radical with 2 or 3 carbon atoms, m = 1 to 3 and η = 2 or 3, in organic solvents according to Patent 12 73 122, characterized in that solutions are used, which in a mixture z $ with A in addition

B. partially esterified or partially etherified polyalcohols or partially esterified polycarboxylic acids with at least contain an unsaturated or branched-chain radical with 8 to 22 carbon atoms in the molecule.

2. The method according to claim 1, characterized in that that one as component A imidazoline derivatives using oleic acid or Oleic acid-containing fatty acid mixtures have been used

3. The method according to claim 1, characterized in that that one as component B glycerol monooleate or pentaerythritol tetraoka or citric acid monooleyl ester used.

4. The method according to claim 1 to 3, characterized in that the organic solvent Petrol hydrocarbons or chlorinated hydrocarbons with 1 to 4 carbon atoms or Alcohols with 1 to 4 carbon atoms are used.

5. The method according to claim 1 to 4, characterized in that 5- to 30% solutions, based on the sum of components A and B, used.

6. The method according to claim 1 to 5, characterized in that the organic used Solutions components A to B in a ratio of 10 to 80:20, up to 90, preferably 15 up to 35: 65 to 85 percent by weight.

7. The method according to claim 1 to 6, characterized in that in the solutions used up to 50 percent by weight of component B are replaced by oleyl oleate.

The subject of patent 12 73 122 is a process ium impregnation of leather or leather substitutes mk salts of nitrogen-containing heterocycles, which is characterized in that one solutions of the Salts of unsaturated or branched-chain carboxylic acids with 10 to 20 carbon atoms and balic acids Imidazoline and / or pyrimidine derivatives of general formula

45

/ λ

R ₁ -C (CH ₂ ) _n

¹ ^

(R ₂ NHL-H

where R _{1 is} a hydrocarbon radical having 9 to 20 carbon atoms, R _{2 is} an alkylene radical having 2 or 3 carbon atoms, m = 1 to 3 and η = 2 or 3, used in organic solvents. The method is used in particular to increase the dynamic water resistance of leather. In Weilerbildung of the process of the main patent it has now been found that the effectiveness of the compounds mentioned in the main patent can be significantly increased if they are used in combination with partial esters or parts of polycarboxylic acids or polyalcohols containing higher molecular weight residues. The invention accordingly provides a process for impregnating leather or leather substitutes by using solutions of the salts

A. from unsaturated or branched-chain carboxylic acids with 10 to 20 carbon atoms and basic Imidazoline and / or pyrimidine derivatives of the general formula

R ₁ -C

(CH ₂ ) ,,

(R ₂ NHL-H

where R _{1 is} a hydrocarbon radical with 9 to carbon atoms, R _{2 is} an alkylene radical with 2 or 3 carbon atoms, m = 1 to 3 and η = 2 or 3, in organic solvents according to patent 12 73 122, which is characterized that solutions are used that are mixed with A in addition

B. partially esterified or partially etherified polyalcohols or partially esterified polycarboxylic acids with at least contain an unsaturated or branched-chain radical with up to 22 carbon atoms in the molecule.

Surprisingly, it has been shown that with such mixtures an unusually good dynamic Can achieve water resistance of the leather finished therewith. The observed effect

ίο

the effect of the individual components to a considerable extent, so that a synergistic effect to accept isL

Preparation of the compounds of group A described in the main patent. High molecular weight carboxylic acids containing a few carbon atoms are condensed with polyalkyleupoly- «, such as diethylenetriamine, triethylenetetramine, ethylenepentamine or dipropylenetriamine at a higher temperature while distilling off the water bathed in the ion. Suitable acids are primarily the fats or fatty acid mixtures obtained from unsaturated fats or oils, such as. B. oleic acid, aolic acid, linoleic acid, coconut fatty acid mixtures of the length of C ₁₂ to C ₁₈ , as well as fatty acid mixtures, from cottonseed oil, tea seed oil, sperm oil, tallow 5Γ fish oil can be obtained. However, there are also synthetically produced branched-chain carboxylic acids with chain lengths of C ₁₀ to C ₂₀ , such as those used, for. B. can be obtained by oxidation of branched-chain paraffins, into consideration. The imidazoline or pyrimidine derivatives formed in this way are then reacted with the above-mentioned higher molecular weight carboxylic acids with salt formation.

In the case of the present invention, the neutralization product of oleic acid is used as component A and a condensation product of oleic acid and diethylenetriamine are particularly preferred.

Of the compounds falling under group B, in are suitable for the purpose according to the invention primarily the partial esters of polyalcohols with 2 to 6 carbon atoms or polyalkylene glycols with 2 to 20 Oxyalkylene residues, preferably oxyethylene and / or oxypropylene residues, in the molecule with higher molecular weight unsaturated or branched chain fatty acids, preferably those with 12 to 18 carbon atoms, and the corresponding partial ethers from polyalcohols and fatty alcohols corresponding to these fatty acids.

From the group of polyalcohols the following should be mentioned: glycols, polyglycols, glycerol, pentaerythritol, sugar alcohols such as sorbitol, mannitol or inositol and the like. The esterification components used are preferably the same unsaturated or branched-chain higher molecular weight fatty acids as are used to prepare the imidazoline or pyrimidine derivatives of group A and have already been mentioned there. In a corresponding manner, higher molecular weight fatty alcohols, such as oleyl alcohol, or alcohol mixtures obtained from unsaturated natural fats or oils, e.g. B. coconut fatty alcohols of chain lengths C ₁₂ to Q ₈ , or tallow fatty alcohols of chain lengths C ₁₆ to Q ₈ are used. There are also branched-chain alcohols, such as those used, for. B. can be obtained by oxo synthesis, into consideration. The addition products of up to 4 mol of ethylene oxide with the higher molecular weight fatty acids or alcohols mentioned, and with higher molecular weight amines, such as oleylamine, can also be used as esterification or etherification components.

Further suitable compounds of group B are derived from aliphatic polycarboxylic acids 2 to 6 carbon atoms. They are made by partial esterification of these polycarboxylic acids with higher molecular weight unsaturated or branched-chain alcohols, preferably those with 12 to 18 carbon atoms, obtain. Suitable polycarboxylic acids are for example

55

60 wise: malonic acid, succinic acid, adipic acid, maleic or fumaric acid, citric acid, tartaric acid, ethylenediaminotetraacetic acid, etc. The high molecular weight alcohols used as esterification components are the same as those used for the etherification of the polyalcohols.

As compounds of group B, the Glycerinuad Pentaerythrite esters of higher fatty acids, especially oleic acid, and citric acid monooleyl esters particularly preferred

The mixtures used in the process according to the invention for impregnating leather are in Form of their solutions in organic solvents, e.g. B. aliphatic or aromatic hydrocarbons, such as mineral oils or heavy gasoline, chlorinated hydrocarbons with 1 to 4 carbon atoms or lower Alcohols with 1 to 4 carbon atoms are used. The solutions contain about 5 to 30 percent by weight of the impregnating agent mixtures, the proportion by weight of component A being 10 to 80%, preferably 15 to 35%, and that of component B is 20 to 90%, preferably 65 to 85%. The products are easily soluble in the solvents mentioned, but practically insoluble in water. They swell however, strongly in the presence of water.

Impregnation takes place either by immersing the leather in the organic solutions of the products or by painting on, brushing on or spraying on. As the alcoholic solutions in the presence Smaller amounts of water can also maintain their low viscosity by milling in the alcoholic solutions in leather that is still moist in the tanning drum can achieve good impregnation effects.

The mixtures used according to the invention are notable for their considerable water-binding properties Swelling power from. Their effect is probably based on the formation of viscous or pasty Water-in-oil emulsions in the interstices between the fibers of the leather. This means that when Moisture closes the pores and prevents further penetration of the water into the leather opposite. In this way, not only does the water penetration through the leather become significant delayed, but also decreased water absorption.

A particular advantage of the mixtures used in the process according to the invention is their stability in leather against repeated wetting. Also through many hours of mechanical stress The impregnation agent is not washed out when wet. The resistance of the stored mixtures from components A and B against washout losses is surprisingly large and outperforms the washout resistance of the individual components is considerable.

To support the effect of the claimed impregnation agent or to achieve special effects Known impregnating agents, fatliquoring agents, silicones and the like can also be used will. Partial replacement of component B by oleyl oleate has proven advantageous.

From the DT-AS 11 66 411 is the waterproofing known from leather by means of partially esterified citric acid in organic solution. It is there too indicated that the citric acid esters in connection with other waterproof impregnations, such as Condensation products from alcoholates of polyvalent metals with acidic phosphoric acid esters of higher

molecular hydroxyl compounds, or silicone oils, use When. However, this does not give any indication of the surprisingly strong increase in effectiveness, in particular the dynamic water resistance and water absorption of leather, if the citric acid esters according to DT-AS 1166411 according to the process according to the invention together with the imidazoline and / or pyrimidine derivatives of the main patent 12 73122 applied As the comparison tests given below show, corresponding combinations of imidazoline derivatives with the above-mentioned water repellants do not lead to such a favorable result.

Type ^of impregnation Glycerine mono- Bends
on the Maeser Alkylimidazoline machine until 3: 1 water passes through Blind test 530 10% solution of 850 oleate (I) 10% solution of 5 310 oleate (II) I + II in relation 49 970

example 1

A sample of a slightly vegetable-synthetic retanned chrome leather was used for 15 minutes in a 10% solution of a technical glycerol monooleate (approx. 44% mono-, 44% di- and 12% triglyceride) (I) or an alkylimidazoline oleate (II) or a mixture of the two components immersed in perchlorethylene

The leathers were then dried in air overnight and then at 65 ° C. after 1 hour. The leather samples were tested together with an untreated piece of leather in the Maeser machine tested for their water resistance. The results obtained are given in the table below. The mixture of the two components shows by far the best water penetration resistance.

The Alkylimidazolinoleat used for impregnation was oleic acid by reacting 1 mol with 1 mol of diethylenetriamine at 220 ⁰ C and subsequent neutralization of the basic reaction product with oil acid.

Table I. Example 2

Vegetable-synthetic tanned floor leather approx. 4 mm thick and of commercial quality Immersed for 15 minutes in a bath containing 20% technical glycerol monooleate (I) or 20% of that mentioned in Example 1 Alkylimidazoline oleate (II) or 20% of a mixture of these two components in perchlorethylene After the impregnation, the leathers were initially at room temperature dried until the solvent has completely evaporated and then to 50 bis one hour 55 C heated.

After the leather samples had been conditioned with an untreated leather sample for 2 days at 20 ⁰ C and 65% relative humidity, they were tested in the Bally Permeometer, the time was determined until the first water passage for water absorption. After the test, the leather samples were dried, air-conditioned and tested again. The two experiments are denoted by 1 and 2 in Table I below:

Type of impregnation

Blind test

20% solution of

Glycerine monooleate (I)

20% solution of

Alkylimidazoline

oleate (II)

I + II in a ratio of 1: 1

I + II in a ratio of 3: 1
I + II in a ratio of 1: 3

No. of the water attempt passes
after
Minutes

Water absorption in% after hours

1
1
2
1
2

1
2
1
2
1
2

11 56

340 2.5

130 7.6

360 3.0

Ί90 3.6

> 525
> 525
> 525
> 525
> 525
> 525

3.2
3.1
3.8
3.0
3.9
3.6

56
5.2

12.0
4.6
7.1

4.0 4.0 5.4 4.7 4.4 5.0

56
11th
16

16.0
8.5

4.8
5.3
6.1
5.4
4.9
6.1

13th
19th

25th
11th

5.3
6.2
6fl
5.9
5.5
6.6

6.3
6.8
7.2
6.6

6.1

7.5

12th
7.2
9.0
7.0
7.0
8.1

18th
8.1

11th

10
7.6
8.7

The results obtained in the test show the superiority of those used according to the invention Mixtures.

Another attempt in which the glycerol monooleate was replaced by a tallow fatty _{acid monoglyceride of chain lengths C 16} to C ₁₈ or by a ricinoleic acid monoglyceride, led to similar results.

Example 3

Vegetable-synthetic tanned, unfinished, flexible floor leather gap approx. 5 mm thick was treated as described in Example 2, but instead of the glycerol monooleate for impregnation Citric acid monooleyl ester (I) is used in addition to the described alkylimidazoline oleate (II)

became. The impregnated leather samples were tested as in Example 2.

Type of impregnation water
by
occurs 380 Water absorption in%
after hours Min. 1 2 3 Blind test 3 41 44 46 20% solution of 10
Citric acid monooleyl
ester (I) "Xf ₁ A 20% solution of Al- 5
kylimidazoline
oleate (II) 40.3 - - 20% solution of
I + II in relation
3: 1 14.1 14.8 15.9

The mixture used in accordance with the process of the invention impregnated leather a significantly higher water resistance than the individual components.

Example 4

Weakly vegetable-synthetic retanned chrome upper leather or vegetable-synthetic tanned Floor leather about 5 mm thick was treated as described in Examples 1 and 2, respectively however, instead of the glycerol monooleate, a mixture of pentaerythritol tetraoleate and oleyl oleate im Ratio 1: 1 in addition to the alkyl imidazoline oleate in perchlorethylene was used.

Type of
impregnation

Chromober
leather
Bends
on the
Maeser machine

Floor upper leather

Water absorption ser- in% after hours

Min. 1 2 3

Blind test
20% solution
a mixture
of pentaerythritol tetraoleate
4- oleyl oleate 1:
20% solution
of alkyl imidazoline oleate (II)

20% solution
of pentaerythritol tetraoleate
+ Oleyl oleate 1:
and II in a ratio of 3: 1

550 3
1620 8

56 660 5

41 44 46 39.8 - -

40.3 -

The test results prove the strong superiority of the "method according to the invention" Application of the mixture.

Example 5

Vegetable - synthetically retanned chrome upper leather of commercial quality was as in the example 1, but instead

ίο of the alkylimidazoline oleate, the neutralization product of an alkylimidazoline prepared using a branched-chain carboxylic acid of chain length C ₉ to C _{1 was} used in addition to the glycerol monooleate. Here, too, the tests carried out on the Maeser machine showed that the mixture used according to the invention was greatly superior in terms of the water resistance of the impregnated leather.

Comparative experiments

Vegetable-synthetic tanned floor leather approx. 4 mm thick in commercial quality by immersion for 15 minutes in a 20% solution in perchlorethylene of

A. an alkyl imidazoline oleate as used in Example 1 together with glycerol monobehenai in a ratio of 1: 1,

B. alkylimidazoline oleate and a commercially available silicone oil for hydrophobing leather irr Ratio 1: 1,

C. Alkylimidazolinoleat and a condensation product of aluminum isopropoxide and mono alkyl (C _12/14) phosphoric acid esters in the ratio 1: 1

impregnated and finished as described in Example 2. The determination of water penetration unc Water uptake values were carried out with the Bally-Per Meter according to Example 2. A test on a non-impregnated leather (blind test) was carried out also carried out. The results are summarized in Table II below:

Table II

Type of
impregnation

Water flow

Water absorption in% after hours

Minutes I

60 325 160 9.0 17.9 21.9

Blind test
(not impregnated)
A.

10 4IN 42.2 42.7 - -

7 41.8 42.0 42.8 - -

> 505 2.8 4.0 5.1 73 8.0

> 515 2.8 4.1 5.2 7.7 10.4

175! 6.7 2Z5 253 28 ^ 29.4

97 12.0 24.6 30.9 35.4 36.3

20 34.0 35.7 37.2 - -

13 34.6 35.6 36.4 - -

Claims (1)

Patent claims: t, method of impregnating leather or Leather substitutes by using solutions of the salts A. from unsaturated or branched chain Carboxylic acids with 10 to 20 carbon atoms and basic imidazoline and / or pyrimidine derivatives the general formula N- R ₁ -C