DE1635592A1 - Vapor-permeable, non-porous, glossy sheet material, in particular for the production of shoe upper leather - Google Patents

Description

Bd. DU ΡΟϋΓΪ DE ÜEMOUES AND COMPANY 10th and Market Streets, Wilmington, Delaware 19 898, V. SteA "

Breathable, non-porous, shiny sheet material j especially for the manufacture of upper leather

The invention relates to non-porous, vapor-permeable sheet material for the production of sole leather, in particular Web material of the type mentioned, which has a high gloss. These fabrics can also be used to make women's handbags, wallets, belts and other items that have high strength, flexibility and a durable Must have surface gloss.

Various fabrics with a high-gloss surface have been available for years. Most of these substances are non-porous and impermeable to vapor, the others have considerable properties lower vapor permeability values than the minimum for upper leather equivalent to comfortably wearable shoes. Besides that

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is the flexibility and abrasion resistance of most these substances so small that they soon jump and or odes? lose their shiny appearance.

The invention provides a durable, high-gloss, non-porous » vapor-permeable sheet material available, which has the disadvantages of the previously known substances does not have and is "special good for making shoe uppers, ladies handbags, Belts and other fashion supplies. This web material is made from readily available raw materials in manufactured using conventional processing equipment *

The high-gloss web material according to the invention has a flexible »permanent» microporous textile base with a non-porous »vapor-permeable plastic coating adhering to it, which has been applied or treated in a special way in such a way that it gives the web material a high degree Lends shine «As a textile base is suitable in the sense of

™ Invention of any flexible and durable sheet material »provided it is only microporous. A preferred textile base is made by coating a fiber carrier »such as a textile fiber fleece, with a colloidal dispersion of a plastic with a liquid mixture of a solvent and a non-solvent, bathing the coated support in a wetting solvent for the plastic to coagulate the plastic into a microporous coating and remove the

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Solvent produced from the coagulated plastic. The coated carrier obtained in this way is then dried under such conditions * that the microporous structure is retained. Such a method is described in US Pat. No. 3 TOO 721. The web material produced according to Belgian patent specification 660,733 is even more preferred.

"Vapor-permeable ¹⁵ " refers to sheet materials and / or coatings whose vapor permeability value (also known as the "low permeability value"), determined according to Kanagy and Tickers "Journal of the Leather Chemist Association", Volume 45 "1950, pages 211-242 , is at least 600. All products according to the invention have vapor permeability values of at least 600 and usually of the order of several thousand.

"Non-porous" is a web material or coating made of plastic, if there is (he) no naked eye or under the

microscope contains pores visible at 300x magnification, ^ and if the plastic is in the form of a self-supporting sheet of 25 μ thickness no significant number of light-scattering gas-plastic interfaces having.

Coatings and sheet materials are referred to as "porous", if they fail the above-described test for non-porosity suffice. Porous materials are referred to as "microporous",

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whose pores are invisible to the naked eye.

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According to a preferred embodiment of the invention, the above besshriebene web material with the non-porous plastic coating is gepräg _t} in order to increase its shine and to improve the purity of its shade and particularly the depth and purity of the black color. For this purpose, the cream

material with the plastic coating in contact with a white ". -
^w . chen film made of Eellglae, cellulose acetate ,. Polyethylene terephthalate or the like can be passed through the gap between an embossing cylinder and an inflated envelope which is supported by a non-rotatable, rigid Fes thai te organ. Such a device is described in US Pat. No. 5,157,723. The embossing cylinder that comes into contact with the foil can be patterned by engraving or also smooth, depending on whether the surface of the paver certificate is to bear a master or not. In any case, the fact that the smooth film is in contact with the plastic coating of the coated textile material under pressure as it passes through the device gives the coating an extremely high gloss, the full strength of which is revealed when the film is removed from the coated textile material. These products are very suitable for the manufacture of shoe upper leather and other commodities.

Eb is important that the applied to the textile base vapor-permeable, non-porous plastic covering a thickness of

about 2j5 to 20> 3μ and preferably from about 5 to 10μ. The coating can be in one layer or in several layers be applied, provided only its total thickness is about 20p3 μ does not exceed «, If the coating has several layers, so these can consist of the same plastic or of different plastics. According to a particularly preferred one Embodiment of the invention, the coating consists of two different types of plastic layers, and the embossing process is carried out between the application of the two layers

The plastic covers can be on the sextile base according to any known processes, e.g. by sow coating, Spray coating, roller coating, with the bakel, through Laminating, or the like, can be applied ^ if only this creates coatings with a uniform thickness. The coatings can be clear, but are preferably pigmented, and It is a particularly surprising feature of the invention "that products whose coatings contain 70% by weight" $ pigments, still show a glamorous going out »

The term "glossy" refers to a surface with a reflectivity of at least 50 $ "at an angle of incidence of 60 ° according to ASTM test standard D-523» 62! S. All products according to the invention have at least as high a reflectivity, and some even have reflectivities of more than 94 $ _D

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The plastics preferred for producing the glossy, non-porous, vapor-permeable coatings according to the invention are the tough, essentially linear polyester urethane elastomers, which are thermoplastic, extrudable, malleable, melted at higher temperatures, practically free of crosslinking and soluble in dimethylformamide are »Such elastomers are produced by adding a mixture containing as essential polyester urethane-forming constituents (1) 1 mol of an essentially linear, terminal hydroxyl group having an average molecular weight between 600 and 1200 and an acid number of less than 10 from a saturated polyester aliphatic glycol with 4 to 8 carbon atoms, the hydroxyl groups of which are bonded to its terminal carbon at 0iB8 »and a diearbic acid of the general formula HOOO-R-COOH, where R is an alkylene oxide with 2 to 8 carbon atoms, or an anhydride thereof, and ( 2) about 1 * 1 to 3 "1HoI of a diphenyldiisoeyanate carrying an isoyanate group on each phenyl nucleus contains, in the presence of (3), about 0 * 1 to 2.1 mol of a saturated aliphatic free glycol with 4 to 10 carbon atoms, the hydroxyl groups of which are bonded to its terminal carbon atom." , heated, the molar amount of the polyester and the free glycols being equivalent to the molar amount of the diphenyl * diiaooyanatfi so that the action product has practically no non-converted isooyanate or hydroxyl groups.

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having pen. Bioh can find details of such compounds in US Pat. No. 2,871,218. Also polyether polyurethanes, especially those described in US Pat. No. 3,000,757, and those obtained by reacting polypropylene glycol with a mixture of toluene-2,4- and i'oluylene Polyether urethanes obtained in a solvent, such as ethylene glycol monoethyl ether acetate, can be used according to the invention, for coating purposes it is obtained in this way tene Torpolymerisat then cross-linked with water in the presence of a solution of adipic acid in cyclohexanone * -

One of the most important uses for the web materials according to the invention is the manufacture of women's shoe upper leather, and one of the most important properties of the web material for this use lies in the fact that it does not suffer any roughening, when the shoes are stretched on the last. When using coated textile material © as shoe upper leather the difficulty has always existed that, ^

when the shoes are stretched on lasts, in the places where the material has to be stretched considerably, especially in the area of the toes and heels where significant curvatures are present, the textile fibers of the! dextile base thereby reveal that they are the. Synthetic leather surface give a textured appearance · This unpleasant appearance is called "roughening" and may be

rial does not occur if it is suitable for sole leather should * Siege roughening is for ban material with high gloss Surface particularly noticeable, and one of the largest Difficulties in making high gloss sheeting for fashionable products, especially women's upper leather, lay in the creation of a material that, when clamped the shoes do not look rough on the lasts *

It has now been found that when using microporous Textile bases with a diene of at least 0.36 g / cm receives high-gloss products according to the invention, the suffer no roughening. This does not mean that textile bases with a density of less than 0.36 g / cnr no valuable shoe upper leather could be produced; if but a roughening is to be avoided, the textile bases must are initially treated in such a way that their density increases to this minimum value. A beneficial method to to do this is to compact the fabric, by guiding him through the mouth of pressure rollers and adjusts the pressure so that the processed Material assumes at least the density given above. Then the textile fabric according to the invention can be made into a high-gloss, non-porous, vapor-permeable web material that is suitable for shoe upper leather and does not have any roughening suffers "

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In the folgenden.Beispielen the parts beziehensich unless andereB stated, based on weight amounts and the basis weights of the top trains on a dry basis> All as "shiny" designated product © have a reflectance of at least $ 50> at an incidence angle of 60 °, as determined by the ASTM test standard D ^ 523 ^ 62T, the steam permeability value of all products in the following examples is over 900 .. "

Example 1 1

A mixture, from which a glossy vapor-permeable coating can be produced, is prepared by dissolving 4 »5 parts of a polyester urethane with an average molecular weight of 90,000 and 2 parts of a pigment compound in 93 * 5 parts of tetrahydrofuran commercially available from the company BsF. Goodrich Company under the name "Bstane 5740 χ 071" available. ? S made from a copolymer of vinyl chloride and vinyl acetate ("Vinylite ' ¹ from Union Carbide Corporation) immersed in the mass

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I am a microporous sheet material dyed with Mgrosine, consisting of a microporous coating on a fiber carrier, will after. Example 1 of the Belgian patent association 660 733 and up to a density of 0.36 g / önr -. compacted by placing it between a rotating embossing cylinder and an inflated envelope is passed through, which is supported by a non-rotatable, rigid retaining element, and above which there is a slip sheet. Such a device is described in U.S. Patent 3,157,723 and French Patent 1,328,115. This sheet material is then conveyed around the immersion tank roller, and although in a Bolchen camp that the carrier side of the Holle and the coated side faces the mixture. The way how the material is fed over the roll, and the mirror of the Mixtures in the container are chosen so that the mixture only the coated side and the edges of the sheet material touched. A web speed of about 1.8 m / min leads for applying a covering with a weight per unit area of 6.78 g / m (on dry basis).

The coated material is dried in an oven at 115 ° C. A vapor-permeable, glossy, non-porous web material with a vapor permeability value of 900 and a thickness of 5 μ * is obtained. The durability

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Flexural strength * Dimensional stability and breathability this soleplate upper surpasses the properties concerned similar shoes with a comparable shine.

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The dried ρ coated i ^ diüEt of Example 1 _f characterized by after the facing side with a polyethylene terephthalate film by the procedure described in Example 1 stamping device tiber cover is performed y being a provided with an engraved pattern Prägeaylinder against the standing with the coating in contact polyethylene terephthalate film suppresses . The polyethylene terephthalate film is then removed and it is established that a shiny, vapor-permeable, non-porous sheet material with a grained surface pattern has formed

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With the aid of the same drain tank arrangement, a clear deodorant coating is applied to the dried, treated product of Example 2. This top covering is produced by adding 23-4 parts of a 60 # solution of a polyether urethane with an average molecular weight of 100,000 in Ä'thylenglykolmonoäthjrlätheraeetat and 1 _P 9 parts of a 4 # solution τρη

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Adipic acid in cyclohexanone with 74 7 ropes of methyl ethyl ketone be mixed-. BaB polyether urethane is made from an egg polyethylene glycol old an average molecular weight of 1200 and a G-eKisßh of toluylene-2 ^ 4- and toluyl-n ~ 2 »6-diisocyanate in ÄthyXengXykolEäonoäthylätherac-etat and crosslinking of the Yorpolymerisatee thus obtained with water in the presence of a Solution of adipic acid 'made in cyclohexanone.

The speed of passage of the web through the solution is. 0145 m / min. After exiting the immersion tank is the deodorant covering by exposure to a temperature for 15 minutes from 127 to 138 ° C with a relative humidity hardened by 40 # »The sheet material obtained in this way is non-porous and vapor-permeable and has an excellent combination made of gloss and durability of the surface ©. It will used for the production of Bamensehoos, handbags and other commodities without roughening.

Example 4

The gloss on the coated surface of the material according to Example 1 produced material is increased if this material in the manner described in Example 2 in contact with a Regenerated cellulose film (instead of polyethylene terephthalate film ©) Treated with an engraved embossing cylinder «After removing the cellulose film received a shiny, vapor-permeable, non-porous

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material with a grainy surface pattern. This material will sur Manufacture of women's shoes, handbags and other consumer goods used.

A dispersion is prepared by mixing 56.5 parts of titanium dioxide, 9.5 parts of polyvinyl butyral and 34 parts of a polyurethane prepared by condensing a diamine, a polyether-bis-haloformic acid ester and a bis-haloformic acid ester. A polyurethane of this type and its production is described in USA Patent 2,929,802. The mixture is dissolved in a mixture of equal parts of toluene and ethanol to form a solution with a pesticide content of 5 ° . According to Example 1, a 1.14 mm thick, uncolored microporous web material is produced and coated with this dispersion using the dip tank described in Example 1. The rate of passage (of the material through the dip tank is adjusted so that the weight per unit area of the coating after drying for 6 minutes at 127 ° C. is 34 g / m 2.

The surface is embossed in contact with a cellulose film according to Example A with the aid of an engraved embossing cylinder. After removing the cellulose film, a high-gloss, vapor-permeable, non-porous web material with a pleasing, leather-like surface pattern is obtained.

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A dispersion which is suitable for producing a glossy, vapor-permeable coating for microporous itaoehicts is prepared by adding 761.7 g of a 58% aqueous dispersion of titanium dioxide ("Primai-Weiss * ¹ )., 802.2 g of an aqueous polyacrylic -Latex with an esthetic grade of 45 # ("Primal" HA-24 ") and 48.4 g of a leveling agent (IMA-65) mixed with 271.4 g of water. The dispersion is sprayed to a thickness of 25 μ (on a dry basis) on a sample of the microporous material used in Example 1 and then dried for 6 minutes at 110 ° C. 3 times the fretted textile fabric is then sprayed in a cold ek © mäicke of 7.6 μ coated with a dispersion made from the following components:

354.2 grams of water.

185.4 "38 ^ ige aqueous dispersion vtm (" primal white ")

^w 217.8 "46 ^ ige dispersion of

. ( ^M Pri3iaT ^K HA-12)

217.8 »45 ^ iges polyacrylic acid i-feril (" Eciraal ¹¹ B-32)

40 "Release agent based on polyacrylic i ^ Tslmal" E-191)

140 "matting agent (20 fSige ifäsBrig © BiBpersion)

20 »Leveling agent (LMÄ.-Ü5)

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The textile fabric is then dried for 6 minutes at 110 ° C., coated in a flat wire of 17 g / m "with a 5 # solution of Csllialoßeaeetat-butyrat and after 6 minutes at 110 ° C. The triple-coated textile is then olnom according to example 4 in contact with a SellgXasfolle imter Terwendmig a iqit-'S-reArierimg provided Prägeaylindörs BU hocliglgTisenden, unporöson, vapor permeable Bahmnatsrisl old marked a pleasing scarred Oberfläöhenmuster "

Example 7

A 1,14-! Din dic! Cee _? black colored microporous sheet material as used in Example 5 ^v _t \ rarde _s by dipping with dsr following dispersion in a thickness of 17 g / κ coated s

• -15.2 ropes "Monastral '^ Hot B

1.9 ""Monastral'V-Blue (

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31? 2 ^{! Ä} mixed polymer of methacrylic acid msthyX-. ester _s butadiene and. partially irainated methacrylic acid ©

48 _f .8 "water...

The coated Xeztllstaff is then embossed β minutes at 110 ° C dried \ ma by a Seliglasfolie against di © beschlöhtete applies down and the fabric having beschiehtete

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the cellulose film between a / with an engraving Embossing cylinder and a printing roller hindur ohge «. Such a method is described in US Pat. No. 2,801,949. A shiny, non-porous, vapor-permeable sheet material with a pleasantly grained surface pattern is obtained, If you use a roller or plate in which matt strips are engraved for embossing, you get a non-porous, Breathable sheet material with alternating matt and glossy stripes.

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Claims (1)

^ U du Pont de Itenoure ³⁰ * ^{Augaat 1966} and Company PF3) -768 Pa t ent ans ρ r ü c h e U Vapor-permeable, non-porous, shiny web material, in particular for the production of shoe upper leather, marked by (1) a fibrous carrier with a microporous adhesive attached to it Plastic covering (A) and (2) a vapor-permeable adhesive adhering to the microporous covering, non-porous covering (B) with a surface weight of * 5.4 to 27.1 g / m, which essentially consists of a plastic consists, which is in the form of a self-supporting film of 25.4 µ. Thickness (1) has a water vapor permeability value of at least 600 and (2) practically completely free from light-scattering interfaces between gas and plastic and from a 300-fold microscopic magnification visible pores. 2ο web material according to claim 1, characterized in that the coated fiber carrier to which the covering B adheres, has been produced by * FED-768. - Jg {15 Manufacture of a plastic solution, the essential components of which are a plastic, which under the Trookmingsb © -
conditions of the following process stage (5) a maximum elastic deformation strength of at least 7 leg / cm and contains a solvent for this plastic, (2) Addition of a plastic that does not dissolve, but with the
Solvent-miscible inert liquid to the plastic solution at a temperature at which a colloidal dispersion forms, to the formation of a colloidal plastic dispersion with a viscosity above about 1 P and a plastic concentration of more than about
7 wt .- #, (3) applying this dispersion to a support, (4) Remove the solvent by bathing immediately
of the resulting coating at the temperature at which
the colloidal dispersion has formed in one of the
Plastic non-dissolving and solvent-miscible liquid, and (5) drying the product obtained. 3. Web material according to claim 2, characterized in that the coated fibrous material carrier has a uniform density of
has at least 0.36 g / onr. - 2 ~
109886 / U (H. ITD-768 '■ / A. . * 4. Sabma material according to claims 2 »characterized.« Characterized in that the ÜberEüg 3 consists of a tough, essentially linear polyester urethane Elastoiiieren that is thermoplastic, extrudable, malleable »melted at higher temperatures, practically, free of crosslinking and soluble in methyl formaride and the Uiasetsungsprödüfct is, which is created by a Geisisch, which as essential polyester urethane-forming constituents (1) 1 get an essentially linear, | from a saturated aliphatic glycol with 4 Ms 10 carbon atoms, in which hydroxyl groups are bonded to the terminal carbon atoms, and a dicarboxylic acid of the general formula HOÖC-R-GOOH, where K denotes an alkylene radical with 2 to 8 carbon atoms * or an anhydride of such an acid, and (2) About 1j1 to 5.1 moles of one s contains an iso-, eyanate group-bearing diphenyl diisocyanate on each phenyl nucleus, bound by heating in the presence of (3) about 0.1 to 2.1 moles of a free, saturated aliphatic glycol having 4 to 10 carbon atoms, in which the hydroxyl groups are bonded to the terminal carbon atoms are «where the molar amount of polyester and free glycol together is essentially equivalent to the molar amount of the Diphenyldiisoeyanate, converted to a product having no free isoeyanate or hydroxyl groups · - 5 -109886/1404 FPD-768. 2O 5 »Web material _9, characterized in that it has been produced from the web material according to claim 1 by the smooth action of heat and pressure on the surface of the thermally deformable web material in contact with an embossing element, in that the web material through the gap between a malleable, heated, rigid embossing element and a rubber-like, inflated cover which is slightly adapted to the movable embossing element and which is supported by a non-rigid holding element, with a sliding film between the sheet material to be embossed and the inflated cover. 6β sheet material according to claim 5, characterized in that the Coating B consists of at least two superposed and adhering layers. 7 »web material according to claim 6, characterized in that the both layers consist of different plastics. " - 4 - 109888 / U04