DE2835293A1 - METHOD FOR MANUFACTURING LEATHER-LIKE FLAT MATERIALS - Google Patents

Description

Möhlstrasse 37 TEIJIN LIMITED. ^D - ⁸⁰⁰⁰ Munich

Tel .: 089 / 982085-87

Osaka, Japan Telex: 0529802 hnkld

Telegrams: ellipsoid Dr.F / da

11 AUG. 1978

Process for the production of leather-like flat materials

The invention relates to a method for producing leather-like flat materials or band-shaped materials. In particular, it is concerned with a method for producing leather-like flat materials from hollow composite fibers of a type that produces particularly fine fibers, each composite fiber being made up of components made of polyester or polyamide and components made of polystyrene.

It has hitherto been known to produce leather-like flat materials using particularly fine fibers. U.S. Patent 4,051,287 and U.S. Patent Application Ser.No. 799 818 describe a suede-like woven or knitted fabric (a leather-like flat or sheet material), which by applying an elastic polymer on a roughened woven or knitted fabric with

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especially fine fibers obtained from hollow composite fibers were made, the composite fibers of at least four alternately arranged components fiber-forming polyester and fiber-forming polyamide exist, which alternately - side by side - adhere to each other and encompass a cavity and which extend along the Extend the longitudinal axis of the fiber to form a tubular body. This hollow composite fiber has the advantage that their constituents

can easily be separated by mechanical influence in order to form particularly fine fibers. All Components are useful as particularly fine fibers. However, the obtained particularly fine fibers must be dried by means of a complicated process, since they consist of two polymers with different from each other Properties exist.

U.S. Patent 3,865,678 is concerned with a suede-like one roughened woven fabric (a leather-like flat material) fder by applying an elastic polymer on a woven fabric made of particularly fine fibers obtained from composite fibers of the Islands-in-Sea type, was produced . The Islands-in-Sea type composite fiber can be divided into a bundle of components in the form of Island fibers (especially fine fibers) are transferred by removing the sea component from the composite fiber will. However, the islands-in-sea type composite fiber has drawbacks that a spinneret is complicated in structure must be used in the process of making the Islandsin-Sea type composite fiber and the process very much difficult to regulate.

Japanese Laid-Open Patent Application 48402/76 describes a hollow composite fiber which is separable into fine fibers is, and a leather-like sheet material that

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by applying a polyurethane to a non-woven fabric formed by means of hollow composite fibers, is obtained. With regard to the separable polymer combination the Japanese patent application describes the combination of polyamide and polyethylene terephthalate, polyethylene terephthalate and polystyrene and also polyamide and polystyrene. However, this Japanese patent application is concerned does not deal with the denier of the fine fibers, nor does it make any suggestions on the structure of the hollow composite fiber with components made of polyester or polyamide and polystyrene.

Due to the experiments carried out by the inventors of the method according to the invention, it was very difficult to obtain a to produce composite fibers with good properties from components made of polyester or polyamide and polystyrene. In the production of a hollow composite fiber from alternately joined components made of polyester or polyamide and polystyrene, which are mutually side-by-side - adhere to each other and form a cavity include, drawing the melt-spun hollow composite fiber was very difficult because of the adhesive force between the constituents of different polymers poor and the physical properties of the constituents different Polymers differed greatly from one another. As a result, it was difficult to find one suitable for commercial use to obtain hollow composite fiber.

It has now surprisingly been found that a hollow Composite fiber made of components made of polyester or polyamide and polystyrene and a special titer and a special Structure good properties in the formation of a melt in melt spinning and drawing shows and are preferably used for the production of leather-like flat materials with outstanding properties can.

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The invention accordingly provides a method for producing leather-like flat materials, which thereby is marked that

a) hollow composite fibers are produced, each of which is composed of 16 to 96 alternately arranged components of polyester or polyamide and polystyrene, which mutually adhere to one another - side by side - and enclose a cavity and which extend to form a tubular body along the longitudinal axis of the Extending fiber, wherein the hollow composite fiber has a denier of 1 to 20 and each component has a denier of 0 ₇ 01 to 0.5,

b) a fabric using the hollow composite fibers thus formed will be produced,

c) the constituents of polystyrene are removed from the hollow composite fibers by means of a suitable solvent and

d) an elastic polymer is applied to the fabric.

In the following figures:

Fig. 1 is a schematic cross section of a hollow composite fiber used according to the invention,

2 shows an axial cross section of a spinneret for producing a hollow composite fiber,

3 shows a transverse partial cross section of the spinneret of FIG. 2 along the line AA ¹ and

Fig. 4 is a transverse partial cross-section of the spinneret of Fig. 2 along the line B-B '.

The following are preferred embodiments of the invention to be discribed:

The hollow composite fiber of Fig. 1 employed in the present invention has a schematic cross-section as shown

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is made by cutting a hollow composite fiber with total 32 components. In Fig. 1, the hollow composite fiber 1 is made of components 2 made of polyester or polyamide, components 3 formed from polystyrene and a central cavity 4. The components 2 made of polyester or polyamide and the components 3 made of polystyrene and the central cavity 4 extend along the longitudinal axis of the fibers 1. The components 2 made of polyester or polyamide and the components 3 made of polystyrene are alternately around the central cavity 4 and adhere alternately side by side - to each other, so as to form a tubular fiber body to build. In the embodiment according to FIG. 1, the cavity 4 is formed around the longitudinal axis of the fiber 1 and the components 2 made of polyester or polyamide and the components 3 made of polystyrene are regular and arranged alternately around the central cavity 4. However, the cavity 4 can also be eccentric in terms of be formed on the longitudinal axis. The components 2 made of polyester or polyamide and the components 3 made of polystyrene can be arranged around such an eccentric cavity 4, being irregular and in cross-section different trainings and areas are available.

The hollow composite fiber used according to the invention consists from 8 to 48, preferably 16 to 36 components made of polyester or polyamide and the corresponding number of polystyrene components. If the total number of components is less than 16, the composite fiber tends to melt-spun and / or stretching to disintegrate or break into the respective component. In contrast, tend to two or more components made of polyester or polyamide in the composite fiber tend to adhere to each other when the The total number of components is more than 96, so that it is difficult to obtain particularly fine uniform Obtain fibers of the desired titer.

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The titer of each ingredient in the hollow

Composite fiber must be in the range of 0.01 to 0.5, preferably are in the range of 0.05 to 0.3 denier. If the Titer is less than 0.01 denier, two or more components made of polyester or polyamide tend to be in the Composite fiber to adhere to each other. Furthermore, the manufacturing process is difficult to manage.

In contrast, the composite fiber tends to separate into the respective ones during melt-spinning and / or drawing Ingredients if the denier is more than 0.5 denier. The denier of the hollow composite fiber is in the range from 1 to 20 denier. When the denier is less than 1 or more than 20 denier, it becomes difficult to hollow Manufacture composite fiber. The ratio of the total weight of the components made of polyester or polyamide to that of the constituents of polystyrene is not necessarily limited, although a ratio between 50: and 70:30 is preferred.

In the hollow composite fiber used in the present invention, there is no limitation on the void ratio; the ratio of the volume of the cavity to the sum of the volumes of the components made of polyester or polyamide, the polystyrene components and the cavity. However, it is preferred that the void ratio be between 1 and 30% by volume, a void ratio between 2 and 15% by volume being particularly preferred. That Void ratio can be determined by the following method. A cross-sectional profile is drawn along a few points of the fiber is observed, measuring the cross-sectional area of the cavity and that of the fiber body. That Ratio of the cross-sectional area of the cavity to the of the fiber body is determined from these measured values. The same procedure is carried out twenty times in different places

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len repeated along the fiber. The void ratio of the fiber represents an average value of the determined ratio values. When the hollow composite fibers have a void ratio between 1 and 30% by volume, the hollow composite fibers can be treated, for example by means of a Melt spinning, drawing and weaving, without individual components being separated from one another. The polystyrene components of the thus obtained hollow composite fibers are easily removed with a solvent suitable for this purpose, in order to especially to form fine fibers that consist of individual polyester or polyamide components.

In the present invention, the polyester used in the polyester components can be selected from the following group: (1) alkylene terephthalate homopolyesters in which the alkylene group is derived from a polymethylene glycol of the formula HO- (CH ₂ ) -OH, where ρ represents an integer from 2 to 10; (2) Alkylene terephthalate copolyesters (composed of 3 components) in which the alkylene group is subordinate to the above definition and the third component has been derived from at least one of the following compounds: adipic acid, sebacic acid, isophthalic acid, diphenylsulfonic dicarboxylic acid, naphthalenedicarboxylic acid, hydroxybenzoic acid , Propylene glycol, cyclohexane-dimethanol and neopentyl glycol in an amount of 10 mol% or less based on the amount of the alkylene terephthalate component. The polyester used to form the polyester components can also be a mixture of two or more of the aforementioned homopolyesters and copolyesters. Among these polyesters, polyalkylene terephthalate is particularly preferred. Preferred polyesters used according to the invention have an intrinsic viscosity between 0.4 and 1.2 when they are measured at 35 ° C. in o-chlorophenol.

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The polyamide used in the polyamide components can be selected from the following group of compounds: nylon 4, nylon 6, nylon 66, nylon 7, nylon 610, nylon 11, nylon 12, polyamides of bis (p-aminocyclohexyl) - methane with a dicarboxylic acid, such as 1,7-heptanedicarboxylic acid and 1, 10-decamethylene dicarboxylic acid, copolyamides of two or more of the aforementioned polyamides and mixtures of two or more of the aforementioned polyamides and copolyamides. Among these polyamides, nylon 6 and nylon 66 are particularly preferred. The polyamides are particularly preferably used in the invention have an intrinsic viscosity between 1.0 and 1.3 when measured at 35 ⁰ C in m-cresol.

The components made of polyester or polyamide can contain antistatic agents, matting agents such as titanium dioxide, coloring agents, such as carbon black, and antioxidants with thermal stability.

The polystyrene, according to the invention in the polystyrene components is used can be selected from the following group: (1) homopolymers of Styrene and (2) styrene copolymers obtained by copolymerization of more than 80% by weight of styrene with less than 20% by weight of another vinyl compound. As vinyl compounds copolymerizable with styrene, are listed as examples: vinyl toluene, chlorostyrene, Acrylonitrile, ethylene, propylene, butylene, butadiene and isoprene. Preferred in the present invention The polystyrenes used have a melt index between 10 and 30.

The method of manufacturing the hollow composite fiber that shown in Fig. 1 will be explained below;

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Figure 2 shows an axial cross-section of a spinneret used to make the hollow composite fiber of Figure 1 (the hollow composite fiber having a total of 32 components). FIG. 3 shows a transverse partial cross section of a spinneret from FIG. 2 along the line AA ¹ . FIG. 4 shows a transverse partial cross section of the spinneret according to FIG. 2 along the line BB ¹ .

In the spinneret of FIG. 2, a cover plate 12 is fastened to the base plate 11 by means of a clamping screw 21 and sealed with respect to the base plate 11 by means of a seal 20. The bottom plate 11 has a recessed one Area which forms a narrow liquid passage 14 between the base plate 11 and the cover plate 12. This Liquid passage 14 is in the form of a circular one Recess, which can be seen from FIG. 4. The bottom plate 11 has a plurality of spinning openings 3, of which each four circularly arranged slots 17 in the area of the bottom, which is shown in Fig. 4, and an upper one Opening with the liquid passage 14 through the plateau-like projection 18 passes through. The number of slots ranges from 1 to 8 and is preferably 4. The cover plate 12 has a guide hole 15 for a first molten polymer and a Plurality of guide holes 16 for the second melted Polymer according to the number of each Spinnöffnun ^ 3 on. Four of the guide holes 16 of the second molten polymer are formed around the guide hole 15 for the first molten polymer formed, which is shown in the figure. The number of pilot holes for the second Molten polymer is not necessarily limited, although a number between 1 and 6 is common to each pilot hole corresponds to the first molten polymer, is preferred. The guide hole 15 for the first melted

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Zene polymer stands with the liquid passage 14 through sixteen small openings arranged in a circle 19 (as shown in Fig. 3) in connection in the bottom of the guide hole 15 for the first molten polymer are formed. The small openings 19 are arranged in such a way that the first molten polymer, which is extruded through the small openings 19, can impact the plateau of the projection 18. The upper The opening of the guide hole 15 of the first molten polymer is connected to a supply device (not shown) for the first molten polymer in conjunction. The lower and upper openings of the guide hole 16, which is provided for the second molten polymer is, stand with the non-protruding areas of the liquid passage 14 or the supply device (not shown) of the second molten polymer in connection.

The number of small openings 19 in the bottom of a each guide hole 15 formed for the first molten polymer must be equal to the number of means of the first molten polymer may be constituents formed in the hollow composite fiber obtained. As a result In the present invention, the number of small openings is in the range from 8 to 48, preferably between 16 and 36.

The first molten polymer is the guide hole 15, which is provided for the first molten polymer is fed from the feeders (not shown) and hits the plateau of the projection 18 through the small openings 19 to form sixteen fine streams of the first melt polymer, these streams to the spinning orifices 13 are performed. The second molten polymer is the guide holes 16, which for the second

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molten polymer are provided from the feeders (not shown) fed and led to the liquid passage 14 and enters with the first molten polymer in contact after it is evenly streamlined through the projection 18 under Education has flowed. The two molten polymers that come into contact with each other form one Composite stream consisting of sixteen fine streams of the first molten polymer, each passing through the second molten polymer are surrounded, the composite stream leads to the spinning opening 1 3 and through the Column 17 is extruded to 'a hollow composite fiber with 32 components, as shown in FIG. 1, to form.

In the present invention, polyesters or polyamides and polystyrenes are used as polymers for the first or second molten polymer used.

Polyesters or polyamides used as the first molten polymer preferably have a melt viscosity of 1000 to 3500 poise, while polystyrenes used as the second molten polymer preferably have a melt viscosity of 500 to 1500 poise. In melt spinning, it is preferred that the temperature prevailing is between 280 and 300 ^° C. and the winding speed of the spun filaments (undrawn filaments) between 500 and 2000 m / min.

In the present invention, the ratio is the feed rate (g / min) of the polyesters or polyamides to that of the polystyrenes in the range of 50:50 to 70:30. It is possible to use a hollow composite fiber with components the desired cross-sectional arrangements and

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Areas can be obtained by changing the ratio within the stated range. Filaments thus obtained and drawn are drawn up to a draw ratio of 2 to 5 to form the hollow composite fibers (drawn filaments) used in the present invention. When drawing, it is preferred that the drawing temperature is between 40 and 130 ^° C. under wet or dry conditions and the winding speed of the drawn filaments is between 300 and 1,000 m / min.

According to the present invention, a fabric is formed using hollow composite fibers thus obtained. The fabric represents in the present invention a nonwoven, woven or knitted fabric as well as a composite from it.

In the case of non-woven fabrics, there is a knitted fabric and a felt-like one Product according to the invention made from hollow composite fibers or a mixture of hollow composite fibers and conventional fibers each having a denier greater than about 1 manufactured. The knitted fabric can be made by using a conventional Apparatus for making non-woven fabrics are formed, such as by means of a carding machine, a cross wrapper and a machine for the production of a random webber, or it can also be made directly. The filzarti-.ge product can be made by needling a variety of in Layered knitted fabrics are produced. The felt-like product can also be produced by that the knitted fabric together with a knitted fabric, a woven or knitted. Fabric made from conventional layers arranged in layers Fibers are formed. The density of the needling can be adjusted according to the requirements of the non-woven fabrics are straightened,

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are correct and is preferably 200 to 800 needles / cm ² . The formation of the knitted products can also be accomplished by stitchbonding using machines such as the Arachne, Maliwatt or Mlipol machines. One or both surfaces of the felt-like product can be roughened using conventional buffing machines, such as a roll sander with sandpaper or an abrasive cloth.

The woven fabric is made from a multifilament yarn or a fiber yarn or web of hollow composite fibers according to FIG of the present invention as the warp and / or weft of the woven fabric using a conventional loom manufactured. Either or both surfaces of the woven fabric can be machined using conventional napping machines are roughened, such as with an emery rougher, a roller card rougher, a metal card rougher or a drum sander with sandpaper or emery cloth. For woven fabrics that are at If roughened woven fabrics are used, a satin fabric is preferably used, which is made from a multifilament yarn or a filamentary yarn made of hollow composite fibers having a denier of 50 to 500 denier as weft and a multifilament yarn, a mixed multifilament yarn, a fiber yarn or a mixed fiber yarn made from conventional fibers (whose monofilament denier more than a little 1) with a titer of 50 to 300 denier is constructed as a chain. If desired, two surfaces Roughening (one surface and the back surface) of the fabric preferably becomes double-sided woven fabric with a satin structure preferred in both surfaces. Atlas materials are triple atlas materials and quadruple atlas are particularly preferred. In particular, a textured yarn with crimp made of polyesters, such as polyethylene terephthalate or polyamides, such as

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Nylon 6 and nylon 66, are preferred as the warp yarn. Of the The knitted fabric is made of a multifilament yarn or a fiber yarn of hollow composite fibers according to the present invention using a conventional one Knitting machine manufactured. If a warp-knitted fabric is used, it is preferred that the yarn be on the outside from a multifilament yarn or a fiber yarn made of hollow composite fibers and the back yarns a multifilament yarn, a mixed multifilament yarn, a fiber yarn or a mixed fiber yarn the conventional titer. When using a fabric in the form of a circular knit, it is preferred that both the front and the rear areas or only the front area thereof from one Multifilament yarn or a fiber yarn made from hollow composite fibers getting produced. One or both surfaces of the knitted fabric can, as in the case of the woven fabric, be roughened.

In the present invention, the multifilament yarns constitute E.g. a single twisted filament yarn, a single twisted filament yarn, a double filament yarn, a triple filament yarn, the textured yarn "Taslan" (trademark of Du Pont) or a textured yarn with crimp, that has been produced by false twisting, upset puckering, edge puckering or air jet texturing. The mixed multifilament yarns represent a multifilament yarn made of two or more different filaments.

In the present invention, a substance obtained in this way is treated with a solvent of polystyrene, iim the polystyrene components of the hollow composite fibers, contained in the substance. All the polystyrene components of the hollow composite fibers are made in the essentially with a solvent such as benzene, toluene,

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Trichlorethylene and perchlorethylene, at room temperature or elevated temperature. As a result, a fabric is obtained which contains particularly fine fibers, the particularly fine fibers consist essentially of polyester or polyamide components, each having a titer from 0.01 to 0.5 denier. The removal of the polystyrene components of the hollow composite fibers can after Applying an elastic polymer to the fabric, as described below, can be carried out.

The aforementioned measure of roughening the fabric can after the removal of the polystyrene components and before Applying an elastic polymer to the fabric can be taken. If desired or required can be sheared, sanded or polished or brushed on the roughened fabric after the polystyrene components have been removed can be made from the hollow composite fibers.

In the present invention, an elastic polymer is applied to the fabric thus obtained (i.e., a substance that is used before or after the polystyrene components are removed obtained from the hollow composite fibers). The elastic polymers include more natural ones Rubber and synthetic elastic polymers such as acrylonitrile / butadiene copolymers, polychloroprene, styrene / butadiene copolymers, Polybutadiene, polyisoprene, ethylene / propylene copolymers, copolymers of the acrylate type, Silicones, polyurethanes, polyacrylates, polyvinyl acetate, polyvinyl chloride, polyester / polyether block copolymers, Ethylene / vinyl acetate copolymers etc .. The process by which a urethane prepolymer is applied to the substance applied and then the fabric is heated to form a polyurethane in the fabric, is used in the present case Invention chosen preferred.

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The elastic polymer is applied to the substance in the form of a solution, such as in the form of a solution with an organic Solvent, an aqueous solution or emulsion of the elastic polymer applied. For applying the solution of the elastic polymer can be a process for impregnating the fabric with the solution, a process for coating the surface or back surface of the fabric with the solution and a method of spraying of the solution can be applied to the tissue. The impregnation process and the process of back coating are preferably used according to the invention. In the case of the impregnation or spraying method, it is preferred to use a solution an elastic polymer with a concentration of 1 to use up to 50% by weight of the solution. In the coating process, it is preferred to use a solution of an elastic To use polymer at a concentration of 5 to 50% by weight of the solution. The amount of elastic polymer (Dry weight), which is applied to the fabric, is determined according to the intended area of application of the leather-like flat materials obtained, although an amount of 0.5 to 150% based on weight of the substance are preferred. After application, the elastic polymer is solidified or after any well known processes coagulate to create a leather-like sheet material.

The following are preferred examples of urethane prepolymers: hygroscopic and heat-reactive urethane prepolymers with one or more isocyanate groups which are blocked by means of bisulfites, in particular those are preferred which contain 10 to 40 wt .-% of an oxyethylene group in the molecule and those in the disclosed Japanese Patent Applications 108 395/75 and 155 794/75. The urethane prepolymer is on the substance in the form of an aqueous solution or an emulsion

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applied. The treated substance is then dried and ^{heated at a temperature of 100 to 180 °} C. for 10 seconds to 15 minutes. During the heat treatment, the urethane prepolymer in the substance releases the isocyanate groups blocked by bisulfites, as a result of which active isocyanate groups are formed and consequently a polyurethane is formed via a self-crosslinking reaction.

The substance obtained according to the invention can be used before or after the application of the elastic polymer according to any conventional method Process to be colored or printed.

If desired or necessary, the fabric provided with an elastic polymer (the leather-like surface material) polished or brushed by any conventional method. If necessary, can decating of the brushed leather-like sheet material can be performed. Furthermore, it is with the present one Invention possible to carry out various treatments during or after the application of the elastic polymer, to make the fabric water-repellent, waterproof, antistatic, flame-retardant and fire-resistant as well as him to impart a good resistance to soiling as well as slime imparting.

The leather-like sheet material obtained according to the invention exhibits a pleasant grip, excellent recoil resilience and excellent wrinkle resistance. Accordingly, this is according to the invention leather-like flat material obtained accessible for a variety of purposes, such as in clothing, such as jackets, sweaters, blazers, skirts, pants, shorts, lighter clothes, formal clothes, costumes, Suits, vests and coats, bags, boots, gloves and chair covers.

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The following examples are intended to further elucidate the invention purify.

example 1

(Manufacture of the hollow composite fibers)

Hollow composite filaments were (determined at 35 ⁰ C in o-chlorophenol) of polyethylene terephthalate having intrinsic viscosity of 0.60 as a polymer for the first molten polymer and polystyrene of a melt flow index of 20 as the polymer for the second molten polymer using the spinneret of Fig. 2 manufactured. The number of spinning orifices was 20. The number of small orifices 19 formed in the bottom of each guide hole 15 for the first molten polymer were 6, 8, 16, 32 and 40 in Experiments Nos. 1, 2, 3 , 4 and 5. The first and second molten polymers were fed into respective guide holes at a feed rate of 9 g / min. The hollow composite filaments were ^{spun at a temperature of 285 °} C. at a winding speed of 900 m / min. The obtained undrawn filaments were drawn at a temperature of 110 ^° C. to a draw ratio of 4.0 to obtain hollow composite filaments, each showing a denier of 2.3 and a void ratio of 5%. The physical properties of the composite hollow filaments thus obtained are shown in Table 1.

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Tabel

Total number of
Components Titer one
every stock
partly in denier
*1 Processing
ability at
Melt spin
nen and ver
stretch
* 2 Separating power
(%)
* 3 Experiment No. 1 12th 0.20 bad 100 Experiment No. 2 16 0.14 Well 100 Experiment No. 3 32 0.07 outstanding 100 Experiment No. 4 64 0.04 outstanding 100 Experiment No. 5 80 0.03 outstanding 80

Notes on Tables 1 and 2:

* 1: From the denier, the hollow composite fiber and the total number of the constituent parts of the hollow composite fiber. The calculated value is equal to that measured value when the separability of the components is 100%.

* 2: Processability in melt-spinning and drawing the hollow composite fibers.

Excellent: The hollow composite fibers hardly separate into their components and can easily subjected to melt spinning and drawing. Good: The hollow composite fibers separate

slightly in the respective components. But they can be under practical Subject to aspects of melt spinning and drawing.

Bad: The hollow composite fibers separate considerable in their constituent parts, so that the process regulation in melt-spinning and drawing is difficult.

* 3: The separability of the components is expressed as a percentage Value given by dividing the total number of polyester or polyamide components obtained - the entire removal of the polystyrene components of the hollow composite fiber by the total number of polyester or Polyamide components is calculated. 100% separation ability means that all components are completely separated dissolve into the individual components. . . 50% separation power means that on average two components were found adhering to one another.

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In experiment no. 1 (in which the total number of components outside was within the scope of the present invention} of Table 1, it was difficult to obtain hollow composite fibers, which is due to the poor processability in melt spinning and drawing of the fibers. On the on the other hand, in tests 2 to 5 (in which the total number of components is within the scope of the invention lag) good hollow composite fibers can easily be obtained

, which is due to the good processability during melt spinning and drawing of the fibers. Under these had the hollow composite fibers obtained in accordance with Experiment No. 5 (being the total number of Constituents 80) had a separability of the constituents of 80%. This means that it is part of the polyethylene terephthalate components it was found that, on average, they stuck to each other in pairs. As a result the releasability of the constituent parts of the hollow composite fiber became poor when the total number of the constituent parts was too large (when the total number of ingredients was more than 96) / which is not preferred in the present invention.

Manufacture of a woven fabric

A woven fabric was made using hollow composite filaments, the obtained according to Experiment No. 3. A simple twisted filament yarn was used as the weft yarn of these hollow composite multifilaments (600 denier / 260 filaments) having a twist number of 150 D / m with an S twist used. A double filament yarn (200 denier) made from two (false-twisted) wool spun yarns was used as the warp yarn 100 denier / 24 filaments made of polyethylene terephthalate and a twist number of 150 D / m and S twist are used. A quadruple atlas was made from the warp and weft yarns, the weave density being 27.5 warps / cm (70 warps / inch) and 22.0-5 picks / cm (56 picks / inch).

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The woven fabric was relaxed in a hot water bath at a temperature of 98 ° C for 30 minutes and then dried for 3 minutes at a temperature of 120 ⁰ C. The woven fabric was then washed 5 times with trichlorethylene to remove substantially all of the polystyrene components. A lubricant mainly containing a mineral oil was allowed to act on the dried fabric. Thereafter, the fabric was napped 15 times with a metal card netting machine having a plurality of 33-denier wires at a running speed of 30 m / min. The roughened fabric was then heat set for 30 seconds thermally at a temperature of 170 ⁰ C, using a thermofixing of the pin tenter type.

The thermally pre-set material was then ^{dyed at a temperature of 130 °} C. for 60 minutes in an aqueous dye bath containing 4% (based on the weight of the material) Duranol Blue G (CI. No. 63305 ₇ trademark of a suspension dye produced by ICI ), 0.2 ml / l acetic acid and 1 g / l of a dispersant with a major proportion of a condensation product of naphthalenesulfonic acid with formamide. The fabric was then soaped off and with an aqueous solution of a non-ionic detergent for 20 minutes at a temperature of 80 ⁰ C for 3 minutes dried at 120 ⁰ C.

Manufacture of a leather-like flat material The roughened and dyed woven fabric was made in the as shown below with a polyurethane completed. The fabric was immersed in a 3.6% by weight aqueous emulsion, which was a mixture the 2.3 wt .-% polyurethane (as a reaction product of methylenediphenyl diisocyanate, polyethylene glycol and

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1,4-butanediol, 1% by weight of polybutyl acrylate and 0.3% by weight of a polyester / polyether block copolymer (a block copolymer containing 40% by weight of a polyester of terephthalic acid and 1,4-butanediol and 60% by weight .-% polytetramethylene glycol contained). The fabric was then up to an emulsion pickup ratio of 70% - based on the weight of the substance based - expressed and at a temperature of 12O ⁰ C dried for 3 minutes, after which it was heat set at a temperature of 150 ⁰ C for 30 seconds to a leather-like to obtain flat material.

The leather-like flat material was once by means of a roller grinder with sandpaper (sieve underflow a sieve with a mesh size of 0.149 mm (100 mesh size) and then brushed or roughened.

The leather-like sheet obtained had a suede-like appearance, comfortable touch, excellent Suppleness and excellent pill resistance.

Example 2

A leather-like sheet was made in accordance with the method for applying a urethane prepolymer on the roughened and dyed fabric obtained according to Example 1.

Production of a urethane prepolymer A urethane prepolymer with isocyanate groups was produced by reacting a mixture at a temperature of up to 105 ^° C. for one hour in a nitrogen gas stream, the mixture consisting of the following components:
(1) 21 parts of a block-copolymerized polyether

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diols having a number average molecular weight of

2 400, which is produced by the conversion of a polypropylene glycol a number average molecular weight of about 1200 was obtained with ethylene oxide; (2) 56 parts of a polyester diol, obtained by reacting adipic acid, 1,6-hexanediol and neopentyl glycol in a molar ratio of 10: 7: 4; (3) 3 parts 1,6-hexanediol and (4) 20 parts of hexamethylene diisocyanate.

The content of isocyanate and oxyethylene groups in the urethane prepolymer obtained was 5.02 and 10.2, respectively Wt%.

After cooling to 4O ⁰ C, 20 parts of dioxane were added to the obtained urethane prepolymer, to form a solution of the prepolymer. The solution obtained was carefully mixed with 65 parts of an aqueous solution of sodium bisulfite having a concentration of 25% by weight at a temperature of 40 ^° C. for 30 minutes. 202 parts of water were then added to the reaction mixture to obtain an aqueous solution of the urethane prepolymer in a concentration of about 30% by weight.

Production of a Leather-Like Flat Material The roughened and dyed woven fabric, which was obtained according to Example 1, was immersed in an 8% strength by weight aqueous solution of the aforementioned urethane prepolymer and then up to an absorption ratio of 70%, based on the weight of the fabric, squeezed out. The squeezed fabric was at a temperature of 100 ⁰ C.

Dried for 3 minutes and ^{heat-treated for 30 seconds at 140 °} C. in order to obtain a leather-like flat material. The roughened surface of the leather-like flat material was then by means of a roller grinding

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machine with sandpaper (sieve underflow of a sieve with a mesh size of 0.149 mm (10 0 mesh size)) brushed.

The leather-like sheet material obtained was pleasant Grip, excellent recoil resilience, excellent wrinkle recovery and excellent writing effect and was thus similar to natural leather.

Example 3

Manufacture of a non-woven fabric

After the production of a fiber bundle using a bobbin frame, the fiber bundle consisting of undrawn hollow composite yarns obtained according to Experiment No. of Example 1, the fiber bundle was at a temperature of 60 ⁰ C in a water bath up to a draw ratio of 3.75 drawn, 5.9 crimps / cm (15 crimps / inch) using a stuffer box, and cut to a length of 38 mm to make chopped fibers.

The cut fibers were fed to a crosswrapper to form a web. Two of the webs of material were placed one on top of the other and needled in a vale density of 800 needles / cm ^{2 in} order to obtain a felt-like product weighing 200 g / m ² .

Manufacture of a leather-like sheet material. The felt-like product obtained - the non-woven fabric - Was in a 20 wt .-% dimethylformamide solution of the polyurethane (reaction product of methylenediphenyl diisocyanate , Polyethylene glycol and 1,4-butanediol). The fabric was then dried to a liquid uptake ratio of 100% based on the weight of the Fabric, squeezed out and then dipped in water

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to coagulate the polyurethane in the fabric. After drying, the fabric was in at room temperature for 3 hours Trichlorethylene dipped to add substantially all of the polystyrene components to the hollow composite fibers remove. The surface of the leather-like sheet material obtained was polished once by means of sandpaper.

The leather-like sheet obtained, which was obtained from a non-woven fabric, showed comfortable grip and excellent recoil elasticity and was like natural leather in this respect.

Example 4

Manufacture of the hollow composite fibers

Hollow Verbundfilamentewurden of poly-e-caproamide (nylon 6) an intrinsic viscosity of 1.10 (at 35 ⁰ C in m-cresol) as a polymer for the first molten polymer and polystyrene of a melt flow index of 30 as the polymer for the second molten polymer under Using the spinneret shown in FIG. 2 produced. The number of spinning openings was 20 and the number of small openings 19 which were present in the bottom of each guide hole 15 for the first molten polymer was 16.

The first and second molten polymers were fed to the respective guide holes at a feed rate of 10.8 g / min and 7.2 g / min, respectively. The hollow composite filaments were ^{spun at a temperature of 255 °} C. at a winding speed of 1000 m / min. The undrawn filaments obtained were drawn at a temperature of 110 ^° C. at a draw ratio of 3.0 in order to produce hollow composite filaments.

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ΊΟ

hold, each having a titre of 2.6 and a void ratio of 6.5%. Each polyamide and polystyrene component had a titre of 0.10 and 0.06, respectively Denier. The physical properties of the hollow composite filaments obtained are shown in Table 2, Experiment No. 6 shown.

On the other hand, two kinds of hollow composite filaments corresponding to the same one have been described above Method prepared with the exception that the feed rate for the first and second molten polymer 13.5 g / min and 4.5 g / min for one type and the feed rate of the first and the second molten polymer were 8.1 g / min and 9.9 g / min for the other, respectively. The former hollow composite filament had a denier of 22.6 and a void ratio of 8.5%. Any polyamide and polystyrene component the former was 0.13 and 0.04 denier, respectively. The latter hollow composite filament had a linear density of 2.6 denier and a void ratio of 3.0%. Any polyamide and polystyrene component the latter was 0.08 and 0.09 denier, respectively. The physical properties of the obtained hollow composite filaments are shown in Table 2, Experiment Nos. 7 (the former) and 8 (the latter). There the ratio of the feed rate of the polyamide to that of the polystyrene is 75:25 in Experiment No. 7 and 45:55 in Run No. 8, which was outside the preferred scope of the present invention the hollow composite fibers have poor processability in melt-spinning and drawing.

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Tabel

Total number of
Components Ratio of
Feed speed
the first
Polymer too
that of the second
Polymer Processing
ability at
Melt spin
nen and ver
stretch
* 2 Separating power
(%)
* 3 Experiment No. 6 32 60:40 outstanding 100 Experiment No. 7 32 75:25 bad 100 Experiment No. 8 32 45:55 bad 100

Making a knitted fabric

A tricot with a weight of 250 g / m ² was produced by using a simple twisted filament yarn (150 D / m with S twist) of hollow composite filaments (600 denier / 260 filaments) as the yarn for the front side according to Experiment No. 6, and a filament yarn (150 denier / 48 filaments) made of nylon 6 was used as the back yarn.

The tricot was relaxed in a hot water bath at a temperature of 80 ^° C. for 20 minutes and then dried ^{at a temperature of 120 ° C. for 3 minutes.} The tricot was then washed 5 times with trichlorethylene to remove substantially all of the polystyrene components of the hollow composite fibers. The tricot was then kept at a temperature of 100 ^° C. for 40 minutes for dyeing in an aqueous dye bath containing 4% (based on the weight of the tricot) Suminol Milling Brilliant Red B (CI. No. 18134, trademark of Sumitomo Chemical Co. produced acid dye) and 2 ml / 1 acetic acid. The tricot was then washed with an aqueous solution of a non-ionic cleaning agent for 20 minutes at a temperature of 70 ^° C. and dried at a temperature of 120 ^° C. for 3 minutes.

Production of a leather-like flat material The dyed tricot was in a 2.4 wt .-% - aqueous solution of a mixture of 1.2 wt .-% of an ethylene / vinyl acetate copolymer (a copolymer of equivalent moles of each component), 0 , 9 wt .-% polybutyl acrylate and 0.3 wt .-% of a polyester / polyether block copolymer, as used in Example 1, dipped and then squeezed out to an emulsion uptake ratio of 70%, based on the weight of the tricot dried for 3 minutes at a temperature of 120 ⁰ C.

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Then followed a Hitzeabbinden for 30 Seloinden at a temperature of 150 ⁰ C. The leather-like sheet material obtained was washed once with a roll grinding machine with sandpaper (screen underflow of a sieve having a mesh of 0.149 mm (100 mesh size)) polished, whereafter a brush followed.

The leather-like flat material had a pleasant feel and excellent flexibility.

909810/0716

Claims (9)

Henkel, Kern, Feiler & Hänzel Palentanwälte TEIJIN LIMITED Möhlstrasse D-8000 Munich Osaka, Japan Te!.: 089 / 982085-87 Telex: 0529802 hnkld Telegrams: ellipsoid Dr.F / da 11 AUG. 1978 Claims .] Process for the production of leather-like flat materials, characterized in that a) hollow composite fibers are produced, each of 16 to 96 alternately arranged components composed of polyester or polyamide and polystyrene, which are reciprocal - Side by side - adhere to one another and enclose a cavity and which are used for training of a tubular body extending along the longitudinal axis of the fiber, the hollow Composite fiber has a denier of 1 to 20 and each component has a denier of 0.01 to 0.5, b) a fabric using the hollow thus formed Composite fibers are produced, c) the components made of polystyrene from the hollow composite fibers by means of a suitable solvent removed and d) an elastic polymer is applied to the fabric. - 2 - 909810/0716 ORIGINAL INSPECTED 283529a 2. The method according to claim.1, characterized in that the ratio of the total weight the polyester or polyamide components to the polystyrene components in the hollow composite fiber is in the range of 50:50 to 70:30. 3. The method according to claims 1 or 2, characterized in that the cavity ratio of the hollow Veround fiber is between 1 and 30% by volume. 4. The method according to any one of claims 1 to 3, characterized in that the polyester is polyethylene terephthalate is. 5. The method according to any one of claims 1 to 4, characterized in that the polyamide is nylon 6 or nylon 66. 6. The method according to any one of claims 1 to 5, characterized in that the fabric is a woven Fabric is. 7. The method according to any one of claims 1 to 5, characterized in that the fabric is a knitted Fabric is. 8. The method according to any one of claims 1 to 5, characterized in that the fabric is a non-woven Fabric is. 9. Ve ι years according to one of claims 1 to 8, characterized in that an elastic polymer is applied to the fabric by an aqueous solution or emulsion of a hydroscopic 9098 10/0716 pischen and heat-reactive urethane prepolymer with isocyanate groups blocked by bisulfites is applied to the fabric and then the coated fabric is ^{heated at a temperature of 100 to 180 0} C to form the polyurethane (in or on the fabric). 10. The method according to any one of claims 1 to 9, characterized It indicates that the manufacture of a fabric using the hollow composite fibers Applying an elastic polymer and then removing the components from polystyrene with a Solvents from the hollow composite fibers of the fabric follow. 9 09810/0716