DE1619288A1 - Flexible sheet-like structure, in particular artificial leather and process for its manufacture - Google Patents

Description

PATENT ADVOCATE PATENT ADVERTISEMENT

bipl-ing. ADOLF SPREER graduate phys. DR. W. JUNfUS

3 HANOVER

ABBESTRASSB 20 TELEPHONE 13 4Ϊ 30

June 15, 1966
' ^: .-. ■ Heine file :. 1085 Dr.j./Hl,

Applicant: SVI2, narodni podnik, Gottwaldov-Zlfn

"Flexible sheet-like structures, especially synthetic leather, and
Procedure to his. Manufacture ".

The subject of the invention is a flexible sheet structure,
in particular artificial leather, and a process for its production.

It is known that the general shortage of natural leathers in the world is being replaced with the production of artificial leathers and leatherwork , which, in terms of their appearance and their point properties, imitate natural leathers. That so far
The best synthetic leather material, whose big properties most closely approximate both the subjective and the objective properties of iiatu leather, eats the fibrous leather - made of very fine oinacled synthetic fibers. The atis this Facorn hex ^r p; created Untorlassmaterial is soaked with suitable poly, gobmiaen and with a surface treatment

, similar to natural leathers or box others

BATH

/ 1141

However, the requirements for the properties of the leather for the shoe uppers and for the clothing purposes are very demanding, both from the standpoint of the mechanical properties, that is, for example. Resistance to repeated bending stress (long-term flexural strength), tear resistance, liahtfestiglsBit (strength when the seam is torn out), as well as from the hygienic point of view, that is permeability for water bowls, air permeability, a certain degree of hygroscopicity and finally also from the point of view of the so-called subjective properties, such as softness, suppleness, leather grip, folding and the like ·.

So far it has succeeded, including most of the requirements the requirements for the development properties, with a artificial, made from elemental synthetic fibers of an extraordinary high fineness- ^ that is fineness of one titer below 1 denier, best suited to the manufactured product. In order to achieve the optimal structure of the artificial leather, it is further proposed Fibers with a so-called profile cross-section and several components to use containing fibers, which bycr. Impact the following mechanical and thermal processing, the space crossing of the fibers in flat structures, suitable mechanical-phy- siklüLische as / ie also hygienic and so-called subjective properties to ensure.

The existing knowledge of the production of artificial leather

009849/1741

with hygienic properties, so lead to the use of aehr demanding raw fiber material and therefore it is understandable that the previous economic viability of producing these plastic artificial leather is by no means cheap «Likewise nut laa :; in the previous "processing of these raw materials high demands in the production of fleece on the card * - od ^ r aerodynamic machines, as well as mechanical ones Solidification of the fleece on the liaäel-Eini ^ hi machines. In both cases, the rollers of the carding machines must be very fine t-soups and the Sinstlchmaseliineyi with .sshi? fine Iladeln be provided what their ■ effective J ^ öeitsleistiffig -pretty sits down and back in the MirtscliaftlieMctlt 4ts ses be "öeri: bar '

t igt »task of the W £ 'SMÄg -is

3-dsteliend-es ^: Stmstlöct @ r ■ - «i

Ka-tiflrrolisoffe in addition to low-demand vöüeia f

next to. '! l

cheap-

Spoiled "iiss? Ö © ^ a» © by. Sioir das Leeciian Siss-tlgkeiteii- unä;

Si

depth «, -;" ü "© n". GSdSi _5. -folding

BATH

■■ - 4- -

The essential * to the products of the invention ordered in '> that of the base fiber material on a mixture of Kollan.enfasern from a greater average length than 1 and manmade fibers., Is formed, in particular of fully synthetic fibers mutually with each other mechanically with Faserbünaeln or Binary threads are connected and mutually impregnated and connected with an adhesive, whereby the adhesive used is suitable to react with reactive functional groups of the colloidal fibers and to form covalent bonds with them,

The artificial leather is rait a woven or knitted (knitted) Textile insert stiffened, whereby the synthetic fibers contained in the basic mixture are • shrinking (pulling in) »

Used for the production of artificial leather; a method according to the invention. The essence of the process of the invention consists in the fact that the fibrous web, produced from a framework of fibers in a manner customary in the textile or paper industry, is consolidated by mechanical crossing of the fibrous material. The solidification takes place, for example by pricking on needle -Einst I machines or shall find, if necessary, adjusted with ii'aserbündeln with binding threads with the aid of the action on the through knitting machines which aum pass-through of the base web this case, either the non-woven, alone, or the nonwoven with a woven or knitted (knitted) textile insert crossed.

009849/1741

BATH

The mechanically crossed structure is condensed in a milieu in which the fibers to be shrunk are drawn in according to their Gharalkter ", 2.B. the synthetic hydrocarbon fibers, vinyl or polyester fibers contract with increased temperature and the polyvinylaluminum fibers run in an aqueous medium or at a higher humidity; The base fabric (fabric) after its compaction by rushing, dipping, spraying or impregnated by Drucksaturation with such substances, soft are capable serve with reactive ITunktionsgruppen of the collagen fibers to reagierene by z _o B _e Iiösungen or dispersions of the Carbamäiiharze, polyurethanes, Polyar. ilde, melamine-formaldehyde, urea-formaldehyde, phenol-formaldehyde or resorcin-formaldehyde resins

Aan is used as an essential component for the basic fiber material Coil-ply fibers, which are made from various sources of collagen, that is predominantly from the tannery waste after the hides have been processed into leather, such as 2,3 »split, subcutaneous connective tissue, machinery! Äbscimitzel and others, are obtained «These materials are ashed with calcium hydroxide, tanned and then mechanically frayed; the average length of iCollagen fibers must be. 1 cm

The Geitendmachung of the collagen fiber made possible with! the reality of the collagen functional groups the chemi cal binding with a suitable type of binding agent, which in particular includes garbamide resins, and also resins based on polyurethanes, Polyamides, melamine-formaldehyde ^, urea-formaldehyde,

Ö09849 / 1741 ₆

BATH ■

Phenol-SOraaldehyde and Eesorzin-Iornaldehyde resins and others place. The choice of the individual binder types depends on the requirements to the final mechanical-physical properties, mainly due to elasticity and toughness --e ^

example 1

Manufacture of plastic leather with hygienic features for shoe uppers »

Rindsspalt, that is cowhide leatherhauu from the neck part without the top After the tannery ashes, it is washed in running water, cut into pieces with a size of about 10 by 10 cm. The decalcification is done with a 0.5 # solution of ammonium sulfate carried out. The necessary liquid coefficient is 200? J, the temperature 25 ° C, the duration of the operation 4 hours. The decalcification takes about 2/3 of the thick pieces.

Pickling follows; the fluidity coefficient makes 200 ⁰ yo , it. 2p of an enzymatic coat "pelin" on the weight of the pelt and 833 casein units are added; pickling takes 24 hours. V times this time / ith the bath replaced, for which purpose a fresh fluid of the same Susa ^ ensetzuns is used, and the material is stained more second ^1V hours »

After the pickling has ended, the pelt is washed for 30 minutes at a temperature of 25 O in running water. Bs follows the pimple with a solution containing 90 ^c Jo water, 7 # sodium

009849/174 1 _ _? ^

• ORIGINAL BATHROOM

Chloride -mid <iy># sulfuric acid _for pimples the material 2 hours *, deli »Then i; eri \ t you rait an aluminium broth of a basic value 40 ° Sch» in an amount of 2 % chromium (III) - öixyd to the Ge-Vfdcüvt. the BIoBe ₄ neutralizes with Q * 4- & Soda for one hour,. then wash in pure running water for 2 hours. These operations are followed by the loosening of the fibers on the be & inteVrator ües iy-pus "Kondux HS-fc ^ ¹ * The defibration is carried out with the addition of water at a ratio water:!.. Paserstoff $ 1 performed Iir.cn the finished shredding the Fäßerstb-ff won '""düreii' Bresäen aviischen Gumiaiv / ialzen entviässert "is vereinheitlidht, before ^ etirocknei; and then at normal ^ .emperatur to end _t ~ etrO'öItneti "Dor, -OVionnene. Collagen fiber material "has a larger average length of the fibers than 1 cm. The fiber material produced in this way is made up of polypropylene staples with a Td value of 5 and a length of 6 inches a total amount of 20ίό stored on the 3? asergemsch »*. The stored iteterial vfirä is mixed when passing through a card grinder»

"The mixture obtained is passed into a roller card with medium-fine coatings _; the three-fold ends with a transversal thickening device on which the larden pile is layered up to the final weight of. The collagen and propylene fibers obtained are introduced into a needle punching machine in which the fleece is mechanically crossed through the repeated pass in such a way that the number of inserts is 200 / cm solidified structures

. ■■ - ■ "-" - "·". "" RAD OiWSWAt ■ "» -i. ^ - ^?

It is then fed into a steam separation chamber, in which it is exposed to the influence exposed to saturated steam for a period of 5 minutes will,

After drying off when passing through the drying chamber the fiber structure is impregnated with a dimethylformamide solution, which is prepared in the following way:

Polypropylene glycol ether having a Molekülargweicht of 5OQQ in an amount of 1.5 Hol is heated with stirring with 4 moles of 2,4-tolylene diisocyanate for three hours at a temperature of 70-80 ⁰ C. The prepolymer is dissolved in 9 kg of dimethylformamide and: 3 mol of distilled water in 10 kg of dimethylformamide are added to the solution. The temperature of the mixture is raised to 110 G and the mixture is allowed to react with stirring for 10-15 minutes. After this time, the mixture is cooled, the solution of 0.7 mol of diethylamine in 8 kg of dimethylformamide is added and, after stirring for 1 hour, 5 mol of 2,4-toluene diisocyanate in 2 μg of dimethylformamide are added «

The final solution is about 20 # and contains free isocyanate groups The mechanically sold fiber structure is impregnated with this solution, After soaking, the binder is precipitated by immersion in water, in which the excess of Dimethylformamide is washed out * After your thorough washing out is dried aas fiber structure and. sanded its surface. The manufactured product is an artificial leather, '., • which can not be provided with a surface treatment Product serves as a lace? · FTir ^ cWun top parts.

"% AD OWGINAL

'Example "2» \

Manufacture of artificial leather with hygienic properties for case: passion2weei; e _e .

Soaked pieces of raw skin from ■ beef cheeks become alicalic In a bath of the following composition for 48 hours

Liquid Lioefficient $ 250. Calcium hydroxide 3.0 - 3.5 P * - - '

Sodium sulfide; 2, ö - 2.5 # on the weight

the schnitzel,

Bath temperature 25 - 28 ⁰ Q.

After dehairing and removing the top, the raw material becomes for 48 hours in a bath composed of:

Calcium hydroxide 3 »5 t °

Sodium sulfate 3 »5 ^

re-ashed. Then it puts into the solution ^5% sodium hydroxide on the weight of Abschnitzel added and let the raw material in the bath another 48 hours are. This is followed by washing with running water over the course of 2 - 4 hours and further work-up according to Example 1 «"

The gewonngne fibrous v / ith NIIT 10? I of BaXyesterfasern with a Td-Wart of 5.5 and a length of 60 mm and with 20 ° J> Yiskosestapelfasern.mit of an ID value of 3 _t 5 anda length of 60 mm with the help of storage and passage over

009849 M 741 _{BAD of (tclNAL} . -10-

- ΊΟ -

mixed a card grinder. The individual genic becomes one when passing through a pneumatic fleece-forming machine. Nonwoven having all Richuungen on | \; ele.3 "gene fibers nia a P v / layer of 1 ^ 0 g / m processed * The fleece is mechanically r ~ £ a special Durcin / iri-uaschine interlaces, which on dor. - built up with loops of the fiber bundles; this is a machine of the "Beva" type * Solution: a polyurethane binder old, ^ eIs, just as v / as it is in Example 1; just vairde. The so-on-paser leather v / ira in grasping - dryBU- ^ ev / alkt. The brewing product is conf elccionell -au ülusen, -Sal ^ .os or .iänteln processed, possibly aient te as the back for 'artificial fur.

Example 1>

Material for inner parts of footwear, for insoles, Midsoles and the like.

Collagen fiber prepared according to Example 1 is mixed with Λ3 $> polyvinyl chloride fibers and with the help of a pneumatic blanket according to Example 2, the nonwoven fabric is produced with an end thickness of 400 g / m2. The obtained fleece is on. a knitting machine of the type "Arachne", ".4GV" or "i-Ialiwat" double-knitted, whereby the binding threads are made of polyamide silk. The total proportion of the binding threads is here 8 ^C J> on the 3ev / icht of the fleece. The ^ ewoiiiiene Gowirl: v / ill be performed by a so We.aserbad oei a Temperabur of 90 ⁰ C, that the Börührimgsdauer constitutes 60-120 seconds. The goods are then dried and fed into a bath containing polyamide resins, which is then carried out in the following

009849/1741 ~ '^

BATH

VfOi.se manufactured

Polyamide is used in alcoholic Wilieu rait paraformaldehyde one is depolymerized at 90 ° C. As a fodification

the temperature of the mixture is increased to 150 ° C. with the aid of stirring. After the modification of the polyamide has been completed, the resulting solution is V / asrcri * transferred, viorin the modified polyamide auBge-TjLLX ν. This is freed from residues of urlioaplioric acid by washing in water. The polymerized polyamide is dissolved in ethyl alcohol and converted into dioctyl phthalate. Krch impregnation of the underlay fiber material on oi: ie ::; usual ^ extilfoulard wirö the alcohol (by dehydration) laei a temperature of 9Ö-100 "G abr-eöampft ·

Dur t «cunir.ch * oil £ Qiomic effect of the invention exists <jirin that the production of artificial leather depends on the use of the * Frees demanding raw materials, which are very fine, shrinkable synthetic fibers. The sufficient one The length of the collagen fibers enables them to be processed in a manner customary in the textile industry, the end product is υ compared with the existing properties of synthetic leather through a new perfection of the subjective properties characterized, v.'elciie especially the softness, the handle, the cleavage mid Geacli;.: represent oath.

0098A9 / 17

Claims (1)

Claims 1. Flexible surface structure, especially synthetic leather,
characterized, · that the basic fibrous ^c from a mixture of Kolla, enfasern from a greater average length than 1 cn and stands by-fibers of synthetic fibers, especially of fully synthetic, which mechanically with one another
r.iit bundle of fibers !! or crossed with binder threads and a ..: are impregnated by adhaesivum, which is capable of JJ ¹ Uiii: üionsfruppen of the collagen fibers to reapjieren and with the same I, to form bonds ovalefite " 2. LiegsaK.-es cursory structure according to claim 1,
thereby -; el: ennaeichnet, Clsß it with a rewoven or knitted textile insert is stiffened " 5 Bie ^ sai.ies fl ^ clien structures according to claim 1 or 2,
as a result, daf: the synthetic fibers contained in the basic mixture are incoming (shrinking). 4. Method of making flexible sheet-like structures according to claim 1 - 3> 00 9849/17 41 characterized, that a lie of a mixture -of JPasern with Hi a Textilod-er Papierherstellungaverfahrens formed nonwoven by mechanical Ver_a? euzüng of the fiber material is solidified, Z ₀ as by piercing spike-Einstichinascilinen or using the Durchwirlzens on knitting machines that of the pass-through Base fleece with bundles of fibers, if necessary with. Binding threads are adjusted, whereby either the fleece itself or the fleece is tied with a woven or knitted textile insert «, 5. The method according to claim 4,. . marked by,. that the mechanically crossed structure in., a milieu is condensed, in which the pasers to be scraped run in according to their character, e.g. synthetic hydrocarbon, Vinyl or polyester fibers at a? -. High temperature, or the polyvinyl alcohol fibers in. an aqueous hilieu or "at a higher" degree of humidity _β method according to / bis claims # and 5, ■, characterized in that ß the compacted basic structure ■ by soaking, spraying -14t BATH 009849/1741 or pressure saturation with such substances ii.inx ·: · πΧε · ζ ·, v / ird, which are able to react with functional groups dor lio.i '^ ren £ aoom , like a. B ₀ solutions Ader Dispex'sio-, αη der G-rbamidharze, polyurethanes, polyamides, Helamin-SOri. i.ik-hyd- _r Urnstoi'i'-Fornaldehyd-, Phenol- ^ ormaldehyd- ode? Hnnorain-SOrmaldenyd-Harzeο 009849/1741 _WOM) «,