DE1469002A1 - Use of sodium zirconyl sulfate containing water-soluble silica for tanning - Google Patents

Description

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national Lead Company, New York, NY, USA

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Use of sodium containing water-soluble silica

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airkonyl sulfate for tanning

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The present invention relates to tanning with a zirconium compound

The aim of the present invention is to carry out a simple, inexpensive zirconium tanning process using a new zirconium material and obtaining inexpensive zirconium-tanned leather.

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It has been known for many years that various zirconium compounds can be used for tanning pelts, hides, etc. with the production of leather. Although such Compounds used in some cash prevented the relatively high compared to chrome-tanned materials Cost widespread use. The use of zirconium tanning agents actually remained practically restricted to the production of your white or light-colored leather types.

The subject of the present invention is a zirconium tanning agent uses »which comes close to chrome tanning agents in relation to the accounts. So the way is opened for the extensive production of light colored, persistently tanned leathers and many Completion problems can be avoided.

The production of a sum of tanning usable water-

■ & - ■ '■> - ·. ■ ■ · ■ ■ ■■. '. _s <sii soluble zirconium product with low cost after two simple steps is described in patent application IT 17 357 IVa / 12 m. In the first step, finely divided zirconium is roasted with an approximately equimolar amount of sodium carbonate to form sodium zirconium silicate. In the second step, we add the dry sodium zirconium silicate with 1.5 to 2.5% sulfuric acid (as 66 ° Be acid) per mole of sodium zirconium

BATH 809813/1023

silicate mixed. A violent exothermic reaction occurs. The reaction product obtained is complex and probably cannot be expressed in terms of a chemical formula. It has been found, however, that these products contain water-soluble zirconium products corresponding to about 24 to about 30% ZrO ₂ and about 1 to about 5 % water-soluble silica. The dry product obtained after the above-described second step will then simply be referred to as "water-soluble silica containing sodium zirconyl sulfate ^{11. However} , this term is not intended to describe the exact chemical nature of the products, but rather to describe them in a convenient manner. As described in detail below becomes very useful for tanning, an aqueous system of water-soluble silica containing sodium zirconyl sulfate.

example 1

116.0 parts of drained goat skins previously pickled at a pH of 1.8 were placed in a drum with 142 parts of water, 9.3 parts of sodium chloride and 16.2 parts of sodium zirconyl sulfate containing water-soluble silica. The latter "contained 4 _t 06 parts of soluble ZrO ₉ and 0.55 parts of soluble

on ^£

ehea SiOp or, / 100 parts drained skins, 14.0 parts water-soluble Sodium zirconyl sulfate containing silica,

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containing 3.5 parts of soluble ZrO ₂ and 0.47 part of soluble SiOo. After three hours of treatment in the drum, the shrinkage temperature of the hulls was 90.4 ° C. A solution of 3.5 parts of anhydrous sodium acetate in 4.8 parts of water was then added to the drum and rotation continued for 20 minutes. The pH of the contents of the drum was then adjusted by adding about 30 parts of an about 5.5% solution of hydrogen carbonate in water. The drum treatment continued for about 20 minutes after the addition. The bicarbonate addition and the turning were repeated and finally enough bicarbonate solution was added that the pH of the contents of the drum rose to about 4.5-5.0, the turning being continued for a further 20 minutes. After standing overnight, the drum was drained of water and the tanned hides were placed on a rack, exposed, sheared, and then washed and drained. 174 parts of water and 0.58 parts of anhydrous sodium citrate, dissolved in 4.8 parts of water, were added to the wet tanned hides in a drum usual type completed. After the fatty liquor treatment, it was found that the leather weighed 6.92 percent more by weight in the air-dry state.

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H69002

«. 5 -

Leg game 2

The procedure of Example 1 was repeated, except that 19.8 parts of water-soluble silica-containing sodium zirconyl sulfate (containing 5.0 parts of soluble ZrO ₂ and 0.67 parts of soluble SiO ₂ ) were used per 100 parts of drained skins. the SchruMpftoniporatur after tanning was determined to be 92.7 ⁰ C and the Fettlaugleder showed a weight gain of 19.2 ^ calculated based on the air-dry state.

Example 5

The procedure described in Example 1 was repeated, except that 26.0 parts of water-soluble silica-containing sodium zirconium sulfate (containing 6.5 parts of soluble ZrO ₂ and 0.88 parts of soluble SiO ₂ ) were used per 100 parts of drained skins. The tanned leather had a shrink temperature of 94.4 ⁰ C and after Fettlaugbehandlung showed the leather a weight gain of 27.1 / ", calculated on the air-dry state.

Comparative inheritance tests were carried out with goat skins, instead of sodium zirconyl sulfay containing water-soluble silica (da3 actually disodium disulfatozirconate dinydrate is) was used, the amounts used in Examples 1 to 3 with respect to soluble ZrO «

+) ooyiel from the more expensive kieoelsäurefreeicn Uatriurauirkonyl-

öulxat - * -

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is equivalent. The results of these tests compared with the experiments using deodorant water-soluble silica containing material are shown in the following table.

Sodium zirconyl sulfate containing water-soluble silica is designated as "KHZii", silica-free product alo "Ii2S" ".

Table A.

Gerbnitt Gl

Soluble tanning agent

ZrO,

lot

Shrinkage step weight gain rature after after Pett tanning, but caustic treatment in front of the Houtr-i- charged on lize the air-dry state

Parts per 100 parts of Iloo

⁰ G

ΚΓ ZS 3.5 14.0 90.4 NZS 3.5 10.5 87.7 KNZS 5.0 19.8 92.7 NZS 5.0 15.6 89.9 KHZS 6.5 26.0 94.4 ΪΙΖ3 6.5 20.3 - 90.4

6.92 6.42 19.2 13.2 27.1 25.3

Evidently, each of the 3 comparison smokes with equivalent amounts of soluble ZrOg with the water-soluble

before silica-containing product both at the achieved

BATH ORIGINAL

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pftemperature al-a also lei of weight 3 sur.ahtte of leather e results achieved. The improved serum body temperature can be attributed to the soluble SiCp present, the presence of soluble ZrOp either has a tanning effect, ie increases the tanning effect of the dee ^ irkoniuisa. Kov / ohl the soluble . -N the insoluble IliesolGüurc v / erden v / o.'il in considerable measure when tanning the skins u £ Ci; Gür.icn, where ... soluble SiOp i'ein acts as a filler material.

the following examples explained v / ird., v / was found, : ^ asar-luscious silicic acid containing a üätriiunzirönyl— also when tanning other L'ederarteii wirkaaa iet ·

. ..-.>: <.: Tanning drums were 100 parts of drained calfskins; Λ: ιΐ ,, which were ⁶ * ⁰⁸ ^ ¹² ^ to a pH value of 1.8 - 2.0 g.

■ · ■■. ■ • v.rin and 200 parts V / aoaer, 10 parts Ivatriumchlorid and i ^. 'I .eile water-soluble ICieuöl3äure enthaltendea Natriuu-. ., ../! sulfate, since 5 parts of soluble ZrO ₂ and 2.9 parts of Ge.:.:■ lOo, of which 0.67 parts waüeerlöalicheo LiO ₂ , contained, .. .l '.: n . ifaeh three-hour'Tror.imelbehandluri {; The temperature was 87.2 ° C. The intestine was dissolved in 2 parts of anhydrous acetate in 4.2 parts of V / aceer and added -,; ic treatment "for 20 minutes ^ «Cc.tst> The ρΐί - '^

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The contents of the drum were then increased by adding a 3.5 igo lion of nitrium bicarbonate in portions to the drum and continuing the treatment 20 minutes after each addition until the pH was 4.0-4.25 . The tanned hides were left standing over kacht in the drum, hung on racks, raised and sheared, then washed and drained green lioh. 150 parts of water and 1 part of anhydrous Eatriui citrai. were then added to the skins in the drum and rotated the drum for about 30 minutes, then drained. The skin was then prepared for the fatty liquor treatment and finished in the usual way. The chemical analysis showed that the leather 89 # of the soluble ZrO had taken up the silica present in dem'Gerbbad ₂ and 52.5 i ". The total weight increase due to ZrOg and SiO / was 22.42 #, calculated on the initial skin substance.

Example 5

The procedure described in Example 4 was repeated except that 26.0 parts of water-soluble silica-containing! Sodium zirconyl sulfate was used, since per 100 parts of drained skins contained 6.5 parts of soluble ZrO ₂ and 3.8 parts of Gesant SiO, of which 0.88 parts were water-soluble SiO ₂ . After three hours of treatment in the drum, the shrinkage temperature was 91-5 ° C. The chemical analysis of the finished leather showed that there were 88% of the soluble ZrO ₂ and 51 % of the total in the tanning

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bad had included SiOp present. The weight gain in relation to uropreney skin substance attributable to SrO ₂ and _{2 was 20.46 pounds.}

Example 6

100 parts of drained calf hides, which had been pickled at a pH of 2.0, were placed in a tanning drum. Then 200 parts of Y / a, 10 parts of sodium chloride and 24 parts of water-soluble silica-containing sodium zirconyl sulfate, which contained 6.0 parts of soluble ZrO ₂ and 3.54 parts of total SiO ₂ , of which 0.81 part of water-soluble SiOp, were added. After three hours of treatment in the Tromael, the shrinkage temperature of the tanned hides was 94-4 ° C. Then 2 parts of anhydrous sodium acetate dissolved in 4.2 parts of Y / water were added and tumbling continued for 20 minutes. The pH of the contents of the drum was increased by adding a 5% solution of sodium bicarbonate to the drum and rotating it for 20 minutes after each addition until the pH was 4.0-425. The tanned hides were left standing overhead in the drum, then hung on racks, exposed, sheared, washed and dried. 150 parts of water and 1 part of anhydrous sodium citrate were then added to the skins in the tray and the drum rotated for 30 minutes, then drained. The skins were then prepared for a bed liquor treatment

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and finished in the usual way.

For the further treatment of the tanned hides produced in Examples 1-6 and the goat hides tanned for comparison with acid-free liatric zirconyl sulfate, a commercially available Starard fatty liquor of the type used for leather is used . containing sulfurized whale oil and Rindsklauönöl 40 fo Waaser It was the usual Pettlau ^ '- used methods and measure the amount of Iettlauge oo which, 4.5 $ came into the leather After Fettlaugbehandlung da3 leather was still a standard treatment. It is of course also possible to use other fatty liquors with satisfactory results which are suitable for soft or light-colored leathers. The preceding examples show that tanning baths which contain water-soluble silica containing sodium zirconyl sulfate are aqueous systems Bind, with about 3.5 to 6.5 parts lb'sliohem ZrOp and about O _f 5 0.9 parts of soluble SiO ₂ per 100 parts drained, g stained hides or pelts. ^v '. ^

Also bathrooms with gröseeren amounts of soluble ZrOp bi3 about 10 Jt parts per 100 parts of skins can be used, but it is not clear from the tests that such amounts are necessary or economically · Since the content of waaperlöe-Iiehe silica containing Hatriujnzirkonylsulfaten to lö · -

ftAD ORIGINAL

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If the SiO is high, the amount of soluble SiO _{2 in the} baths can vary between 0.3 and 1 »9 parts per 100 parts of drained skins. Sodium zirconyl sulfate containing bio-water-soluble silicic acid can also contain other customary and known materials, for example potassium chloride for various purposes. The leather tanned according to the present new process can of course also be tanned again with other suitable materials. In the examples, although only goat, calf hides in aqueous systems with water-soluble silica-containing Katriumzirkonylsulfaten were tanned, 3 ^{e (*} och can dieoee tanning process even in cattle and sheep skins and other animal hides and skins einachliesalich reptile skins are applied. In the following claims is to The quality of the leather paperboard obtained by tanning with water-soluble silicic acid containing sodium sirconyl sulfate was judged to be very satisfactory in terms of look, feel and strength. Leather tanned in this way is coarser than chrome-tanned leather with similar hides.

In numerous places in the preceding description and in the following claims, reference is made to soluble ZrO _P and soluble SiO ₂ . The quantities and

soluble

Percentages of soluble ZrOg or /SiOg relate to zirconium, expressed as ZrOg * and silica, expressed as ala

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OK ,,, that according to the standard analytical method in the liquid was found, which was not dissolved by filtering off Material from a mixture of 4 parts of product with 100! 'Rush Krasser was obtained after ample time to dissolve the soluble substance was given.

In the preceding description and the following claims be, werji not otherwise said, parts by weight, Weight percentages and weight ratios are given.

ORIGINAL

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Claims (2)

Subject * Patent application Ii 15 698 IYc / 28 a national Load Coinpany claims 1. Use of water-soluble silica containing riatrixiuizii'lconyl sulfate for tanning, characterized in that a water-soluble silica containing liatriun ^ irkonylsulfat the following formula "is used: 23 ~ 31 / · '2r0p (24 - 30 $; ZrO ₂ in water-soluble form) ; 13 - 16>"GiO ₂ (1 - ₂ in water-soluble form); 34 - 40 ^r / - SO »; 13 - 16 '/. Ua ₂ ^; 0.5 - tf * H ₂ O. 2. Use according to claim 1, characterized in that in an aqueous Syatem water-soluble silica Vure containing ITatriUEizirlconylsulfat in such an amount used v / ird, v / ie about 3.5 "to 10.0, preferably 3.5 to 6 .5 ropes of soluble ZrO ₂ and about 0.3 to 1.9 parts, preferably 0.5 to 0.9 parts of soluble SiO ₂ per 100 parts of drained, stripped hides is equivalent. f:: U J U · -. .Ci: agen (M- 7 11 Abe. I No. 1 sentence 3 of the * nd.mng »ee _3. Of 4.9.196?) 809813/1023