DE2435880A1 - WATER VAPOR PERMEABLE, FLEXIBLE FLAT MATERIAL, PROCESS FOR ITS MANUFACTURING AND ITS USE AS LEATHER REPLACEMENT - Google Patents

Description

Water vapor permeable, flexible flat material, process for its manufacture and its use as a leather substitute.

The invention relates to a sheet material which is vapor-proof. This material has a wide range of uses, in particular as a shoe upper material and for clothing purposes.

It is already an excellent, microporous, flat polyurethane material known that it does not contain any preformed fibrous reinforcement and that it is made of a microporous, strength-reinforced material Substrate layer approximately 1.35 mm thick with a density of about 0.55 g / cm, which on one side is integral with connected to a thinner, less dense surface layer, The surface layer is typically about 0.35 now thick has a density of et v / a 0.35 g / cm. The free surface of the surface layer is given a very thin surface finish equipped.

This material has good tear strength (cut tear strength), which makes it suitable for the manufacture of shoes, as well as a suitable water vapor permeability before the Applying the finish so that the hat he LaI after the finisher * sufficient water vapor permeability to use

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as a shoe upper material. For certain purposes? however, the material is a bit stiff. This stiffness could be reduced by increasing the thickness of the strength-imparting Substrate decreased; However, it has been found that this measure leads to a material with inadequate Tear strength leads. In addition, a material with a thickness of less than 1.5 mm does not have enough substance in terms of commercial use as a shoe upper for men's shoes.

For these known materials, the ratio of tear strength to stiffness (as defined below) is generally about 2 to 3.4.

Eg it has been found that if one considers the thickness of the substrate layer and at the same time gives it a firmer structure, as well as another surface layer (hereinafter referred to as Underlayer (referred to as flesh layer) on the side facing away from the outer layer of the substrate forms a considerable reduction the stiffness while maintaining satisfactory values in terms of tear strength and water vapor permeability and material thickness can reach.

It is therefore an object of the invention to provide a material which is permeable to water vapor and which does not contain any fibrous reinforcement and which has a ratio of tear strength to rigidity of more than 4, preferably more than 5 _f .

In US Pat. No. 3,284,274, it is described that in the production of synthetic suede and leather-like material with a smooth surface for shoe upper material a layer of cellular, honeycomb-like, macroporous, polymer material can be applied to both sides of a flexible, porous substrate, which is a layer of non-fibrous, porous, polymeric Material, for example a tough / microporous film, can act.

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It has been found that they provide the desired improvement in terms of the ratio of tear strength to stiffness cannot be achieved if one does not have both the substrate denser as well as thicker than either the underlayer or the top layer.

The subject of the invention is thus a water vapor permeable, soft, flexible, flat material for use as a shoe upper material instead of leather, of at least 0.3 mm thickness, for example 1.0 to 2.0 mm or 0.9 to 1.7 mm thickness , with at least three superimposed porous layers of elastomeric polymers, whereby the material does not contain any fibrous reinforcement, has an elongation at break of more than 200 $ and a strength-imparting, porous, elastomeric polymer substrate layer, which is sandwiched between a porous, elastomeric polymer sublayer and a porous, elastomeric polymer top layer, the substrate layer having a higher density than the backing layer or top layer and being thicker than either the bottom layer or top layer, and the total thickness of the bottom layer and top layer in the range of 30 to 175 ° The thickness of the substrate layer is, for example, 65 to 125 ° ß>) in particular 70 to 110 5 ^, the thickness of the substrate layer, and preferably the thickness of the top layer in the range of 150 to 50 fo the thickness of the lower layer.

The thickness of the top layer can range from 10 to 95 / £, for Example 30 to 80 5 &, the thickness of the substrate. the Underlayer can have a thickness in the range of 10 or 20 to 95% of the thickness of the substrate.

The ratio of cover layer thickness to substrate thickness is preferably in the range from 1.5: 1 to 0.5: 1, in particular 1.2: 1 to 0.8: 1 and particularly preferred is a ratio ' of about 1: 1, the material being essentially symmetrical around a center of the inner layer (substrate layer) leading level is located.

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In a preferred embodiment of the invention, the strength-imparting, porous elastomeric polymer substrate compact gaps or cavities that, statistically, across the layer distributed and interconnected by pores penetrating the walls between the gaps, which is the underlayer microporous and possesses compact gaps that are statistically distributed over the layer and over pores that form the walls between the Gaps penetrate, are interconnected, the top layer is microporous and has compact gaps that are statistically about the layer is distributed and interconnected by pores penetrating the walls between the gaps, and the substrate is characterized in that it has wall thicknesses between the gaps which are generally greater than those in the undercoat or the topcoat.

The invention enables the production of a preferred material by a tear strength (as defined below) of at least 1.5 kg, for example at least 2.3 kg, a ratio of tear strength to stiffness (as defined below) of at least 4.2, for example about 5.0 to 10.5, preferably 6 to 10, and a stiffness (as defined below) of not more than 0.65, preferably et v / a 0.25 to 0.60, for example 0.30 to 0.50.

According to a particular embodiment of the invention, the substrate layer consists of a porous matrix of elastomeric * polishers, which forms a large number of interconnected gaps by pores, the substrate layer 0.5 to 1.2 or 1.5 ffiia, for example 0 , 6 to 1.0 mm, preferably 0.7 "to 0.9 mm, thick, has a total void volume or porosity of over 50 f>, at least 65 ° β> the porosity through pores and the gaps, with which the pores are connected, and the pore diameter of at least 5.0 u, preferably below 20 u, determined by the mercury penetration or mercury penetration method (hereinafter referred to as the mercury penetration bottom). The mean pore diameter of the substrate layer is preferably in the range from 5 to 20 u, preferably 7 to 15 u,

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for example 10 to 12 yes, each determined according to the mercury method.

The bottom and top layers are preferably fesüiaftaxL with the Substrate layer connected. The bottom and top layers have preferably thicknesses in the range from 0.20 to 0.45 mm. The top layer and the bottom layer preferably have densities of below 0.40 g / cm, for example in the range from 0.2 to 0.4 g / cm "', for example 0.25 to 0.35 g / cm.

The elastomeric polymer is preferably an elastomeric polyurethane, but mixed with other thermoplastic polymers such as polyvinyl chloride or vinyl chloride copolymers, as well as polyacrylonitrile or acrylonitrile copolymers can be used.

The preferred polyurethanes are essentially linear polyurethanes which are composed of a diisocyanate, a monomeric one Diol and a polyester or a polyether having a molecular weight from 1,000 to 3,000 produced. The polyurethane preferably has an intrinsic viscosity in dimethylformamide of at least 0.8 dl / g.

Polyurethanes based on polyesters with a Shore hardness of 75 A or 90 A to 60 D, preferably at least 98 A, are particularly preferred as a solid continuous film at 25 C. This material can be used for all three layers. In a preferred product, however, it is only used for the strength-imparting substrate layer, a polyurethane with a lower Shore hardness than the substrate polyurethane and thus a softer handle being used for the top layer and the lower layer. This softer material has a nitrogen content of about 2.5 ^ or 2.8 to 3.0 or 3.5 to 4.0 $. This soft material can be achieved by increasing the ratio of polyester to glycol, which results in a lower need for diisocyanate. The polyurethane for the substrate preferably has a higher nitrogen content, for example at least 4.0 or 4.5 ⁰ Jo or more.

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With the soft polyurethane for the top layer and the bottom layer it can be a polyether polyurethane instead of one Act polyester polyurethane.

In a particular embodiment of the invention, the polyurethanes used for the outer layer, lower layer and substrate are made from the same polyester, diol and diisocyanate, and the polyurethane used for the substrate has one Nitrogen content of at least $ 4 while that for the top layer and backsheet have lower nitrogen levels than the substrate polyurethane.

The substrate layer preferably has a porosity in the range of 50 to 65 ^, and less than 7 ° f the Gesaintporosität is formed by pores and the gaps with which they are connected, wherein the pore diameter --ναιüber 100 jl besitzai / and at least 50 fo the Gesaiatporosität is formed by pores and the gaps with which they are connected, wherein the pores have diameters in the range from 6.4 to 17.5 Ji.

When looking at a cut cross section is the substrate layer furthermore preferably -characterized by compact gaps, the majority of which have maximum dimensions in the plane of the Cross-section from 30 to 10Ou. owns the majority of these Gaps smallest transverse dimensions in the plane of the cutting surface 1/4 of its maximum dimension and above, the shape of the gaps is non-spherical and despite irregular outer lines is compact, the gaps are separated by denser regions (which can be viewed as thicker walls), the smaller, contain pores visible at 150x magnification, the majority of which have a diameter of 1 to 30 u (across) and 1 to 10 μ away from each other, and the plurality these denser regions have diameters (across) of 30 to 100 u between adjacent larger gaps.

When looking at a cross-section created by cutting are the microporous bottom and top layers are preferably characterized by irregularly shaped but compact gaps

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from 5 to 75 u in diameter, the majority being diameters of 20 to 50 u, and these gaps are limited or surrounded by thin walls 1 to 5 u thick, the gaps are connected by pores that pass through these thin walls.

The new water vapor permeable sheet material of the invention can be made so that one layer of a coagulable, elastomeric polymer sub-layer material on one applying a porous support to form the sub-layer, a layer of a coagulable, elastomeric layer before coagulation Applying polymer substrate mass on top of the layer of underlayer mass and then a layer of one prior to coagulation Applying coagulable, elastomeric top layer material on top of the layer of substrate material, and then the composite material forming an integrally tightly bonded, microporous, three-layer structure that contains no fibrous reinforcement , 'coagulated, with at least the substrate mass and at least one of the underlayer or outer layer masses having a removable, contains particulate filler, and the filler in the undercoat or topcoat composition has an average particle size which is smaller than the particle size used in the substrate mass.

The elastomeric polymers are preferably elastomeric polyurethanes with intrinsic viscosity numbers of at least 0.3 dl / g, for example 1.0 to 2.0 or 1.0 to 1.4 dl / g (in a dilute solution in dimethylformamide). The polyurethanes the bottom layer and top layer are preferably softer than those of the substrate layer. The substrate polymer possesses for example as a thin, gap-free film from 0.2 to 0.4 mm

Thickness has a module at 25 ° elongation of at least 55 kg / cm, for example 60 to 100 or 70 to 80 kg / cm, and the bottom layer and top layer polymers are thin, gap-free films 0.2 to 0.4 mm thick for example a module at 25 $ elongation of less than 55 kg / cm, for example 30 to 45 or 50 kg / cm.

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Preferably, the substrate composition contains the substrate polyurethane dissolved in a polar organic solvent, such as dimethylformamide, in a concentration of at least 20 percent by weight, for example 25 to 40 percent by weight, for example 30 to 35 percent by weight, with a particulate, soluble filler, for example a water-soluble inorganic Salt dispersed therein and essentially insoluble in the organic solvent. The filler preferably has an average particle size, determined with the Coulter counter, in the range from 20 to 200 μ, for example 25 to 75 or 50 γ., And the ratio of filler to polymers! ranges from 1.8: 1 to 2.7: 1, for example 1.9: 1 to 2.2: 1, parts by weight. In particular, it is preferred for particle sizes from 30 to 95 μm, namely a filler / polymer ratio in the range from 1.8: 1 to 2.8: 1 with a salt particle size of 30 μm, and in the range from 1.8: 1 to 4.0: 1 for particle sizes of about 95 microns.

As can be seen from DT-PA 24 13 461.0, to which reference is made here in full, one obtains when working in this Area a material with improved strength. The aforementioned patent application is in particular with regard to preferred formulations for a substrate for an artificial leather or synthetic leather and the disclosure with regard to the preferred Filler particle sizes noted. Preferably the Information from DT-PA 24 13 461.0 in connection with the substrate used for carrying out the method according to the invention.

Similarly, the undercoat and topcoat compositions contain dispersed fillers; however, the filler preferably has an average particle size of less than 20 iu, for example in the range from 1 to 15 or 5 to 10 u. The filler / polymer ratio is preferably at least 2.5: 1 and is for example in the range of 3 '· 1 up to 6: 1 parts by weight.

The polymer composition is preferably prepared by dissolving the polymer in solution of low molecular weight reactants

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to form a polymer solution of the desired concentration and then mixing the particulate filler (which is preferably water soluble) into the polyaner solution, for example with a high energy mixer. The mixture is then coagulated with a liquid which is a non-solvent to the self-supporting state. This is preferably done so that extruding the mixture onto a porous belt and with a non-solvent, for example water (for example at 20 to 60 ⁰ C) or Wass he / Lö sungsmit tel-Geraischen, for example, with 5 to 30 $ Solvent content that have a non-solvent effect, for example by immersion in the liquid non-solvent. The non-solvents used can contain proportions of dissolved filler, for example filler quantities of the order of magnitude of up to 15 ° can easily be tolerated in continuous operation. Pure non-solvents are equally effective.

The coagulated self-supporting layer is then preferably peeled off the porous tape while still wet and immersed in a non-solvent, for example of 60 G, immersed. Hereby the soluble filler becomes to a satisfactory extent extracted, for example, should not exceed 1 000 mg

ρ
Filler remains per m of the sheet material.

The leached layer is then dried and can ' be subjected to any suitable final treatment.

The preferred density of the substrate layer of the material is 0.4 to 0.7 g / cm. For certain purposes, the density up to 0.8 g / cm.

It is preferred to have such filler particle sizes and filler / polymer ratios apply that the diameter within of the range from 0.4 to 0.5 or 0.55 g / cm ^ remains. So v / ground at lower values within the range there? allowed

Particle sizes preferably lower values within the allowable range of filler / polymer ratios, and

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higher values within the range of particle sizes are preferred higher values within the range of filler / polymer ratios are used. For example, at middle Particle sizes from 20 to 30 µ the pulp ratio preferably 1.9! 1 "to 2.1: 1, with 30 to 60 ix filler 2.1: 1 to 2.2: 1, 2.3: 1 or 2.4: 1 and for filler particles of over 60 and the salt ratio over 2.2: 1 or 2.4: 1.

In the following the invention is described with reference to the drawings.

Figures 1 through 8 are photomicrographs, the preferred three-layer water vapor permeable materials of the invention described in Examples 1-8. In each case, it is a question of vertical cross-sections through the microporous flat material at 55x magnification.

FIG. 9 shows a schematic side view of a test device to determine the rigidity of the manufactured according to the invention flat products.

The photomicrographs of Figures 1 through 8 are taken with an electron microscope (Stereoscan Mark 2, Manuf. Cambridge Instruments Limited). This becomes a smoother, cleaner one Cross-section laid through the two-dimensional samples. The cut surface is then covered with a thin, metallic, reflective Layer, for example of gold or palladium, coated, as is the case in the preparation of specimens for electron microphotography is common. Then an electron beam is directed at the cut surface at an angle of 45 °, and the electrons reflected from the surface at 45 ° are collected and used to generate an optical Image that is photographed. As a result, the depth of field of these photographs is considerably greater than that of the optical photography, which in turn has the effect that you can see into the gaps and cavities.

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The examples illustrate the invention.

Various polyurethanes are used in the examples. You are in dimethylformamide as a solvent from a polyester or polyether by reaction with a diol and a diisocyanate produced in an inert atmosphere.

Polyurethane 1

880 parts (I) of pure Ν, Ν-dimethylformamide are placed in a 1500 parts (II) reaction vessel which has been flushed with dry nitrogen. After 0.027 part (IX) p-toluenesulfonic acid and 0.020 part (X) dibutyltin dilaurate have been dissolved in the dimethylformamide, 205.0 parts (III) of a hydroxypolyester ("Desaophen 2001", terminal hydroxyl-containing polyester with a molecular weight of 2000) are added an acid number of less than 2 and a hydroxyl number of about 55 (in each case mg KOH / g), which has been prepared from about 1 mol of 1,4-butanediol »1.12 mol of ethylene glycol and 2 mol of adipic acid) and 48 parts (IV) 1,4-butanediol, which will be dissolved in the mixture; the temperature of the mixture is adjusted to 25 ⁰ C.

Thereon are employed 171.6 parts (V) 4,4-diphenylmethane diisocyanate gradually added portionwise to, care being taken that the temperature does not exceed 50 ⁰ C. When the addition is complete, the mixture is ^{heated to 60 °} C. and kept at this temperature for 1.5 hours with stirring. The excess of unreacted isocyanate is determined by titrating a sample. A sufficient amount of butanediol (3.0 parts (Vl)) is then added to prevent it from being converted to stoichiometric isocyanate borrowed in the wes. The mixture is then kept at 60 ^° C. with stirring and the viscosity is measured periodically until it has risen to a value of about 3500 poise (using a Brookfield viscometer with spindle no. 5 or 6), corrected to 24 ^{° C.} is. 4.10 parts of (VII) 1,4-butanediol, dissolved in 3.5 parts of (VIII) Ν, Ν-dimethylformamide, are then added as a masking agent in order to terminate the reaction.

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The nitrogen content is about 4.5 percent and the polyester content is about 50 percent. The polyurethane "has a Shore hardness of 55 D as a solid continuous film at 25 ^° C.

The polyurethane has the following physical properties:

The solution has a viscosity of 4,100 poise with a pesticide content of 33.2 <fo and 24 ⁰ C (Brookfield RVT, spindle no. 7, 2.5 rpm), an intrinsic viscosity of 1.08 dl / g, as well a k value (Huggin's constant) of 0.60. A gap-free film cast from the solution by slow evaporation of the solvent has a tensile modulus at 5, 25, 50 and 100 $> elongation of 27.3, 74.5, 95.8 and 120 kg / cm, respectively, a tensile strength of 589 kg / cm _3, an elongation at the crystalline point of 480 <fo and an elongation at break of 615 $, a tear strength of 180 kg / cm, and a ratio of tear strength to the 25 56 module of 2.4.

Polyurethane 2

Production takes place in the same way as for polyurethane 1, but the amounts of the reactants are varied. The following recipe is used:

Component parts

DMP (I) 900

p-fluuenesulfonic acid (IX) 0.06

Dibutyltin dilaurate (X) 0.027

Desmophen 2001, Hydroxypolyester (III) 232.4

Butanediol (IV) 30.0

4,4'-diphenylmethane diisocyanate (V) 132.6

Butanediol (VI) 5

Butanediol (VII). 5

DtIF (VIII) 100

A polymer with a nitrogen content of 3.3 f ° is obtained from this.

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- 1 λ -

The solution has a viscosity at 33 "2 fo Peststoffgehalt and 24 ⁰ C of 4 100 poise, an intrinsic viscosity of 1.145 and a k value of 0.48. A film cast from the solution, as in the case of polyurethane 1, has a tensile modulus at 10, 25 and 50 ° of 23.5, 37.9 and 49.6 kg / cm, a tensile strength of 465 kg / cm, an elongation at a crystalline point of 620 fi and an elongation at break of 710 fo, a tear strength of 113 kg / cm and a ratio of tear strength to 25 ^ modulus of 2.98.

Polyurethane 3

Production takes place in the same way as for polyurethane 1, but the amounts of the reactants are changed and it becomes the Bayer Desmopher.Yesuchprodukt PU 1816 instead of Desmophen used in 2001. Desmophen PU 1816 is a polyester with terminal hydroxyl groups with a molecular weight of 2,250 and an acid number of less than 2 and one Hydroxyl number of 50-2 (each mg KOH / g). This hydroxyl polyester is Desmophen 2001, apart from the Diolkoiaponente, very similar. The following recipe is used:

Component . Parts;

DMP (I) 900

p-toluenesulfonic acid (IX) 0.06

Dibutyltin dilaurate (X) 0.027

Polyester PU 1816 (III) 271.3

Butanediol (IV) 33.0

4,4'-diphenylmethane diisocyanate (V) 140.6 butanediol (VI) 5.1

Butanediol (VIl) 5.0

DMF (VIII) 100

A polymer with a nitrogen content of 3.5 ° is obtained from this.

The solution has a viscosity at 33.2 <fo solids content and 24 ⁰ G of 3,400 poise, a limiting viscosity number of 1.11 and a k value of 0.49. One out of the solution, as in the case of

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Urethane 1, cast film has a tensile modulus at 10, 25 and 50 fo of 19.0, 36.0 and 48.2 kg / cm, respectively, a tensile strength

of 519 kg / cm, an elongation at the crystalline point of 56O fo, and an elongation at break of $ 640, a tear strength of 143 kg / cm and a ratio of tear strength to 25 # modulus of 3.98.

Polyurethane 4

It is produced in the same way as for polyurethane 1, but with the dibutyltin dilaurate catalyst, component (X), is omitted. The following recipe is used:

Component parts

DMP (I). 900.00

p-toluenesulfonic acid (IX) 0.06

Polymeg 1930, polyether (III) 254.20 '

Butanediol (IV) 33.30

4,4'-diphenylmethane diisocyanate (V) 152.70

Butanediol (VI) 3.00

Butanediol (VII) 5.00

DMF (VIII). 20.00

A polymer with a nitrogen content of 3.8 ^ is obtained. Polymeg 1930 is a polytetramethylene glycol with terminal hydroxyl groups with a molecular weight of 1930, a hydroxyl number of 53 to 59 and a very low acid number of not more than 0.05. It has a melting point of 38 ⁰ C and a specific gravity of 0.985 g / cm ⁵ at 25 ⁰ C.

The polymer solution has a viscosity at 33.2 fa solids content and 24 ⁰ G of 4,400 poise, a limiting viscosity number of 0.38 dl / g and a k value of 0.65. A film cast from the solution, as in the case of polyurethane 1, has a tensile modulus at 5, 25, 50 and 100 fo elongations of 9.6, 37.4, 50.8 and 66.9 kg / s, respectively, and a tensile strength of 447 kg / cm, a defanxing at the crystallization point of 68O $> and an elongation at break of 715 # 1

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a tear strength of 95.8 kg / cm and a ratio of tear strength to 25 # modulus of 2.55.

Removable filler *

Sodium chloride (or other equivalent, preferably water-soluble, removable filler) is put into a pin mill (pin and disk mill) ground with air classification, undersize grain separated and oversized grain returned to the grinding stage. Before dispersing in the polymer solution, the particle size of the sodium chloride powder B is determined using the Coulter counter method determined.

The measurement of the particle size with the Coulter counter is one well-known method that is widely used and in the literature} for example in "The Coulter Principle of Particle Size Measurement "by T. Allen and K. Marshall at the National Library of Science and Intention. ' (Patent Office Branch), London.

Nonetheless, a brief description of the method should be given. Bas sodium chloride, whose particle size is measured is to be used as a highly diluted suspension in a saturated 4 percent solution of ammonium thiocyanate in isopropanol suspended, which has previously been saturated with sodium chloride.

The mixture is subjected to ultrasonic vibrations to ensure that no particles are agglomerated.

The suspension is then placed in the measuring chamber of the apparatus described in US Pat. No. 2,656,508. An electrode is placed in the chamber. A tube, which contains another electrode and has a very small opening corresponding to the particle size, is immersed in the suspension, which is then drawn through the tube. For sale with an average particle size of 9 to 126 u, a tube with one or more openings of 23O u is used. Each time> v9rin a particle dxa ö

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happens, a voltage pulse proportional to the particle volume is generated generated; the bigger the momentum, the bigger the particle.

The electronic circuitry of the measuring instrument can be set in this way that only pulses are counted which have a volume within a certain range, and the number of pulses within a given time within the respective Area is counted for a series of areas. The results are then plotted to give a distribution of the Particle sizes based on weight obtained.

The concentration of the particles in the sample is adjusted so that they are below the so-called coincidence concentration, the is the concentration at which there is a probability that more than 1 particle will open the opening at the same time happens and measured as a single particle becomes significant. For example, for salt with a particle size of about 10 u of a 0.05 to 0.1 weight percent suspension, for Salt of about 50 p. a 0.1 to 0.3 weight percent suspension and for salt of about 90 µ, about 0.3 to 0.5 percent by weight Suspension used.

All values for mean particle sizes given in the examples are with a Coulter counter (industrial model For example, measured with a volume transducer (model M2) using a tube with an opening of 280 u Except for the results in Table III.

Purely any given mean particle size is the value for the negative deviation is the particle size below which only 16 percent by weight of the total amount, and the value for the positive deviation is the particle size above which only 16 percent by weight of the total amount is. The positive and negative Deviations from the mean do not have to be the same. The mean particle size is the size at 50 percent by weight fall on both sides of the given value.

This means that at least 84 percent by weight of the filler

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preferably a particle size of at least 10, 15 or 30 n, and at least 68 percent by weight a particle size in the range from 15 to 100 or 25 to 75 U, in particular 30 to 70 U.

The positive and negative deviations are preferably less than 50 <fo _t, for example up to about $ 45, for example 30 to 45%.

In the examples, the reference numbers relate to FIGS. 1 to 8.

example 1

This is a three-layer material according to the invention.

The substrate 15 has a coarser pore structure than the cover layer 16 and the backsheet 17, which is made of a softer polymer (polyurethane 2, as described above) than the substrate are made.

The method used to create the interconnected layers is described below.

First, an underlayer paste is spread on a porous polyethylene film with a doctor blade. A substrate paste is then spread over the layer of underlayer paste, and finally a top layer paste is spread over the substrate paste. The cohesive, superimposed paste layers on the porous support are then immersed for 1 hour at 30 ° in pure, standing water (water-solvent-salt mixtures are equally effective) with the coated side down, in order to make the polymer in the paste self-supporting to coagulate. Thereupon, the three-layered composite material is free of cracks peeled from the support and / ater immersed for 5 hours at 60 ⁰ C in stagnant V to the DMF substantially completely remove the sodium chloride content and a very low. Reduce the amount, i.e. well below 1,000 mg / m, in order to obtain correct density measurements.

The material is then dried in a hot air oven at about 70 ^{° C. for about 2 hours.} The properties are shown in Table I.

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s hurried.

The substrate paste 1 is made by mixing and grinding the polyurethane solution referred to above as polyurethane 1 (diluted to 32 fo pesticide concentration) with 1.90 parts, per part of polyurethane, sodium chloride particles with an average particle size of 27 u (negative deviation 12 μ; positive deviation 21 u ) and subsequent degassing in a vacuum.

The top layer and bottom layer paste 1 is made by mixing and grinding the polyurethane solution referred to above as polyurethane 2 (diluted to 25 f ° solids concentration) with 3 parts, per part of polyurethane, sodium chloride particles with an average particle size of 9 u (negative deviation - 3 u; positive deviation + 4p) and subsequent degassing in a vacuum.

The properties of the material are given in Table I. Example 1 A

A single layer material made from the same paste as substrate paste 1 and in the same 7 / iron, however, is produced with a considerably greater thickness (1.4 mm), has the properties given in Table III. With Results obtained by the mercury method are summarized in Table IV.

Example 2

This example is a three-layer material, similar to that of Example 1, but with a thicker substrate 18, the structure of which is less coarse.

The material is produced in the same way as in Example 1, the only differences being that-one Sodium chloride with a mean particle size of Hu (negative Deviation 6 u; positive deviation 15 w) in the substrate

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paste used.

The properties of the material are summarized in Table I.

A sine-layer made from the substrate paste with the same thickness Material has a density of 0.56 g / cm.

Example 3

This is te is a three-layer material, similar to Example ^ However, Rait _t another polymer in. The topsheet and backsheet.

The procedure and the recipes are the same in the example 1, with the only difference that dia is prominent as Polyurethane 3 denotes · Polyurethane solution is used in the bottom and top layers, and the layers are different Own thick ones.

The properties of the material * are summarized in Table I.

Example 4

This is a dry-layer material, similar that of Example 1, but with a different polymer, namely the aforementioned polyurethane 3 »in the top layer and Lower layer paate. Furthermore, the substrate pairs are being used of coarser sodium chloride with an average particle size of 31 ρ (negative deviation 12.5 u; positive «deviation 18 u) and made with 2.0 parts of salt per part of polymer. Otherwise, the process and the recipes are the same as in example 1.

The properties of the material are grouped together in Table I

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Example 6

This example is a three-layer material, similar to that of Example 1, but with a different polymer, namely the aforementioned polyurethane 3, in the top layer and bottom layer paste. Furthermore, the substrate paste is produced using coarser sodium chloride with an average particle size of 49 microns (negative deviation 18.5 n; positive deviation 31 microns) and 2.2 parts of salt per part of polymer. Otherwise, the procedure and the recipes are the same as in Example 1.

The properties of the material are summarized in Table I.

Example 6 A

A single layer material is made from a substrate paste similar to that of the substrate paste of Example 6 is very similar and differs from this only slightly in the salt particle size. It will be the same procedure applied, but the layer has a considerably greater thickness. The properties of the material are in Tables III and the results of the mercury method are given in Table IV.

Example 7

This example is a three-layer material, similar to that of Example 1, but with a different polymer, namely polyurethane 1, in the top layer and underlayer paste.

The procedure and the recipes are the same as in the example 1, with the exception that 1.90 parts of sodium chloride per part of polyurethane are used in the substrate paste.

The properties of the material are summarized in Table I.

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Example 8

This example is a three-layer material, similar to that of Example 1, but with salt of smaller particle size in the substrate, and a harder polymer in the bottom layer and top layer, namely the same polyurethane 1 as in the substrate, can be used.

After the application of sub-layer substrate and covering layer is coagulated, leached, and dried according to the method described in Example. 1 ■

The substrate formulation differs from Example 1 in the use of sodium chloride with an average particle size of 17p and 2.05 parts of sodium chloride per part of polyurethane. The undercoat and topcoat formulations are the same as in Example 1, with the exception of the different polyurethane.

The properties of the material are summarized in Table I.

All of these examples have an elongation at break in the range of 375 to 500 # ..

Examples 10 to 24

Further examples showing the influence of variable substrate thickness (Examples 10 to 13 and 14 to 17) and of variable Salt ratios (Examples 18 and 19, 20 and 21, and 22 to 24) are shown in Table I. Own all of these examples an elongation at break in the range of 375 "to 500 5 &.

Examples 25 to 31

These are further examples that (in example 25) the use of a polyether polyurethane (polyurethane 4) in the outer layers, and in the other examples the influence

409886/1416

the change in the layer thickness and the density ratios demonstrate.

The details regarding salt ratio, polymer layer thickness, Salt particle size and physical properties are given in Tables II A and II B.

A comparison of Examples 26 and 27 shows that only a very small improvement in the ratio of tear strength to rigidity is achieved when the standard top layer is applied in the form of two thinner layers on both sides of the substrate. Comparison of Examples 23 and 27 shows that the use of coarser salt in the substrate significantly improves the ratio of tear strength to stiffness, and comparison of Example 28 with Example 29 shows the further improvement obtained in reducing the substrate thickness.

The comparison of example pairs 27 and 30 or 29 and 31 leads the drastic reduction in the tear strength / stiffness ratio from auras that occur when the substrate clears is not thicker and denser than the lower deck and deck.

Examples 5 and 6 and 25 are compared with regard to their resistance to hydrolysis. For this purpose, test specimens measuring 51 x 51 mm are kept separately in the vapor phase of a closed chamber kept at 90 C, the liquid phases of which consist of distilled water or aqueous ammonia (0.085 g / liter). The test samples are examined daily for the first formation of surface cracks when bent by hand (the first value is noted) and for crumbling of the material when bent by hand (the second value is noted). The material of Examples 5, 6 and 25 shows surface cracks after 17, 17 and 21 days in the aramonia steam and 33 t 33 or 46 days in the water steam, and crumbled (complete failure) after 18, 18 and 29 days in the ammonia steam and after 36, 38 or 50 days in steam.

409886 / Ut 8

-23- 243588Q

This shows the improved hydrolysis resistance of a material a Polyath.erpolyureth.an in the outer splints owns.

4098867U16

91U / 98860 *

NJ. - “O

OO vj

UI »oil

U) U) U) (Jj (JJU) UU) U) U) OOU) NJNJtVJWtON) NJ (OMtONJtO

U) U) U)

*>. U) 00 NJ - »N)

νο cn ■■ * vj I ^ vj

~ »-» - »N) N) -» NJNJNJ-i-i- »

VOVOVOOOvONJ-iOvovOVO Ul ul

example

Substrate polymer solids concentration

Salt particle size

Salt ratio

cn

he

cn

π

do rf

U> U) - »-» - »U) U) U> U) N) N) OJU) U) OOOJ (JOU) OoU) U) U)

NJNJN) N) NJN) NJNJNJNJtONJ

Ui υι υι ui ui ui Ui Ui on ui ui ui

oPdPdPdPdPdPäPdPdPüPdPdP polymer

Salt ratio

Solids concentration

VO N) U)

U) VO

O
U)

U) OO

U) NJ

cn - »

U)

NJ VO

UI U)

NJ OO

UI U)

cn

CM UI

Total thickness, mm

U) U)

Ul

U) OO top layer thickness, mm

N)

p ^

VO NJ
UI

OO
UI

CO

OJ
VO

OJ
VO

OJ N)

Ul
NJ

OO NJ

U)

OO CTi

u>

UI

VO VO

NJ OO

Substrate thickness, mm

Sub-layer thickness, mm

cn vj CO 00 σ » O oo Ul U) UI U) CO 00 U) σι

U)

vj

O j

CO

to cn

00

N)

Weight, g / m ²

NJ

N)

U)

N)

υι

NJ

VO

N) N) N)

00 00 ι £ »

UI O

NJ

U)

NJ

N) OJ ^. vj

U)

σι

OJ

oo
cn

NJ N) OJ OJ

cn

Ui

U) U)

N)
VO

N)

U) OJ

U)

σι

• t * ui

N) U)

NJ

U)

NJ

σι

N)

00

cn cn

- »-vl

οο

Tear strength, kg

Stiffness, kg

H N)

S υι + (*>

Weiterreißfestig- _'n ness / stiffness>

co

vj

UI
UI

oo

vj

Ul

N) UI

Ul

OJ

υι

σι
on

vj

(D C

H-rt

η cn S (D

cn & vQ ¹ T!

I Ml

Hj

■ Jq

• CQ

'ο

tt-

TABLE I cont.

rH I. _c - ... α) 1 ι
N co Top layer ι 05 1 I I C. CU ■ ι S ι
■ 1 κ. ι Cn
X 4Y 25% ι
Cn ■ Η
Q)
Ai I ■■ ";
Steam- B. U Q) -P O rH -H and under
layer M. ■ Η 1 HH (d O Ai 1
-P ι j E3 + ■ *
Xl 4-> CQ ■ Η
4- ·
05
ill U '
• Η permeable . ^ approx I Ij Substrate : 0 1 approx C. Q) C.
4-> ■ Η CJ approx ο Xl • Η Yy Q) W.
HH HH , ability (WVP) CU
05 Ii 05 Hh approx (H cn N rH 1 O 4-> -P •H υ ε U - υ
-H μ Q) • Η χ CQ • Η 05 Q) HH U Cn 1 , 9: H 05 H : <d -P C Τ3 • η ε YY Q)
05 Ai Λ 1 S ε U QJ Cn • Η Φ
50 Q) U O + J ι Q) 1 wd
Xt Q) approx Xl 1 05 Cl)
4Y N 4-) Xl Λ U υ ω \ U X • Η Φ 4-> co PQ Q) +) C rH X! 1 , 9: M. cn 1 05 C e
approx Ό - 3 · Η 05 * CJ Cn Q)
4Y Cn HH
• Η U cn 75 cn 13th cn S 05 Q)
S 4-) N • Η ϋ Q) Q) 3: Q) O 05 05 Q)
X X cn τ3 U Q)
Q) X 809 ■ Η +> Q) kg / cm U 4- · CD 1 <-H 05 CJ Q) 2 , 9: ε 1 UaX ο) ε Ό O 1.00 4-> Ü Q) 05 4-> Cn Q)
4Y • Η A. 70 cx> 14th O Q) O 4-)
N 1 , 9: 1 H 3: 25% ο ε Q) · Η Ö "H 803 Q) cn Ai -H Φ 55 1 Λ Pn. * rH 2 , 9: O 1 1.66 Q ¹ IJ 0.62 D Ό 3.2 HH 0.59 Q) Ai - 15th 32% approx / 9: 1 3: 1 25% 0.38 0.28 820 3.0 IS 55 16 ^ cn , 0: 3 3: 1 1.69 0.72 860 2.9 0.28
* 5.4 j
80 70 O
CO 17th 1 32% 31 2 / 9: 1 3: 1 25% 0.48 0.87 0.59 900 2.2 56 00 18th 1 , 0: 1 3 3: 1 25% 1.59 0.97 703 3.5 0.38 10.4 85 68 OO 19th 1 32% 49 2 /1: 1 3: 3: 1 25% 1.61 0.48 0.77 0.39 707 3.7 0.45 2.5 62 co 20th ; 1 32% 1 3 3: 25% 1.60 0.37 0.80 0.37 727 4.7 0.63 2.9 9.2 75 21 ; 1 32% 49 , 2: 1 3 3: 25% 1.50 0.28 0.72 0.35 713 2.4 0.34 3.4 8.2 55 58 .22 j
1 32% 49 1 3 25% 1/53 0.34 0.82 0.39 662 2.3 0.36 2.4 7.5 ; 45 OT I.
1 32% 49 , 3: 1 3 3: 25% 1.57 0.33 0.85 0.40 2.7 0.35 2.3 7.1 : 87 * 70 23 32% 31 1 3 25% 1.53 0.43 0.42 688 2.4 0.33 2.3 6.4 115 1 32% 31 3 3: 1.35 0.28 0.93 0.43 2.9 0.34 2.3 7.7 87 24
t 32% 36 1 3 25% 0.26 0.24 677 ι 2.4 7.3 112 i ¹ 36 3 1.42 0.83 3.0 0.35 8.5 95 32% 49 1 25% 0.29 0.20 2.3 3 1.41 2.8 , 0.35 8.5 95 32% 49 0.29, 0.29 . 2.4 3 8.0 98 49

91U / 98 8 607

oj oj ro ro ro ro ro - «· O VO Cu --3 Cn Ul

OJ OJ OJ OJ OJ OJ OJ OOOO ο Ο ro

j> 42. ->. -j. Ul vo VO OO -J -JO

ro I \ J ro ro ro ro ro ro ro ro ro ro ro OJ -j.

example

Substrate polymer Pesticide concentration

Salt particle size w

Salt ratios

03 cf

- * - * · OJ - * - * _i, OJ Polymer Oj OJ OJ OJ OJ Salt ratios

ro ro ro ro ro ro ro

Ul ul ul ul ul ul ul

CD HH

CF CD

¹ concentration of pesticides

ο ^

o -j vo vo vo vo ve j salt particle size

Ui CTi ui σ · \ ui o \ ui Oj Ui oo -J ui - * -j

O O O O O O O

Ch CTi OJ I \ J- ^l OJ OJ -ι 4 =. ΓΟ OJ 4 = »O 4 * ·

O O O O O O I

4 = »-F ^ Oj Oj ro OJ ui ro ο Oj vo -» ·

O O O

oj oj vo ro ro ro co vji cn -j · -Jk ui -j ui

O O O O O O I

OJ OJ
VO -O

45 »45» 45. cn j> oj

O 0 O O 0 I. 0 Ul
VD cn
ro OJ
—K _ & OJ O O O O 0 1 I. O OJ
-j ro
VO OJ 664 cn
Ul cn
OJ
Ul OZL 650 660 680

Total thickness
τητη

Top layer thickness, mm

Surface layer density

Substrate thickness, mm

Substrate density

Difference in thickness, mm

Underlayer density e

I ^r

: Total weight, g / m

Table II B

CD OO OO

at
game Tear on
strength,
kg Stiffness,
kg 25 i> IM,
kg / cm Tear on
strength/
Stiffness Steam-
permeable
ability (WVP) " B. Tensile strength
ability,
kg / cm Fracture d
tion, $ A. 73 25th 2.33 0.35 2.1 6.7 110 - - - 26th 1, 61 0.47 1.8 3.4 140 - 10.3 440 27 1.59 0.43 1.8 3.7 140 - 10.4 440 28 2.08 ■ 0.38 1.7 5.5 100 - 9.4 420 29 1.59 0.25 1.5 6.4 120 - 8.0 400 30th 1.41 0.46 1.8 3.1 150 - 8.8 390 1.84 0.51 2.1 3.6 115 9.3 390

Comments on Tables I, II A and II B

The cut tear strength is sewn method (H) described in connection with Table III.

The stiffness is measured as follows:

The method aims to reproduce the forces that have to be exerted by the tendons of the foot in order to make a fold to effect in a shoe upper leather. Reference is made to FIG. 9 for the following explanations. A test sample 50 of 7 cm length and 4.5 cm width is clamped in a clamping device 51 so that the outer or top layer surface, e.g. is clamped with the clamped ends 20 cm apart to form an inverted U shape.

The fixture is in an Instron tensile strength device arranged. A metal rod 55 15 cm in diameter, attached to the crosshead is applied at a rate of 2.5 cm / min onto the top end 56 of the inverted U-shaped Test specimen lowered, the rod 55 parallel to the flat bottom ends of the specimen and perpendicular to the longitudinal axis of the inverted U-shaped test pattern is (see Figure 9). the Stiffness is defined as the load that is required to create a 2.5 now deep indentation in the lowest part of the inverted U-shaped test piece. The £ 25 - AnfaigsnaoiiL (IJKO and the water vapor permeability (WVP) are like as described for Table III.

WVP A is the value for the material before the surface finish was applied.

WVP B is the value for the material after; i

409886/1416

Application of the surface finish. Each sample receives the same Surface finish treatment. This increases the resistance to the penetration of liquid water and to pollution improved, the surface is transformed from a dull, matte finish to a glossy, deeper colored finish, the treated surface takes on an artificial color, and the material has a crack similar to one another.

Spraying is carried out as follows:

12.9 parts of a 31 percent solution of the polyester polyurethane prepared above (Polyurethane 1) are mixed thoroughly with 7.1 parts of DMF and 0.4 parts of black paint (Superba black). 7.52 parts of the mixture obtained are mixed with 43.24 parts of additional DIvIF, 34.53 parts of cyclohexanone and 14.71 parts of acetone. This mixture is sprayed or sprayed onto the flat material, while hot air is directed from a slot nozzle against the surface of the sprayed material. The temperature of the air, measured 5.1 cm inside the slot nozzle, is about 110 ^° C .; however, after it has left the slot die, it mixes with the cooler ambient air, so that the temperature of the hot air stream just above the surface of the material (for example, 2.5 cm above it) is presumably about 80 ° C.

During the spraying process, the solution is pumped out with compressed air (5.6 atü) atomized in a standard spray gun that is 30 cm across the microporous material is arranged.

As soon as it leaves the spray zone, the sprayed material hits a stream of hot air which is directed at a small angle (for example an angle of about 15 °) towards the surface, so that the stream runs almost parallel to the upper surface of the material. The air flows from a flattened tube (a slot nozzle), the outlet of which is about 5.1 cm above the material and about 30 cm from the center of the spray gun, measured horizontally along the path of the running material, which is at a speed of

A09886 / U16

153 cm / min moved. The hot air flow serves to melt the DMF-containing polyurethane on the surface of the material.

The material then passes through a hot air oven (with an air temperature of 93 ⁰ C in the first zone and 121 G ⁰ in the second zone) to remove residual DMF. The dwell time in the oven is 3 minutes. The end product has a black, shiny, but finely grained appearance, like that of a smooth, fine black calf. The thickness is about the same as that of the original material. The dry weight gain is about 1 to 2 g / m 2.

for water vapor permeability (WVP) In all examples, values of / of 50 or above are obtained after the finishing treatment, and these values are in view of the use as a shoe upper material is completely satisfactory, since values of 40 for the production of comfortable men's shoes are suitable.

Additional finishing treatments such as coating, printing and / or embossing can also be carried out.

The results of the density measurements in Tables II A and II B were obtained by splitting the layers with a band knife splitting machine, Measure the thickness and weigh the sample obtained.

Example 32

According to Example 1, a material is produced, with the top layer and underlayer polymer the polyurethane 3 and as the substrate polymer the polyurethane 1 can be used.

The topcoat and bottomcoat formulations are as in Example 3. The substrate formulation contains 32.5 percent by weight polymer, based on polymer and solvent, 2: 1 parts by weight of sodium chloride, based on polymer, and the sodium chloride has a mean particle size of 40 microns when measured with the Coulter counter.

409886 / U16

The material without finish is split with a band knife splitting machine, and the properties of the top layer obtained, The substrate layer and sub-layer are measured.

The top layer and bottom layer are microporous layers 0.35 mm thick, while the substrate is about 0.75 mm thick.

The tensile strength of the substrate is over three times greater than

of both
that of the more solid layers, it is about 6 kg / cm; and the initial modulus is over ten times greater than that of the stronger of the other two layers, it is about 1.5 kg / cm. The elongation at break is, however, in the same range as the values for the other two layers, namely in the range from 300 to 450 $>.

40 9 8 86 / U1 6

Table III example

mean particle size positive. deviation Negative deviation salt / polymer ratio density

Thickness (ram)

Weight (g / m ² )

Cut tear strength

Tensile strength

Tear strength / notch tear strength Tensile strength

Initial modulus (IM) water vapor permeability (WVP), A porosity

mean pore diameter

Comments on Table III

'uncorrected results

2 ) λ

' Results corrected to 1.45 mm thickness and 0.45 g / cm ³ density

(A) This is the ratio in parts by weight.

(B) These values are measured by sedimentometry. Here receives
one values that go very well with those using
results obtained with a Coulter counter agree.

^ ' This represents the mean particle size.

'This represents the positive deviation.

'This represents the negative deviation.

A09886 / U16

LA 4)
f— \ 6 A (B) 27.5 5) 50 + 10 6) + 17 - 10 : 1 - 17th (A) 1.90 2.20 (C) 0.45 0.45 1.40 2) 1.43 652.5 652.5 (H) 1.33 2) 2.47 1.92 2) 2.50 (P) 4.17 2) 4.45 46 f. 2) 56 f ₃ (D) 11.9 11.5 (E) 2.3 ² 2.3 ² (G) 140 125 (M) 63 59.5 (N) 7.2 10

-33- 243598Q

(C) Density in g / cm · ^, obtained by weighing a certain area of the sheet material of a certain thickness

(D) Tensile strength in kg / cm

(E) At 25 percent elongation in kg / cm

(F) in kg

(G) water vapor permeability in g / m / h. at 100 percent relative humidity and 37 ⁰ C

(D), (E), (F), (G) and (H) are according to the in BE-PS 732 452 methods described.

(H) The tear resistance (cut tear, tear propagation) is measured in kg. The measurement is made with a tensile tester at constant speed in the transverse direction carried out, for example, as described in BE-PS 732 432 (Instron Tensile Tester). The test sample with rectangular dimensions of 75 x 45 mm, with a single blow of a press with a razor-sharp punch manufactured. A 20 mm long cut is made in this test specimen with a sharp knife, the starting from the middle of a short side, parallel to the long sides. The claws of the tensile strength S-Lie 3 device are placed 20 mm away and an edge 22.5 mm long is gripped from each claw. The test sample becomes an increasing strain from pulling apart the claws at 10 cm / min until the test specimen is torn along the cut. The tear strength is defined as the mean equilibrium value of the maximum Load value that is recorded.

(M) porosity

First, the apparent volume of the sample is determined using the

409886/1416

Geometry determined. The actual volume of the pest in the sample is determined in such a way that the sample is evacuated, then helium flows in up to atmospheric pressure and measures the volume thus introduced. The difference between the apparent and the actual volume results the total void volume or porosity (X).

(N) Mean pore diameter and mean pore size

The terms "pore size" or "pore diameter" used here these are the values obtained using the following experimental method: Pore size in this sense is not the maximum dimension of the gaps in the material, but gives the dimensions the holes or pores in the walls that surround or define the gaps, with the holes connecting ensure between the gaps.

The pressure required for mercury to penetrate a pore is inversely proportional to the pore diameter. The volume of mercury pushed through the pore into the gap corresponds to the volume of the pore and the gap. The porosity of a sample is plotted against the pore size, by determining the volume of mercury forced into the sample from all sides at given pressures can be. The total void volume (see above under (M)) is composed of pores and larger gaps into which these pores open, covering the entire area of pore diameters and each of which requires mercury for its filling at certain pressures. By defining the mercury pressures (P), the volume (V) of the mercury pressed in is, and therefore also that relationship

409886 / U16

determined at this pressure. This is the porosity in this one Pore size. By changing the mercury & ruclrs - The porosity can be applied as a puncture of the poreiidameter v / earth. Here you get a flattening at a certain value, which represents the total porosity of the sample, that is, all pores and gaps are filled with mercury «0.03 U is considered the smallest diameter. The value obtained in this way is in very good agreement with other methods, but offers the advantage of to show the range of pore diameters. The angular point the curve is taken as the mean pore diameter.

The initial pressure applied is 0.35 kg / cm absolute.

The water vapor permeability (G) is determined as follows: A 33 mm high screw vessel with a diameter of 70 min and which is provided with a screw cap with a hole of 60.5 mm diameter is filled with a sample of the microporous ilaterial with a diameter of 67.5 mm covered. The assembly is held in a climatic chamber at 37-1 ⁰ C in which the relative humidity is maintained at a value of zero by means of silica gel.

25 ml of distilled water are placed in the screw-top jar and the change in weight (w) in a certain time (t) is measured 4 hours after the jar has been placed in the chamber and again at least 5 hours later. The water vapor permeability (WVP) in g / m / h. at 100 percent relative humidity and 37 ⁰ C is given by the equation

- 336.6 w t

certainly.

A0S886 / U16

Table IV

example 1 A B. C. 6 A B. C. A. 6.4 6.4 A. 1.7 1.7 100 4th 7.9 1.5 1 2.7 1 75 5 7.9 0 1.6 2.7 0 50 5 8.7
9.5 " 0.8
0.8 " 1.6 3.4
57o 0.7
Ύ, 6 _25 _
20th 5.5
6th 9.5 0 2
3 5.6 0.6 17.5 6th 12.7 3.2 3.3 50.4 44.8 ■ 10 8th 64.3 51.6 30th 69.8 19.4 6.4 40.5 77.8 13.5 41.5 • 75.7 5.9 5.0 49 87.3 9.5 45 79.8 4.1 3.2 55 90.5 3.2 47.5 82.4 2.6 2.0 57 90.5 0 49 84.1 1.7 1.6 57 92 -. 1.5 50 85.7 1.6 1.0 58 93.7 1.7 51 85.7 0 0.8 59 93.7 0 51 87.4 1.7 0.75 59 95 1.3 52 89.9 2.5 0.5 60 95 0 53.5 92.4 2.5 0.4 60 98.4 3.4 55 97.5 5.1 0.2 62 98.4 0 58 99.2 1.7 0.1 62 98.9 0.5 59 99.2 0 0.075 62.3 100 1.1 59 99.2 0 0.05 63 100 0 59 100 0.8 .0.035 63 59.5

Notes on Table IV

In column A, the percent porosity of the sample is due to Pores indicated which are larger than the value in u indicated in the left column. This includes both the pores and the Gaps with which the pores are connected.

In column B derProzentanteü vm since ¹ Gesamfcprcsität specified, the
represents the value in the same row in column A. In example 1A, for example, 4 percent of the porosity corresponds to pores that are greater than 100 u, and this value represents 6.4 pro

409886 / U16

percent of the total porosity of 63 percent in Example 1.

In column C is the difference between that in the same Line entered in column B and the value entered in column B in the line above. Thus, the value in column C represents the percentage of the total porcsity that is due to pores between this value in this one Line and the line above it. For example, in Example 1A, 1.5 percent of the total porosity is pores that are greater than 75 U but not greater than 100 u.

On closer inspection of Table IV, it can be seen for Example 1A that 51.6 fo the porosity correspond to pores between 6.4 and 10 u. 13 »5 f ° are between 5.0 and 6.4 U, that is 65.1 / ^ between 5 and 10 ρ and 9 | 5 $ between 3» 2 and 5.0u, that is 74.6 fo between 3 »2 and 10u. 68.3 ? ° are between 5.0 and 17.5 u; the mean particle diameter is 7.2 μ.

In Example-6 A, 40 fo between 12 and 17.5 U, 4.3 ^r / o between 10 and 12 u, i.e. 44.8 fo between 10 and 17.5 u. And 19.4 $ between 6, 4 and 10 u, that is 64.2 fo between 6.4 and 17.5 u. 70.1 f ° are between 5.0 and 17.5 u; the mean pore diameter is 10u.

Regarding the further details of the examples porous carrier used and the nature of the polymers, solvents, Non-solvents and removable fillers that can be used are referred to in DT-PA 24 13 461.0 to which reference is made here in full.

As already stated, the top and bottom layers are integral firmly bonded to the substrate.

As can be seen from examination of the photomicrographs (Figures 1 to 8), this adhesion is not enhanced by a denser layer at the interface between the layers, but the walls between the gaps continue unchanged, apart

A09886 / U16

hen of a change in the wall thickness of one layer to the other. This desirable, highly permeable structure stems from the preferred method of working of simultaneous coagulation where all three layers are applied prior to any coagulation, and then the entire structure to the coagulant is exposed.

As mentioned above, the top layer is preferably given a finish. The preferred embodiment of this finishing treatment involves the formation of a thin, densified, but still permeable zone on the outer surface of the cover sheet. This compacted layer is normally no more than 30 microns thick in products that are similar to grained leather, and has generally a thickness of less than 20µ, for example 1 bic or 3 "to 10µ.

After applying the finish according to the aforementioned method, the surface of the material shows the following general properties during microscopic examination: It has a thin, molten surface layer, typically 1 to 15 μm thick, with fewer pores penetrating the surface than the untreated one Material, i.e. ^ less than about 300 pores are visible at 200x magnification in an area of 360 χ 360 u. The material typically has fewer than 200 pores, for example not more than 100 pores, for example 10 to 100 pores, mostly 30 to 70 pores, for example about 50 pores, which at 200-fold magnification in an area of 430 χ 430 u are visible. These pores are located in shallow craters, which are typically 5 to 20 γ., For example 10 µ, deep and 20 to 90 µ, for example 50 y., Wide. The pores in the bottom of a crater typically appear

tied together
bridge-like and allow access to further pores in the interior of the material. The remaining pores typically have a diameter of 5 to 30 µm, for example 20 µm, and are thus generally larger than the pores in the unsprayed material.

409886/1416

Each crater can contain several such pores, typically 3, 5 »6, 8 or 10.

Own all of the materials made by these methods good properties in terms of the hernia or furrow pattern, which shows a fine pattern of furrows on the fold line when the material is with the top layer on the inside the fold is folded sharply.

Figures 1 to 8 show preferred embodiments of the invention Laminates. Figures 1 to 8 are photomicrographs made using an electron microscope, which show the laminates in cross section at 55x magnification.

The laminates have a thickness of at least 0.8 mm and consist of three superimposed layers of elastomeric polymers that are firmly connected to one another, namely one strength-imparting, porous, elastomeric substrate layer 15, 18, 21, 24, 27, 30, 33, 12, which is sandwiched between a porous, elastomeric Polymer lower layer 17, 20, 23, 26, 29, 32, 35, 14 and a porous, elastomeric polymer outer layer 16, 19, 22, 25, 28, 31, 34, 13 is arranged.

All further details regarding the special nature of the layers and their thickness ratios are given in the description refer to.

409886 / U16

Claims (12)

. Water vapor permeable, soft, flexible sheet material of at least 0.8 mm thickness with at least three superimposed porous layers made of elastomeric a polymer, whereby the material contains no fibrous reinforcement, has an elongation at break of over 200 % and a strength-imparting, porous, elastomeric polymer substrate layer which is arranged between a porous, elastomeric polymer underlayer and a porous, elastomeric polymeric cover layer, the substrate layer has a higher density than the underlayer or cover layer and is thicker than either the underlayer or the cover layer, and the total thickness of the underlayer and Cover layer in the range of · 30 to 175 fo the thickness of the substrate layer. 2. Material according to claim 1, characterized in that the da.3 strength-imparting, porous elastomeric polymer substrate layer has compact gaps that statistically over the layer is distributed and connected by pores that penetrate the walls between the gaps, the sub-layer is microporous and has compact gaps that are statistically distributed over the layer: and by pores that the walls between the gaps connect, are connected, the top layer is microporous and has compact gaps, which are statistically distributed over the layer and connected by pores that penetrate the walls between the gaps and the substrate has wall thicknesses between the gaps, which are generally larger than those of the lower class or the top layer. 3. Material according to at least one of claims 1 and 2, characterized thanks to a tear strength of at least 1.5 kg and a ratio of tear strength to rigidity of at least 4 * 2 4. Material according to at least one of claims 1 to 3, da- A09886 / U16 characterized in that the substrate layer consists of a porous matrix of an elastomeric polymer which ensures a multiplicity of compact gaps interconnected by pores, the substrate layer is 0.5 to 1.5 mm thick and a total gap volume or porosity of over 50 fo , and at least 65 ° of the porosity are formed by pores and the gaps with which the pores connect, the pores having a diameter of at least 5. Ou and preferably not more than 20 u, determined by the mercury method. 5. Material according to at least one of spoke 1 to 4, characterized in that the lower layer and top layer are integrally adhesively connected to the substrate layer. 6. Material according to at least one of claims 1 to 5, characterized in that the substrate polymer is a polyurethane based on polyesters and has a Shore hardness of 75 A to 60 D, preferably at least 93 A, measured on a solid, continuous film at 25 ⁰ G, and the polyurethanes used for the bottom layer and the top layer are made on the basis of polyesters or polyethers and have a lower Shore hardness than the substrate polyurethane. 7. Material according to at least one of claims 1 to 6, characterized in that the substrate layer has a porosity in the range from 50 to 65 λ>, less than 7 $ of the total porosity of pores and gaps connected to the pores, with pore diameters of over 100 µ, and at least 50 % of the total porosity originate from pores and voids connected to the pores, with pore diameters in the range from 6.4 to 17.5 µ. 8. Material according to at least one of claims 1 to 3, characterized characterized in that the substrate layer upon observation compact gaps in a cut cross-section 409886/1416 whose teaching number has maximum dimensions in the dec Cross-section of 30 to 100 μ, the reciprocal number of these gaps has the smallest transverse dimensions in the plane of the cut Has a surface of 1/4 of its maximum dimension and above, the shape of the gaps is non-spherical and despite being irregular Outline is compact, the gaps through denser regions, (which can be viewed as thicker edges) are separated, the smaller one, at 150x magnification contain visible pores, the majority of which have diameters of 1 to 30 µm, and which are 1 to 10 µm apart with the majority of these denser regions being 30 to 100 µm in diameter between adjacent larger ones Has loopholes. 9. Material according to at least one of claims 1 to 3, characterized in that the bottom and top layers are microporous are and, when observing a cut cross-section, irregularly shaped but compact gaps of. 5 to 75 U in diameter, with the majority 20 to 50 U in diameter, and the gaps of thin, 1 to 5 ρ thick walls are limited or surrounded, and the gaps are connected by pores that are thin through them Pass walls through. 10. Material according to at least one of claims 1 to 9 »characterized in that the substrate polymer as a thick, gap-free film of 0.2 to 0.4 mm thickness has a module at 25 $ elongation of at least 55 kg / cm, and the lower layer and outer layer polymers as thin, gap-free films from 0.2 to 0.4 mm thick have a modulus at 25 ° elongation of less than 55 kg / cm. 11. A method for producing the material according to any one of the claims 1 to 10, characterized in that 'a layer of a coagulable, elastomeric polymer sub-layer material on a porous support to form the sub-layer, a layer of before coagulation 409886/141 © a coagulable, elastomeric polymer substrate mass on top of the layer of underlayer compound and then before coagulating a layer of a coagulable, Applying elastomeric top layer mass on top of the layer of substrate mass, and then the composite material under Formation of an integral, firmly connected, microporous, three-layer structure that does not have any fibrous reinforcement contains, coagulated, with at least the substrate mass and at least one of the underlayer or top masses having a removable, contains particulate filler, and the filler in the undercoat or topcoat composition is a medium one Has particle size smaller than the particle size used in the substrate mass. 12. The method according to claim 11, characterized in that a substrate mass is used which contains an elastomeric polyurethane dissolved in a polar organic solvent in. 25 to 40 percent by weight concentration with a particulate soluble filler dispersed therein which is essentially insoluble in the organic solvent and an average particle size measured by the Coulter counter, in the range of 20 to 200 ju has, and the ratio of filler to polymer in the range from 1.8: 1 to 2.7 x is' 1 parts by weight, and the undercoat and topcoat compositions are dispersed filler having an average particle size of less than 20 / u. contain. 13 · Use of the sheet material according to one of the claims 1 to 10 as a leather substitute, preferably as a shoe upper material. 98 8 6/1416 - if U- blank page