DD154826A1 - METHOD FOR THE IRREVERSIBLE SURFACE MODIFICATION OF SYNTHETIC FLUID IMAGES - Google Patents

Abstract

The synthetic surface formations whose surface design is achieved by the process according to the invention are used as synthetic leathers in the clothing, Taeschner, upholstery sector and the like. a. Fields of application used. The aim and object of the invention is in a simple and economical way, without complex technical solutions or complicated post-treatments, such as grinding, engraving, finishing u. a. To achieve an irreversible surface design already during the manufacturing process of the surface structures. By deliberately influencing the crystallization process of the matrix former contained in the reaction melt, as well as the condition of the application sheet, application in the turbulent or laminar flow region, introduction of foreign substances before and during the crystallization process, differently patterned surfaces of the crystallizing melt are achieved which irreversibly remove the surface structure after removal of the matrix former distinguished.

Description

Title of the invention

Process for irreversible surface patterning of synthetic fabrics

Areas of application of the invention

The invention relates to a. Process for obtaining patterned surface designs with irreversible character directly in fabric production'O 'The synthetic fabrics patterned according to the invention are used as synthetic leathers in the outerwear sector and in fields of application

Moreover, the method according to the invention can be used in all * processes for the production of sheets, which use crystalline solidifying liquids to achieve a porous polymer structure »

Char akteristik of the known technical solutions

It is known _t .that Oberflächengestaltungen.von synthetic and / or native .Flächengebilden.durch subsequent treatments of this sheet _f as embossing, printing, sanding or finishing be achieved könneri ₀ 'These and other Zurichttechniken, the targeted fashion effects and unwanted irregularities in appearance of leather and synthetic leather, have the disadvantage of additionally required work steps and investment-consuming special machines (Ulimanns.Enzyklopädie der technischen Chemie; 4 »Edition Bd. 16, 3 _e 259 ff) · · 'In each of these cases the production of a certain surface design becomes a principle finished surface

forming native and / or synthetic type later on special designed for die'entsprechende Hachbehandlungsart and combined special machines refined It is also known that specific Oberflächenappreturen of synthetic leathers which are produced by transfer coating, by .spezielle profiled release papers ,, profiled endless belts u ä _e "The disadvantage of this method is the limited usability of the release papers and tapes. It is also known that macromolecular products of fibrous structure are formed by polymerization of olefinic monomers in crystalline matrix. It is also known that all or part of it is polyaddition Crystalline solidified liquids to produce porous sheet-like structures with textile or leather-like properties. In these two last-mentioned processes, the monomers and / or precondensates are ground with a crystalline solidifying liquid t, the solution or dispersion poured on cold surfaces to the thin layer and. a sudden temperature drop below-Y / _e .

As a result, the substance preferably crystallizes out perpendicularly to the substrate surface, while the monomers or. Deposit precondensates in the capillary spaces between the crystals «,

Object of the invention

The aim of the invention is a simple and economic. Verfahren.zu in which without great technical effort during the continuous production of fabrics according to the principle of direct coating in crystalline solidified liquids or dispersions, the surface is patterned so that no further operations are necessary ' _o

.VD / KSB-LP / 43/80/1/3

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Explanation of the essence of the invention

The object of the invention is, by a controlled influencing the crystallization of a melting device, those of crystalline solidified liquids, preferably mixtures of liquids and polymerizable monomers and / or compounds having at least two reactive Wasserst at atoms, and di- or polyisocyanates having molecular weights between 500 and .010000 and additions of chain extenders and catalysts and / or in.den crystalline solidifying liquids of soluble-macromolecular plastics consist, by means of suitable substances and devices to achieve an irreversible surface pattern of fabrics.

BZV as liquids / ₀ solvents especially those in Fragej.die in the range of 273? 15 K to 373.15 K crystalline freeze "Examples include water, benzene, dioxane, diphenyl, benzophenone, p-dichlorobenzene, naphthalene, phenanthrene and preferably trioxane ,,. According to the invention, the object is achieved in that, when the melt mixture is discharged via a heatable cylindrical body having a row of nozzle holes whose axis assumes a horizontal position with respect to the general direction of movement of a band-shaped base which moves longitudinally, this position is 90 ^° C. the melt passes on a continuous flow sheet at the defined angle and. arranged at a specific distance to the base isf _o "· '·

It has now been found that in the continuous production of fabrics in crystalline solidifying melts, solutions or dispersions by adjusting the angle of attack of the drain and Verteilungsbleches of 20 to 3O ⁰ C and a specific distance flow sheet to the steel strip in the range of 0.1 to 2 mm, preferably 1 imn, produces a patterned surface of the resultant honeycomb structure sheet. remains after removal of .matrixbildenden substance * As Material.für the continuous .Ablauf- und.Verteilungs ~ sheet is preferably spring steel sheet of 0.8 mm

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In the described processes a woven fabric, knitted ö.der knitted textile material (mesh roughness or goods) or ^tf non -ν are conveniently / ο "out ν s fabric on the crystallization surface which are coated with the melt mixture"

The strip-shaped base is guided over tempering zones which, over their length, have a temperature profile which determines the desired crystallization and, in particular, the polymerization sequence and transfers this to the substrate.

By setting this defined gap, it comes in conjunction with the moving in the direction of solution moving continuously covered with a textile bandy being used in the special case, a highly polished steel strip _s to form a turbulent flow which resulted in a honeycomb surface structure This is independent of nature the matrix-forming substance used ,, ,,

Only the size of the crystalline intermediate spaces and thus the porosity of the resulting sheet is influenced in a known manner by the concentration ratios of the starting materials, the temperature conditions in the crystal region and the crystalline form of the crystallizing substance.

It has now been found _? in that when performing polyaddition reactions in crystalline matrix after the direct coating, the size of the surface patterns forming can be controlled by several factors. Once it succeeds by targeted application of the release agent film required in such reactions., ·. which is applied in liquid form to the advantageously highly polished endless steel strip surface to adjust _$ the pattern size, in the limit, with the omission of the release agent j is preferably from emulsified in chlorinated hydrocarbons silicones or _e waxes is an unpatterned surface can be produced * '14Lt increasing the Release agent film thickness increases as a result of reduced heat dissipation, the pattern, with a limit of the top, a Trennmitte'lauftrag of 100 g / m

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detected -was »' ¹ '

The reduction of the release agent allows a much faster removal of heat as the melt cools, which leads to more or less crystals growing perpendicularly to the crystallization surface at cooling temperatures substantially below the solidification point of the melt, resulting in a reduction in patterning According to a further embodiment, the addition of substances whose melting points do not differ substantially from that of the substance used as the matrix-forming substance and which influence the crystallization process of the coating melt, solution or dispersion in such a way that, as the addition of foreign matter increases a reduction of the surface pattern takes place, "Suitable substances are higher fatty alcohols, fatty acids, Äthylenglykole.und paraffins with melting points between 315.15 to 353.15 K ¹ ; ' ...

These are used in amounts of from 0.05 to 5% by weight, preferably from 0.1 to 0.5% by weight, based on the matrix-forming substance.

Of particular interest is in the implementation of diisocyanate polyaddition in crystalline matrices in which low molecular weight compounds are reacted with terminal isocyanate groups under the influence of conventional catalysts in polyurethane chemistry with water, the water content in the continuous process by conventional recovery methods such as melting , Subliming and extracting the crystallizing substance used, wherein in the preferred case trioxane is used., Contained in this, is'o "With a water content of 0.3 ~ 1 _y 0% by weight based on matrix-forming substance is one with small crater obtain surface provided. like patterns, while at a content of 1.2 "2.5 mass percent, the surface \ pattern große'wabenartige Facility" Zur- when lowering the recovery process des.Matrixbildners which accumulate water content can such

VD / CFE LF / 43/60/1/6

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Substances used to bind water in the form of hydrates or 'chemically

These include metal salts and, for example, the unsaturated fatty acids mentioned above,

Furthermore, it has now been found that the content of dyes used for the mass coloration, in particular 1.2 metal complex dyes, in the matrix former is also decisively responsible for the size of the surface pattern. In each case a honeycomb-like pattern is produced. In a specific embodiment solubilizers are required for the introduction of the dyes "which are used in amounts of up to 1 percent by weight based on the matrix-forming substance." This significantly enlarges the honeycomb pattern. As solubilizers, alkanols, glycol, cyclic ethers and dimethyl sulfoxide can be used such substances increase the rate of nucleation and accelerate the rate of growth of the crystals. Conveniently, these are the substances that lead to the growth of tetrids.

Although das.erfindungsgemäße method is particularly suitable for the production of sheet-like leather-like properties by the diisocyanate polyaddition in crystalline solidifying substances, it can also for the production of similar fabrics of linear high molecular weight polyurethanes or »polyureas and other high molecular weight plastics Molar masses above 10,000 have, as they can be prepared by the customary polymerization and polycondensation processes, come into consideration insofar as they are soluble or dispersible in the solvents used in the process. The content of the matrix-forming substance preferably ranges from 60 to 95 percent by weight based on the total solution. The solution according to the invention makes possible the continuous production of purposefully patterned surfaces of fabrics which in the liquid which liquefies in a crystalline manner are in the way of the. Direct coating be made of a textile material.

VD / CFE LF / 43/80/1/7

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The invention is intended below. some examples are explained in more detail »

Example 1

540 parts of trioxane are with 3 _S 2 parts of triethylamine. and 1 _$ 0 divide water in a heated container with stirring at 353? 15 K homogeneously mixed '...'. , , 60 parts of a prepolymer ^ that by reacting a linear, polyester alcohol of molecular weight 1000 mit.1,6 .Hexa ^ * - _s was prepared diisocyanate are heated to 353 K 15 and intensively mixed with the above mixture and heated via a? Order nozzle hole row _? the axis of which is horizontal, in the general direction of movement of a band-shaped pad, which moves in a longitudinal direction at a speed of 0.5 m / min. forward 5 and around 9O ⁰ C, by means of a spreading plate applied to the tape underlays within 30 seconds as a thin layer over a width of 900 mm '

A highly polished endless steel belt is as a tape backing is advantageous to use ',''In order to increase the strength of the sheet is directly .on the steel strip surface is a textile material entrained (tissue ^ knitted u. Ä _o), which is enclosed by the melt in direct coating "In order to increase of the separating effect. the steel strip is coated with a release agent film

of 100 g / m ~ provided.

As release agents are suitably distributed in chlorinated hydrocarbons silicone oil products or waxes ₀

used ''. * ...

Immediately after the discharge of the melt, the endless steel strip is passed over a tempering bath. The temperature is controlled by liquid media, for example

Water" . , , , , '

In this case the coating clump is cooled to 293 »15 K and allowed to crystallize«,. "

By setting up the angle of attack of the drainage plate used for distributing the application melt against the underlay

At a temperature of 25 ° C and a distance of 1 mm to the base, a turbulent flow is generated which leads to the formation of large honeycomb-like crystal aggregates. After completion of the spontaneous polyaddition reaction, the matrix former is separated by known methods. The fabric has a honeycomb patterned surface.

Example 2

In a modification of Example 1, the amount of water in the matrix-forming substance is reduced to 5 $ 4 parts. After removal of the trioxane, a white surface is left behind with a pattern distributed over the entire area in a punctiform manner

B EISP iel 3

With the composition and embodiment of Example 2 and an addition of .1.2% by weight of a 1,2-metal complex dye (for example Wofalan schwarz GRL) based on trioxane, a honeycomb-patterned, black-colored surface is formed after removal of the matrix former receive"

Example ^ 4

With the composition and execution of Example 1 and additions of 0.01% by mass of a mixture of 3 parts of Wofalanbraun BL and 1 part Wofalangelb 2 RL and 0.3.mass percent octadecyl alcohol to the matrix-forming substance also a dot-patterned light brown fabric is obtainedV. "

.Beispieles.

With the composition and design according to Example 1 and a reduction of the distance from the drainage plate to the steel strip to 0.05 mm and the release agent application to 50 g / m, a punctiform, patterned white surface structure is also obtained after removal of the trioxane.

Claims (1)

VD / KSE-LF / 4 3/80 / 1. / 9 225512 Erf induing claims 1. A method for irreversible surface patterning of synthetic fabrics, preferably from mixtures of liquids and polymerizable monomers and / or compounds having at least two reactive 'hydrogen atoms, and di- or polyisocyanates having molecular weights between 500 and 10,000 and additions of Kettenverlängerernj) in particular water and catalysts and / or in crystalline solidifying liquids'macromolecular'Kunststoffen in the continuous production process, characterized in that a coating melt containing crystallization-affecting substances in a concentration of .3 ~ 1 mass %, based on the crystalline solidifying substances, via a heatable cylinder-shaped body with a row of jet holes, the axis of which assumes a horizontal position oriented 90 ° to the general direction of a band-shaped base ... and a continuous flow and distribution Sheet, which is in a vein of 20 ~ 30 ° and at a variable distance of 0.1 to 2.0 mm to a moving forward and in its speed. bleen, with a textile material, provided steel strip located _? cast on this steel strip *, immediately passed through a temperature zone and cooled so that a crystallization takes place, whereupon the matrix former is "cut off" completion of the reaction by known methods, 'VD / KSE-LF / 43/80/1/10 10- 2e method for irreversible surface patterning of synthetic fabrics according to point 1 _S. characterized in that the diisocyanate - polyaddition reaction in "V / ater-miscible liquid crystalline solidifying""speeds at a water content of the solidifying liquid crystalline from 0 1 to 2.5% by mass conducted _wirdV? 3 "process according to items 1 and 2, characterized in that, as crystallization-influencing substances, higher fatty alcohols, fatty acids, ethylene glycols or paraffins having melting points of between 315 g.sup.-3 to 35.sup.j.sup.-3 are added to the coating melt, 4'e method according to the points 1 - 3, characterized in that * textile material for the melt coating fabric ^ knitted fabric. or knitted mesh or nonwoven fabric or nonwoven fabric become, ' Method according to items 1-4 »characterized by,. in that a film of silicones or waxes emulsified in chlorinated hydrocarbons is applied as the separating liquid of the hardened fabric by the steel strip.