DE1444986A1 - Leather treatment - Google Patents

Description

During the tanning process, the leather becomes the most natural Removed oils and fats. In order to prevent the resulting drying out and becoming brittle, the Acid-free vegetable and animal fats are added to tanned leather, which makes it supple, soft and elastic.

In the past, oils and fats were mainly supplied by smearing the leather surface and then letting it dry. When the leather is greased when dry it remained greasy after drying and was dark in color because the fatty substances did not penetrate the leather could, but were only distributed on the surface. On the other hand, if it was greased while it was wet, the leather remained brightly colored after drying and was not greasy because the water content prevented the penetration of fatty substances promoted so that these were better distributed.

Then followed the greasing with fatlickers. Thereby the oils Applied to the leather in the form of oil-in-water emulsions. These oil-in-water emulsions are produced by either emulsifying of the oil is made with emulsifiers, such as ordinary soap, or the oil becomes partially water-soluble through sulfation made.

With the leather fatliquoring technique by fatliquoring the leather

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not only which and flexible "but also become waterproof"

In accordance with the invention, leather is now treated with synthetic Fatliquors, which make the leather not only special is made soft and pliable, but also water-repellent in a high hat Post-treatment of the usual non-aqueous silicone impregnation solutions this water-repellent effect can then be further enhanced

The method according to the invention consists of greasing and making water-repellent of leather by means of synthesized fatliquors and possibly an additional post-treatment with niehtwlSrlgeü Organopolysiloxane solutions are thus recognized » that they are water-soluble copolymers as synthetic fatliquoring agents and / or containing salts with 1-5 carbon atoms Monocarboxylic acids are applied to the leather * the by ttasetsung ton Sllanen the general formula

'3-a *
where R is a divalent aliphatic hydrocarbon

- 2a -

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remainder with 3 bit 6 carbon atoms, R * alkyl residues with 1 to 7 carbon atoms, R "alkyl residues with 1 to 3 carbon atoms or residues of the formulas -CH ₂ CH ₂ OCH ,, -CHgCHgOCgH- ° & ev -CHgCHgOH, Z hydrogen atoms or monovalent, optionally-aminosubstl- ^ uierte hydrocarbon radicals, wherein the ZGH group at least at the third from the Si atom distant C-Ato "is bound and not more than 10 carbon atoms t and η is 0 or 1, with The thy1-polyslloxanes containing hydroxyl groups have a viscosity of at least 30 ° C./25 ° C., in the usual ratio of 1 to 1 to 1 50, preferably 1 to 3.

Xm against * this is done with commercially available synthetic Fatting agents, e.g. sulphated and / or emulsified oils a greasing, but practically achieved only a slight water-repellent effect. Will leather bloomed with these handis Grease fillers have been greased, then in the usual way Folysilojcanimprftgnierung is subjected, which is thus achieved Water-repellent impregnation is sufficient, but considerably less effective than when using the inventive one Sealants and subsequent treatment, such as those from the Comparative verses in Table X, page 10 (see under 'Control') clearly evident.

Dimethylpolysiloxanes containing hydroxyl groups are those

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Bit about 3.5 to 4.5 ßew «£ 03 groups and a viscosity tob 35 bte 50 c8t./25°Ö beroreugt

The root R can be any saturated or unsaturated linear or branched aliphatic hydrocarbon radical J with 6 carbon atoms β

The Alkylreet E * can s.B. a Uethy 1-, Ethyl-, Propyl-, Iaopropyl-, Butyl-, Anyl-, Hexyl- or Kept / lreat θοin · Before «ugeweiae means B * of a fiethylreat

Examples tu * alkyl radicals R "are methyl, ethyl, propyl or Xeopropylreete« whereby the Sethylreet lets ·

The ZgS group can, for example, correspond to the following formula group »

(C ₁₀ H ₂₁ ) H »- _t ^ (C ^) gZß» -, (C ₆ H _n ) HH-, (O ₇ H ₁₅ ) HH-,

g - _t CH ₂ -CHCH ₂ H ^ and

Instead of liieehpolynerieate ala such a can whose waeeerltJjllche Salt · nit iäonocer ^ naäuren used »· dl Ttrmiechen by the acid with the silanes and the hydroxyl group-expanding Dlnetliylpolyslloicanen be produced · Examples of Sonooarbonsäuren are Aaeieen- _ff Eaeig- and propionic

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• acid, the rare manufacture of joraiat, acetate b »w. Propionate • to be used as «« Aeetatsalse are, however, avoided ·

Particularly advantageous eur reinforcement of the water-repellent Effect · let a «sueätslloh · wrong treatment de« leather old non-aqueous solutions, the following components contain »ι

(a) 15 Me 50 wt. 56 aliphatic titanium or zirconia of the general formula Ti (OIt " ¹ ) * baw. Zr (OR" *), where B ** ge "optionally aliphatic" carbon atoms containing hydroxyl groups are old less ala 13 carbon atoms and less than 4 mean Bydroayrlgruppen and / or their partial hydrolyzate which is soluble in aliphatic carbons

(b) 5 to 70% by weight of methylpolysiloxanes, which are essentially composed of Triaothyleiloxane and SlOg units built up * ind, eo dad the ratio of ilethylreeton to Si-Atoaen of 1 to 1 bie 1.5 t 1 and

(o) 15 oi '80 Gew.Jt organopolysiloxanes of the formula H duroneehnlttllohea ä "" SiO. _, wherein H "" has an alkyl or alkenyl radical

means less than all 6 carbon atoms or monocyclic aryl create, a has a Durohoohnitt value of 2 to 2.9 and an Each · Si-Atoo aindeetene a coal waeseretöffreet bound let.

The Zueasaeneetsung this, door dl · Haohbehandlung advantageous leather Lueungen let known 1 * see DBP 928,118 and 048,667.

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After the treatment according to the invention and, advantageously, the finishing, the solutions are applied to the leather for post-treatment. let trookenes leather preferred. Al · Löeungeaittel can be used β.B «Kohlenwaeaeretoffe and halogenated tohlenwaaeeretoffe wit Perchlorüthylen» Methylohlorid, toluol or petroleum fractions with boiling ranges tob U1 ^o - 188 * 3 ° C (naphtha aineral spirit ») or 175-210 ° 0 (Stoddard-Löeungemitttl) ·

IKLo laoh treatment can be done by simply immersing the trooked leather · in the «Löeiuag» ilengos tone 5 here 10 ötw.jt Feetetoffsehalt, lied to dao Gewioht doa dry leathers, deliver the beetea results, although a smaller or larger honing · on fts open can be used «

Inventive treatments körsnea 1 »egg according to any ▼ experienced tanned leathers vorgenomaen wsFie & i However lot chroagegerbtoo Leather

Bio faaoerabwoioung dor treated Lodorsorton was added to a leather tea tea, which in its effects i ¹ ^ lent that lot _t described in the "Journal of tho A &erloa" Leather Cheniete AssooiaUoa "Atiguet 1957" Soite 401 - 402 ". Dio Maeohiiio has oi & ea Jrobehalter, dor auo swoi vertical urine "aera beetcht" Jedo Klaaaer has a fixed and a movable intine dor Haaaem iet attached to a horizontal reciprocating board, by which an eentereo wheel is moved · bio leather sample is folded and clamped,

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dad bit «In« Hold · picture · *. Za this MuId · becomes Blelsohrot brought in «The under« rope of the hollow is immersed in the water uad the am «·« ad giving shaft »with 60 movements operated per minute. Si · AnMhI of the movements that up * ur Durohfeuohtung dee leathers are needed »is durob a electrical counter determined * X to determine the Durohfeuontung An electrode is attached to the inside of the specimen and an iron width on the outside the water contains SsIs for increasing the conductivity. That Sindringen τοη barrels in the leather triggers a road tour off »which autoaatieoh shut down the electric counter ™ will"

for applying the fatty substances to the leather siad athrere ▼ experience * known, but see the following aa best reinforced Has i bar the start will be aaoh! « First the leather 90 is iliacitated with water in a horizontal position Drehtroaael gewasohen «Then daa lasssr is derived and that Leather again old 150 J * laeeer, besogoa on the oewioht of the leather, Tereettt uad dl · Trosael becomes to KIa. long turned. if If necessary, the pH value is divided into 7. Aneohllefend is the usual frost content of the solids " der fettttsgsmlttel, lied to daa Gewioht dee trookensa leather « given in dl · tronael and dl · Iroaael turned for 70 minutes * The lasser is extracted from dsr froaasl and daa leather 90 min. Blown in flowing water «The leather is spellbound again laid dry, then stretched, piled up and over iaoht

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trookaen read. This procedure was used in all examples used for the application of the iettungeaittel «

Di · DTR amount used can fettungeaittel wide in "in ·" Bereioh Terlieren, beiepieleweiee "wipe 1 10 bio 0EW" jC _f rorsugewei ·· are rerwendet about 9 Gew.ji. When using less than 5 pieces of leather, the treated leather becomes less white and can even become less blegea "to hard and brittle." When using more than 9 wt achieved, on dea da · leather can no longer absorb any «fatliquoring agent ·

dd

For the treatment of leather, the following Yereohietfenen iettung- and Laehbehandlungaforaulierungen were made

(1) Dureh Tenaieohen τοη 28.4 Gew.fS a ·· hydroxylated di-Bethjlpolyeiloxane as "about 5 J _t bie öew 4.5.) I hydro ^ i-"'groups contained and a viscosity τοη 55 ^ bie 5O o8t./ S5 ° 0 had £ 8.4 wt. * Of the silanes of the formula ^ (0Rg) ₂ KH (CH ₂ ) JSi (OCHj) Jt 1 $ _t 4 Ge *. * Glacial acetic acid and 27 * 8 OtWtJf Ssopropyl alcohol was "in Mieohpolymerieateal * hergeeteUt.

(2) Duroh Vermieehen τοη 48 # 4 Oew · ^ hydroxylated «Dimethylpoljeiloxas from (I) ₉ 8 _t 6 Oww.ji de · Silanes from (1), 4 # 6 Gew.ji Eissssig and J3 _# 4 Gew.Ji Ieopropylalkohol was a Mieohpolymerieateal · divided here.

909821/0839

(3) Duroh Yermlechen ron 42 ₁ 7 wt. Jf hydroxylated a Dinethylpolyslloxan au · (1) »14 §2 8ew» # dee Silan · au «(I) ₉ 7» 7 Öe »* ji Bleeseig and 35 # 4 öew.ji Ieopropyl alcohol is produced by "Mieohpoly ** rieateal".

(4) By Teraleohtn τβη 45 * 93 wt. ^ Hydroxylitrt «Die · thy1-polyelloxan au · (1) »5» 6Q 0tw.?4 dee Silone dtr Toratl HjHCCHgJjSKOOfljJj, 2.76 G * w.? T EieoBoig and 47 * 63 Gtw.jt Ieopropyl alcohol was divided as htrg.

In the ioraulitrun ^ tn M mentioned, Scr Iiopropyl alcohol functions only as LiJeungealtttl and Tri-'gereutatana. Although the «s« r al «LO- ■ unold ·! fcrroriugt lat, can also methyl alcohol ethyl _t * alcohol or other suitable solvents · be rerwendet. Sideloads 1-4 were used as fatliquoring agents.

for the Haohbehandlune de leather the following formulas were suherelteti

(5) ForÄUlieran «au · in · weeentliohen gl« lohen Gewioht · share

(a) Eis ·· Di »ethylpolyeiloxane · · 1η · Γ Tiekoeität tos about 330, • St. / 25 ^e Ö _t

(d) einee Mi "obpelyM" rl "· at · au (CHj) ₅ SiO _1/2 units and 8iO ₂ -Iinheiten ait a" Terhältnie (CHj) ₅ Bl 1 BlO ₂ Ton 1 1 1 bl · 0 _p 6 l 1, and

(0) Tetra-2-ethylhexyl titanate, in Yereohiedenen concentrations la Perohlorathylen

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(6) Formulation (5) in Yeraohiedenen consentrations in petroleum fractions (Stoddard solvent).

Hit tiieeen formulations were dyed, ungreased leathers from the companies Armor, in the table old Λ beselohnet ”and Pfleter * Vogel, in the table referred to as old P&T, in the specified amounts (weight: 56 solid content ₉ sucked on the Oewioht dee dry leather ) treated "Each of the formulas was applied to three leather covers, the τοη rereohiedenen filing of the animal skin etaoaten and the usual white old side core and sharks are called" They bo treated types of leather were old of the described leather teaaeohine tested for their woeeerabweleende firing "They Brgebnieee and In the following table I "ueaaaengeateilt · you numerical values mean the JüMsafcl of bends dee Leclerc, the bie sun Streadurohgang required eind · Venn for dieee numeric values Be · iet reioh indicated eo let dae on untereofaiedliohe Dioke the three τοη an animal skin · thousands Lederetüoke Burüokeuführen. The different Sloke Tereohledener Jierhttute also plays a role in these values.

909821/0839

6880/138606

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Ir *

Led «

d «r s * utli

At »hl dtr at» n »chli« flcnd «r

«TI ΊΤοήηΟΙι

■ it

IO

5 3 5 5 5 5 5 5 5 5 5 5 5 10 5 5 5 1 3 5

! astron *
joatroll 5

PIT

PAT

PAT

9,193-58,274

530-687 2,966-6,340

1.423-4.309

51-111

5,950-23,725 874-5,050 1,031-5,028 546-1 * 564 5,950-15,956 12,031-14,040

67-116 1.561-4.OCO *

35-119 1,978-5,159 10,524-22 * 267

582-1 · 131 1,266-1 * 593 680-1,629 141-190 29-52

22,000 "

95,000+

95,000 *

60,000+

24.914-69.COO *

60,000+

35,440-80,000 +

15,095 * 100.

50.137-100.

57,871-60,000+

11,392-70 * 000 +

70,000+

2,936-48,246 85,000+ 85,000+ 12,053-50,000 + 50,000+ 4.258-50. ^ 00 + 3.722-14.233 55-127

100,000+ 75,000+ 72,000+ 60,000+ 58,627-80,000 + 60,000+

80.734-100.1 46.361-100 000 -

8,452-67,170 +

3 * 268-20,000 + 74-138 60,000+ 3,417 * 68,392

• lUBAtMUlA · F.tt ^ _8a ittel _f t'le 4-12 G «*. * Sulphated · 85,000+
85,000+

11.291-50.ObO + 50,000+ ι -

47,607-50,000 + 11 * 562-20 * 000 + 147-258 I.

eaulclert »oils ratbsfttea.

CD CD CO

lie co »the table ereiehtlloh is improved by dl" erflndungsge ~ ■ iiüt treatment, the flexural strength and Waoaerabwelsung wesentlioh, its comparison with the tungenitteln with commercial FMX Torgenouaenen treatment dee ledere ·

They ronaullerungon (?) And (5) are called "greasing" - for example, "HachbeJbandlungGiaittel advised.

example Currently

By Veraisohen of 47 »23 wt · ^ hydroxyliertom Dlmethylpolyeiloxaa aua (1), 5.73 wt. ^ Dee Silano aue (1) and 48.98 aew · ^ Ieopropylalkohol eih Uischpolynorioat was prepared x P Y Lüdcr wurdo old 5 (solid content , Bosso ^ cn "treated dae Gewloht dee troolcenea ledere) this FettunssformtaHerung you checkout tait dor LGdertostmaochino revealed oinen Biegebereioh tone $ 7 103 tie" through an aftertreatment old 9 Gew.ji το "for-Bulierung (5) (Feetetoff content" on besooes the weight of the dry leather) a bending area τοη 6 687 to 53 602 was determined «

Example 3ι

In Poraulation (4), instead of the silanes used there Silanes of the Porsel

HÄ (CH ₂ ) ₃ Si (QCH ₅ ) ₃ or the fonael (ΟΉ _; ) ₂ Ι7 (ΟΒ ₂ ) _? Π1 (ΟΟΗ ₃ ) _? embed QBd practically the same results with the leather

909821/0839

Example 4t

Za foraulierung (3) was · anet «lle d ·· there rerwendetea silanes the blaa of the fom «l

0H ₉ ) ₂ best and practically different results obtained in leather treatment.

Bolapiel 5ι

Duroh Ttreleohtn του 42 ₁ 7 wt. ^ D ·· hydroxylitrttn Dla «thjrltintr Viekoeität τοη« twa 30 oSt./23°0, 14.2

de · silanes of Fontel H ₂ I (OH ₂ J ₂ HH (CH ₂ J ₃ Si (OCHj) ₃ , 5.9 Oew.Jf Aaeietaeätire and 47.2 Oew.J * methanol "and dae «it gates achievement al · Pettungtaittelst« has been ·

Duron Termleonea of 42.7 oew. J * a hjrdrojgrlierte Dimethylpolyeilexaaer Tiekoeität γοη about 75 o8t./2> ^e 0, 14, t »ew, * d ·· Sllan · der fora« l H ₂ I (0B ₂ ) ₈ IB (0B ₂ ) ₃ Si (00H ^ ₃ , 9 "5 Jt Propioa * • Bar" and 33 "• Öew.ji Ethanol was made in Hleohpolyverieateal, since it was used as a fatliquor with good success.

Za roraalienag O) were instead of the silanes used there Silaa · der for «·! (OH ₃ OB ₂ O) ₃ SIOB ₂ OH ₂ OH ₂ Ih ₂ or the formula (H ₇ C ₃ O) ₃ BiCH ₂ CH ₂ CH ₂ IH ₁ and practically achieved di · gleiohea Brgetai ··· in the Ledor treatment.

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Example 8i fl <f

The following formulations were hergeetellt and di · treated therewith Ledereorten described with and without aftertreatment wi · in Beleplel one, you sat · water repellency tested ι · - ™ - ---- - ^ ^ - ■ - ^. R '/ -y; .- \ _

(7) Buren contains 42.7% by weight of a hydroxylated diethylpol / aiXozan, since it contains about 3.5 to 4 * 5 β * * £ hydroxyl groups and has a viscosity of 39% i> 50 oSt ./ 89 ⁰ O had »14 _t 2 Oew.ji dee silanes of the formula H ₂ I (CH ₂ ) ₂ IH (0H ₂ ) ₃ SiZC> 0H {0H ₃ ) ₂ 7 _3t 7 # 7 öew.ji Eieeeaig and 39 »4 öew.jt xeopropyl alcohol became a hollow polymer ateal«

(8) Identical with formula (7), but with the floodplain, that SlIaM the porael H ₂ I (CH ₂ ) J ₁ HHOH ₂ CH (OH ₅ ) OH ₂ Si (0OHj) ₃ ▼ was used. ^: -. , ■ ■. · ^: ■ ..

(9) «with Poraulation (7) identieoh, but old of the Auenahae,

deJ da Bila »of the formula H ₂ i (CH ₂ ) ₂ BHCH ₂ CH (CH ₅ ) 0H ₂ 8i (CH ₃ ) (00B ₃ ) _£

;.: ^; > * t »« ndtt was. ":;.;-; -., v ⁵ ■■; .; '■' - '■' - ''

Formulations 7 - 9 were teaed in as a fatliquor and her «vaaeerabweieeiid · flrkuBg in Tergleioh old pornography (3) with and without hair treatment with the terms ($) and (i) checked for example 1.

The rivets are subdivided in Table XI below.

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Tabtll II

OO 1S3

foam * α · »· 5 I * «« r Looked! umr Bi · »
CUBfltB aatfh ABMhI 4 · ρ Bi «« ttn * «j%« 1 aneclOl * fl «nd« laeh ^ chaaCto « 7th * 5 8th 5 19.994.57.Ä1 (5 Oiw.Ji) 3 5 3 A. 17.Ο41-5Ο.ΟΟΟ + · 50 * 000 + 50 * 000 + 9 5 5 ■ A 1,085-2,235 50,000+ 50,000+ 8th 5 A. 3,415-5,895 50,000+ 50 * 000 + 3 A. 50 * 000 + 50,000+ 50 * 000 + 9 A. 178-945 50,000+ 50 * 000 + 8th P&Y 258-877 5 * 324-50 * 000 + « 2,412-12,904 x ^ MT 460-1,549 48 * 654-50 * 000 + 8 * 972-19.797 ^ MT 50 * 000 + 8,764-50,000+

Aral the

50 * 000 + BieguD «s

Claims (1)

Claimed Method of sun greasing and water-wrapping of leather by means of synthetic fatliquoring agents and optionally one jusKtEliohen aftertreatment of non-aqueous organopolyeiloxane solutions « d a d u r o h gekennselob.net « all synthetic fatliquoring agents are water-soluble copolymers and / or the strings of which are applied to the leather with monocarboxylic acids containing 1-3 carbon atoms, which by Implementation of Sllanen of the general formula Z ₂ NRSi (OR ") _{> n} , where R is a divalent aliphatic hydrocarbon radical with 3 to 6 carbon atoms »R * alkyl radicals with 1 to 7 carbon atoms, R" alkyl radicals with 1 to 3 carbon atoms or radicals of the formulas -CHgCHgOCH «, -CHgCH ₂ OC ₂ H ₅ or -CH ₂ CHgOH, Z denotes hydrogen atoms or monovalent "optionally amino-substituted hydrocarbon radicals" where the .U U 9-8 6 is bound at least to the third carbon atom removed from the SI atom and contains no more than 10 carbon atoms in total and η 0 or 1 is, with hydroxyl-containing methylpolysiloxanes with a viscosity of at least 30 eSt, / 25 ° C, in a ratio of 1 ι 1 to 1 s 20 "preferably 1 to 3" have been produced. 909821/0839