CS196447B2 - Leather simulating fibrous web - Google Patents

Abstract

1362806 Non-woven fabrics KALLE AG 28 Oct 1971 [30 Oct 1970 (2)] 50201/71 Heading D1R The fibres of a needled non-woven fabric are coated with a wash-proof synthetic material and the coated fibres are in turn surrounded by an organic elastic polymeric matrix, there being no adhesion between the matrix and the synthetic material. The matrix comprises 10-80% by weight of the product, which has a density of 0.1 to 0.28 gn/cm<SP>3</SP>, a tensile strength of at least 0.01 kg/mm<SP>2</SP>, a tear propagation resistance of at least 7 kg/mm and a tensile stress of not more than 0.03 kg/mm<SP>2</SP> at 10% elongation. The fibres, are staple length polyethylene terephthalate, polyamide, polypropylene polyacrylonitrile or mixtures thereof, which fibres shrink longitudinally on heating, optionally mixed with up to 50% of wool, hair, cotton, hemp, jute sisal or flax fibres, are in the form of a matted needled fleece. The synthetic coating material comprises 2 to 20% by weight of the product, and may be an ethylene urea, a fatty amine, paraffin wax, etherified fat modified synthetic resin, cross-linkable or non cross-linkable polymeric siloxane compounds such as dimethylpolysiloxane and hydrogen-methylpolysiloxane, or crosslinkable polymers having perfluorated aliphatic side chains of preferably 6 to 14 carbon atoms, or a melamine/formaldehyde or urea formaldehyde precondensate. The coating may be applied by immersing the fleece in an aqueous solution or dispersion and then heating to remove the liquid and fix the coating upon the fibres. Alternatively the coating may be applied in a halogenated hydrocarbon solution together with a phenol which swells the fibres. The fleece is then washed with solvent to remove the phenol and heated. The matrix is then applied either as an aqueous dispersion which is then coagulated to 38-45‹C or in a water-miscible non fibre swelling organic solvent, coagulation then being accomplished by addition of water. Heating at 100-180‹C drys the product and deswells the fibres if they have been swollen by a phenol. The matrix may be natural or synthetic rubber, polyacrylate, butadiene-acrylonitrile-methacrylic acid copolymer or polyurethane.

Description

The invention relates to a fibrous web having leather-like properties. comprising a polymeric elastic strengthening agent. The invention also relates to a method for producing said fibrous web.

The nonwoven prepared by the process of the invention is used as an intermediate. for the preparation of a skin substitute material, which is obtained by applying a microporous layer of plastic material to the web, in particular by applying polyurethane.

Composite webs are known in which the fibers are interrelated. glue. While the webs thus bonded have - in demand - high tear strength, they are stiffly rigid - and cannot. therefore, be used for purposes where soft touch is required and / or - textile drapiness and flexibility of the skin, • Other fibrous webs. contain k. elimination of said drawbacks as binders by elastomers. Although these webs are elastic, they have the disadvantage of rubbery character, so that they are not suitable for making leatherette.

None. The fleece does not have a textile drapiness, soft feel and flexibility similar to natural leather.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fibrous web which does not have the drawbacks of chemically bonded fibrous webs and which, by virtue of its physical properties, merges 196447. '. 2 '' · π ·· .;

Flexibility · Suitable for - further - processing into actively - breathable multi-layer materials - suitable for footwear - uppers, for clothing and for upholstery - and - abrasive purposes.

The invention is. it also relates to a method of making such webs. ?

The object of the invention. thus, it is a fibrous web with similar properties. leather - based synthetic. fibers,. especially based. mixtures of polyamide. - - and - polyester fibers in a ratio of 1: 1 or - based on - heat - shrinkable fibers,. organic reinforcement. material marked by:. The composition comprises a polymeric-elastic reinforcing material of 10 to 80. % by weight, based on - the total - weight of the raw nonwoven fabric. 0.1. to. 0.28 g / cm ^{3 of} fiber thickness 0.8 to .3 - dtex,. a tensile strength of at least 0.09 MPa, a tear strength of at least 7 kg / nm; in a tensile test at 10% elongation at a tensile stress of 0.27 MPa, wherein. the fiber surface is a synthetic material coating of 2. up to 20% - by weight of the nonwoven web, which has - in comparison to the fiber surface - ad-nice. fortress. anti-scrubbing, in contrast to it - has no adhesion to the - elastic polymeric reinforcement. The non-woven material bordering the coating penetrates the nonwoven while surrounding the nonwoven fibers.

The fleece according to the invention is used for the production of actively breathable sheet-like structures with leather-like properties for apparel, shoemaking, upholstery or bagging purposes. The physical characteristics of the web according to the invention give rise to special properties of the web. The physical characteristics of the fleece are given by its structure. The web is characterized in that there is a coating on the fiber surface that is adhering and non-washable, while bordering the coating, the web penetrating and yet the fibers surrounding the organic, elastic polymeric reinforcing materials have substantially no adhesion to the web.

The method of preparing a web according to the invention is characterized in that the web is treated with a solution or dispersion of a synthetic non-washable coating composition, the excess treatment bath is removed and the impregnated web is heat treated for 10 seconds to 10 minutes at 100 to 180 ° C. after which the impregnated web is treated with a solution or dispersion of the polymeric reinforcing material, the polymer precipitates and the web is dried for 2 to 30 minutes at a temperature of 100 to 180 ° C.

According to the advantageous. process variants are treated with impregnating liquid · consisting of liquid · halogenated hydrocarbons, benzene compounds with free phenolic hydroxyl group · as a fiber swelling agent and a coating composition of higher fatty acid esters and polyhydric aliphatic or polyhydric aliphatic alcohols carboxyl groups. acids and long-chain aliphatic alcohols, the impregnating liquid containing a greater amount of chemical coating composition than the free benzene compounds. the phenolic hydroxyl group as swelling agents, or both are present in the same amount and then washed in the solvent from the web, the impregnating liquid is removed and removed for 30 seconds to 10 minutes. nonwoven / heat treated at 100. Up to 180 ° C, after which the impregnated web is treated with a liquid solution or dispersion of the polymeric elastic reinforcing agent, the polymeric reinforcing agent is precipitated in a manner known per se and the web. then dried at a temperature of 100 to 180 ° C. for .2. up to 30 minutes.

This process variant can be modified particularly advantageously. by letting it act. The web is an impregnating liquid in which the amount of swelling agent is greater than the amount of the coating composition. then rinsing the impregnating liquid and drying at room temperature and then proceeding as described above.

This particularly advantageous process variant. is · however. can be further modified such that, after impregnation and removal of excess impregnating liquid, the web is thermally treated at 100 to 180 ° C for 30 seconds to 10 minutes and then the process is terminated as described above.

The starting webs for the process according to the invention are those made from swirled synthetic fibers. They are either purely synthetic fibers, or half are native fibers, or consist of a predominant proportion of synthetic fibers and a small proportion of native fibers. These webs are preferably densified by needling, preferably 200 to 600 punctures / cm ² . The synthetic fibers for such webs are polyacrylonitrile fibers, polyamide fibers, polyester fibers, in particular said fibers along the length of heat shrinkage. Polyester shrinkable fibers are preferred.

Suitable webs of mixed fibers are webs containing 75 to 50% by weight of polyester fibers and 25 to 50% by weight of other synthetic fibers, such as polyamide, polyacrylonitrile, polypropylene fibers. A 1: 1 blend ratio is preferred with respect to polyester and other chemical fibers. It is also possible to use nonwovens which comprise said proportion of polyester fibers and native fibers. Of the native fibers, wool and the like animal hair, as well as cotton, hemp, jute, sisal or flax are suitable.

Suitable synthetic fibers have a thickness of 0.8 to 3.5 dtex. particularly 1.2 to 1.7 dtex.

The raw nonwoven has a density of 0.10 to 0.20 g / cm 3, preferably 0.14 to 0.2 g / cm 3. By raw web is meant a needled web which is free of both coating and reinforcing means. The needled webs have a basis weight of 50 to 400 g / cm ² , preferably 100 to 250 g / cm 2 ^{: They} are suitable as reinforcing material. elastic polymers such as. synthetic rubber; polyacrylates, in particular elastomers, especially mixed polymers of butadiene, acrylonitrile and methacrylic acid and polyurethane. · Natural rubber is also suitable as a firming agent.

By elastic polymers is meant polymers having a rubber-like plastic-elastic reinforcing behavior at a temperature of -20 to -50 ° C. Elastomers refer to the polymers disclosed in &quot; Textbook of Polymer Chemistry &quot;, New York, 1957, p. 154 (Bielmeyi, Jr.).

The reinforcing agent is introduced into the web in the form of a liquid solution or dispersion of the elastic polymer, for example by dipping the web in liquid. Suitable solvents or dispersants for the polymeric reinforcing material are solely solvents which neither swell nor dissolve the web.

Suitable solvents for preparing a liquid solution of polymeric elastic reinforcing material are: dimethylformamide, dimethylsulfoxide as well as tetrahydrofuran for polyurethane. For synthetic rubber or acrylate dispersions it is dispersible. The reagents used water.

The solution or dispersion of the high molecular weight strengthening material has a dry weight of 10 to 70% by weight.

The density of the web is determined according to the IUP 5 method. ·

The web according to the invention has a proportion of reinforcing material of 10 to 80% by weight, based on the total weight of the web, in particular 30 to 65% by weight. Fleece. containing elastic. The reinforcing material according to the invention has a basis weight of 60 to 600 g / m ² , in particular 200 to 600 g / m ² .

The liquid 'containing the synthetic coating composition' which is 'treated' in the first step on the web is 'hereinafter' referred to as 'impregnation'. liquid.

Synthetic coating means chemical substances capable of forming a coating on the fiber surface which, after sufficient heat treatment of the coated fibers, has a high adhesion to the fibers and is washable.

These coatings are suitable for solutions or dispersions whose solvents or dispersants do not swell the nonwoven fibers; an ethylene urea of the formula h-nh-c-n. |

O, i. . . .

where

R is an aliphatic chain of 14 to 22 hydrocarbon atoms, fatty amines having a carbon chain of 16 to 18 carbon atoms, paraffins, etherified aliphatic modified artificial resins having a side chain of between 12 and 18 carbon atoms, crosslinkable and non-crosslinkable silicones such as for example dimethylpolysiloxane and hydrogenmethylpolysiloxane, or pro. a 'textile finish suitable' crosslinkable polymers having 'perfluorinated aliphatic side' chains '(for example Scotchgarn (R) protected' trademark of Minnesota Mining and Manufacturing Co., USA). Suitable crosslinkable polymers have a perfluorinated side chain having a carbon number in the range of from 6 to 14, in particular from 8 to 12 carbon atoms.

For example, in a 'crosslinkable polymer containing carboxyl groups, the perfluorinated crosslinkable aliphatic' side 'chain may be linked via a sulfonamide group to the carboxyl group of the polymer;

A fleece whose fibers are treated with said coating means is referred to as an "impregnate".

The web comprises 2 to 20% by weight, in particular 5 to 15% by weight, based on the impregnated web, of chemical. an washable coating composition as defined above capable of forming a coating associated with the surface of the fiber.

As a basic property of the coating composition, it is noted that there is no or substantially no physical bonding force between the adjacent surfaces of the coating and the surface of the reinforcing agent, i.e. the adhesion between said surfaces is so low that it is under external mechanical force on the web, for example when bending or drawing the web, 'possible sliding relative movement of the surfaces against one another'.

According to one variant of the process, the coating composition is introduced into the web in the form of a liquid solution or dispersion by impregnating the web with liquid, for example, and then stripping off the solvent or dispersing agent, e.g. A bath ratio of 1:10 to 1 '50 is preferred, in particular 1:10 to 1:30. For the preparation of a solution containing the coating composition, liquids which do not dissolve the fleece are suitable. nor swell, for example water. As dispersants for the preparation of a liquid dispersion. of the coating composition are suitable non-solvent-borne liquids, such as water.

The proportion of the coating composition in the impregnating liquid used in the first stage of the process is 2 to 30, in particular 6 to 12% by weight, based on the total weight of the liquid. '.' '

In carrying out the process according to another preferred variant, the impregnating liquid consists of liquid halogenated aliphatic hydrocarbons, benzene compounds with a free phenolic hydroxyl group, as well as higher fatty acids and polyhydric aliphatic alcohols or polyhydric aliphatic carboxylic acids and long-chain aliphatic alcohols. ''

Liquid. hydrocarbons, preferably 'chlorinated' aliphatic 'hydrocarbons, may be saturated or unsaturated. Suitable saturated chlorinated aliphatic hydrocarbons are 1,1,1-trioiloretane and carbon tetrachloride. Particularly suitable are liquid chlorinated aliphatic unsaturated hydrocarbons, in particular trichlorethylene and especially perchlorethylene. Mixtures of the above hydrocarbons may also be used.

Said liquid halogenated hydrocarbons are also used as solvents for flushing the web. .

Of 'benzene hydrocarbons' with a 'free' phenolic 'hydroxyl'. particularly suitable are p-cresol, o-cresol and peroxybenzoic acid, especially salicylic acid methyl ester and especially phenol. Mixtures of the solvents mentioned, for example phenol, in admixture with methyl salicyl ester, may also be used.

The free phenolic hydroxyl benzene compounds contained in the impregnating liquid act as swollen agents. 7.

fiber fleece. .

The impregnating liquid contains as one of its constituents a chemical agent in the form of esters capable of forming coatings on the fibers. This composition consists either of higher fatty acids and of polyhydric aliphatic alcohols, wherein:. the fatty acid ester component is preferably saturated but may also be unsaturated or also from polyhydric aliphatic carboxylic acids and monovalent long chain aliphatic alcohols. In this case, the aliphatic alcohols are preferably saturated, but may also be unsaturated. They can also be. mixtures of the esters mentioned. ...

According to ·· convenient. process variants are particularly suitable for the following chemical substances for coating the fibers: monostearyl ester, citric acid, glycol dioleate, especially glycol monooleate, glycerin stearate, especially glycerin monostearate, erythritipipmitmitate; especially erythritmonopalmiate, sorbitmonostearate and sorbitol dearate. Of these suitable coating materials, glycerin monostearate is particularly suitable. · .-, ···.

The impregnating liquid according to a preferred variant of the process comprises either a swelling agent, i.e. a benzene compound with free form. phenol hydroxyl group in excess or in excess of the chemical coating material for the fibers in the form of the esters mentioned, or both components in the impregnating liquid are contained in the same parts.

If the impregnating liquid contains more chemical coating composition than the swelling agent, or if the individual components are contained in the impregnating liquid in equal parts, the web is exposed after the impregnation liquid has been removed. bypassing · excess impregnating liquid by flushing for 30 seconds · to · 10 minutes · exposure to temperatures of 100 to 180 ° C.

In a preferred process variant in which the impregnating liquid is used with a predominant amount of swelling agent for the fibers over the coating composition, particularly advantageous results are obtained, in view of the easy displaceability of the fibers, over the elastic strengthening agent which surrounds the fiber. however, the industrial process is technically more demanding than variants in which impregnating liquids are used in excess or in the same amount as swelling agents. Also this variant leads to chemically bonded webs which, by virtue of the very good fiber-binder separation, are very suitable starting materials for the manufacture of leatherette, having regard to the said advantageous properties, then take precedence over the known webs. '.

The unreasonable anchoring of the coating composition on the webs of fibers is achieved by using an impregnating liquid in which the chemical coating composition in the form of the ester component exceeds the amount of the swelling agent in the form of a benzene compound with free phenolic hydroxyl group The coating composition is contained in the same amount to impregnate the web and heat treat for 30 seconds to 10 minutes at a temperature of 100 to 180 ° C.

The fiber-binder separation effect can be substantially increased by the use of: impregnating liquids in which the swelling agent predominates the coating composition, with the final swelling of the nonwoven fibers occurring only after the binder has been introduced into the nonwoven during drying. at, temperature · · 100. . to 180 ° C during 2 to 30 minutes.

De-swirling will cause a reduction. the cross-section of the swollen fibers. The coating composition on the surface of the fibers and after the processing of the binder reduced cross-section of the fibers results in a particularly good displaceability between the fiber and the elastic reinforcement by the means surrounding the fibers. _ '. · ...:

The coating composition is inextricably / bonded to the fiber surface if. --Hide grip between. the fiber surface and the coating composition is so large that there is no or substantially no release of the coating composition from the fiber surface when the mechanical wash at 60 ° C is repeated several times at 60 ° C. . ,

Suitable work: the liquid is 5 g / l soap and 2 g / l calcined soda; The wash time is 30 minutes, bath temperature · 60 ° C and bath ratio 1: 50. . :

The polymeric reinforcing material, when introduced into the web, for example by precipitation of the polymer in a polymer solution or dispersion in a manner known per se, is not present in the form of a large number of discrete polymer particles in the web but forms continuous shapes. which fill more or less hollow spaces of the web, depending on the amount of reinforcing agent used. This reinforcing material envelops all or part of the fleece fibers. .

According to the invention, it is essential that there is a coating means between the surface of the webs of the web and the surface of the fiber-reinforcing means. which, on the one hand, is inextricably bonded to the surface of the fiber, on the other hand, is free or substantially free of any adhesion of the surface of the polymeric reinforcing agent to the surface of the coating composition bordering it, thereby permitting parallel displacement of the two surfaces. In the known nonwoven bonding through the polymeric binders, the binder penetrates in a similar manner to the nonwoven as in the present invention, but in the known nonwoven, the adhesion between the fiber surface and the bordering polymeric binder surface is so high that it cannot slide. fibers against the 'surface' of the polymeric binder that surrounds them. However, this possibility is given to the nonwoven according to the invention based on its. special buildings. This particular construction affects particularly good physical values and advantageous properties for its use. .

The fleece is prepared as follows:

The spunbonded polyester fiber web is treated with a liquid solution or dispersion of the coating composition, for example by soaking in a bath consisting of said liquid, and then being drained of excess liquid, for example by squeezing. A bath ratio of 1: 20 is particularly preferred for impregnation. Then the web is heat treated at a temperature of 100 to 180 ° C. 20 minutes.

During this heat treatment, the remainder of the dispersing agent or solvent is driven off, and the coating agent is anchored irrevocably on the fiber surface. The heat treatment of the web is carried out, for example, in a manner known per se in a tension frame dryer.

Then · se. The impregnating agent imparts in a manner known per se a liquid which comprises a highly polymeric elastic reinforcing agent or in dispersed form. For example, a soaking bath is used. The impregnating bath comprises 20 to 70% by weight, in particular 30 to 50% by weight, of a strengthening agent, based on the total weight of the liquid. Then, the polymeric reinforcing agent is precipitated in the web. The precipitation can be carried out in a manner known per se, for example by applying a precipitation liquid to the impregnated web, wherein the precipitation liquid is miscible with a solvent or dispersant, but the polymeric reinforcing agent does not dissolve therein.

Water is suitable as a liquid precipitant, especially when the reinforcing agent is dissolved in a water-miscible organic solvent. When aqueous dispersions of the reinforcing material are used, the polymeric reinforcing material is precipitated by coagulation in a manner known per se.

After the polymeric reinforcing material has precipitated in the web, the solvent or polymer dispersant is largely removed from the web, for example by heat treatment of the web at 100 to 180 ° C until it is sufficiently dry . The drying is carried out, for example, in an oven or in a dryer with a tension frame.

Preferably, the web according to the invention is prepared as follows:

The spunbonded polyester fiber web is treated with an impregnating liquid containing a chemical coating agent in the form of said esters in excess of a swelling agent which is a benzene compound with a free hydroxyl group or in which both components are contained in the same an amount, for example in a bath, containing said impregnating liquid; it is then removed from the bath · and the excess · impregnating liquid · is removed by sufficiently intensive irrigation. A 1: 20 bath ratio is preferred for impregnation. The nonwoven is impregnated and rinsed. heats · processes · 10 · seconds. Up to 10 minutes at 100 to 180 ° C. . //

In the course of this heat treatment, the volatile components of the impregnating liquid are removed. Still remain between the fibers of the web and the vein. The fibers, on the one hand,. with an 'thermal treatment' it is an inextricably anchored coating material on the fiber surface. ,

The polymer-containing fluid is then introduced into the impregnate in a manner known per se. The elastic reinforcing agent is dissolved or dispersed. This is possible, for example, in a soaking bath. .

The impregnating bath contains from 20 to 70% by weight, in particular from 30 to 50% by weight, of solids. % by weight of the liquid. Then, the polymeric reinforcing agent precipitates in the web, for example in a manner known per se, by the action of a liquid on the impregnated web which is miscible with a solvent or dispersant but does not dissolve the polymeric reinforcing agent.

Water is suitable as a liquid solvent, especially when the strengthening agent is dissolved in an organic solvent which is miscible with water. When an aqueous dispersion of a reinforcing material is used, the polymeric reinforcing agent is precipitated by coagulation in a manner known per se, for example at a temperature of 38 to 45 ° C.

After the polymeric reinforcing agent has precipitated in the web, the solvent or polymer dispersant is largely removed from the web, for example by heat treatment of the web for 2 to 30 minutes at a temperature of 100 to 180 ° C, with the web sufficiently , dries. The heat treatment is possible in an oven or in a dryer with a tensioning frame.

A particularly preferred variant of the method of preparing the web is based on the use of an impregnating liquid in which the swelling agent is in excess of the coating composition, after impregnation, the web is dehydrated as described above and dried in a drying process. the elastic reinforcing material is applied as described above.

• After precipitation · · · elastic '· rigidifying' polymeric fixing means, heat treating the web '· for 2-30 minutes treatment at 100 to 180 ^·: C. This treatment is conveniently carried out in an oven or dryer with a tensioning frame into which hot air is introduced. With the aforementioned composition of the treatment bath, there is a swelling which is associated with a reduction in cross-section and leakage of solvent and swelling agent from the fiber, thereby causing separation between the fiber surface and the polymerization of the strengthening agent. means. At the same time, it will be anchored inextricably. coating means for the surface of the fiber. · Oběma processes to create the possibility obzvláště výhod198447 ¹¹ Joint · posouvání; the fibers against the elastic reinforcing material that surrounds the fiber.

'That. · The variant can still be changed. So that. after impregnation. The web and the removal of excess impregnating liquid are heat treated by the web at a temperature of 100 ° C to 180 ° C for 10 seconds. up to 10 minutes and then impregnated in the manner described above.

In the following examples, parts and percentages are by weight unless otherwise indicated. . . . ...

Example 1 '

Spun fiber fleece, 5Qi. % of heat - shrinkable polyester. . 50 ·% polyamide, · density · 0.14 g / cm 3 · [length of staple 30 · mm, fiber thickness 1.3: · dtex], · impregnated in a bath q containing 7Q g 22% per liter of water · Water,. octadecylethylenemachine dispersion (Primenm · FD, Farbwerke Hoechst AG). bath is · 1:20. The fleece is then squeezed, dried. · Se · at ·. 110C in dryer with tensioning frame. 10 minutes and then. is processed for 2 minutes at. 140 ° C in a dryer with a tensioning frame, crosslinking the coating composition. surface. fibers

The impregnated web is impregnated in a known manner with an aqueous 50% dispersion of a mixed polymer of butadiene, acrylonitrile and methacrylic acid (Berbunan N · 3405 M, Farbenfabriken Bayer) and is squeezed and then coagulated by heat in a known manner and dried . in the oven · 20. .mnut at. 150. · ° C. · The fleece has a tear strength of 7 kg / mm [measured according to IUB · 8] and is. flowing ·. slippery elastomers can be observed when torn. The fiber fraction of elastomers. Yippee· . 58 ··% · Fleece is suitable as a substrate for leatherette.

Example · 2 ‘

Fleece »fall, example! 1, · · se. ·. in the desert . a bath consisting of 8% aqueous; dimethylpolvsiloxane dispersions [Primenit SV, Farbwerke

Hoechst. AG j · and squeeze. Dry with warm air at. 120 ° C for · time; · 7 minutes and processed, in a dryer; with tensioning frame '30 seconds with air at · Temperature. 150 ° C. The fleece has a soft feel and is water repellent.

At the following impregnation, 50% is impregnated by an aqueous dispersion of the mixed. butadiene polymer; acrylonitrile; and. methacrylic acid · [Perbunan N · 340.5 · Mj, · containing

2.5%: titanium dioxide and wrinkles .. Fleece. then warms up. in a dryer with a tensioning frame where precipitation occurs. polymer. in fleece '. It gets very flexible. fleece. tear strengths of 8 · and 10 · kg / mm (according to IUP). Ready. The web is preferably suitable as a carrier web for. preparation of artificial leather,. which; . is comparable in mechanical properties to the training box. . Content of elastomers ·· fleece. is about 62 ·%, · · based on · total weight. fleece. '

Example 3

The fibrous web of Example 1 is soaked in a liquid containing a liter of water 70; g of detectable hydrogen-methyl-polysiloxane [e.g., Arkophah. SN · Farbenwerke Hoechst AG) and 7 · zirconoxvchlori.du as. catalyst ([ratio 1: 20]) and squeezed, dried at 120 ° C for 8 minutes and swept. is treated for 3 minutes at 150 ° C in a tensioning dryer. framed. In this treatment, crosslinking of the methylpolysiloxane on the fiber surface occurs. The fleece is soaked in a known manner: in 50% aqueous dispersions. butadiene-acrylonitrile-methacrylic acid-methacrylate [Perbunan N.N. 3405 M by Farbenfabriken. Bayerj,. which it contains

2.5 part. titanium dioxide, calculated on the solids content,. . and · coagulates. with heat at 38 to 40 ° C ·. In doing so, it almost gets. á · full · separation, elastomers ·, tear strength of the web 9 kg / mm. pode. IUP 8 and high fleece flexibility ...

These 'fleeces are. a suitable base material for the preparation of a leatherette of the bovine box type. .

. · Content . . The elastomers in the web are 61%. the elongation characteristic is similar. as - . in the case of a natural beef box.

Ex. k 1 a d · 4a ·

The tufted web of Example 1 is soaked at 30%. aqueous dispersions of the crosslinkable polymer with perfluorinated side. aliphatic. &.t ^: ^ <^ l [Scotchard. Te?) ·, For example, Cteophobol FC 218. fy. Ehemlsche. Fabrik. Pferse J. Ratio · bath L20 .. '

The soaked web is then. squeeze and dry · 120 minutes at 120 ° C.

Then it is exposed in a dryer with a tensioning frame. 2; minutes temperature · 15 ° C,. while it occurs. cross-linking. polymer.

it is expedient · to process the web before the soaking. with a dilute agent. wetting solution [e.g. Marlon · A by Chemische Werke H ^ hsJ ,. strongly squeeze and · impregnated · in the wet state with 50% · aqueous dispersion of mixed polymerate. butacliee.— —acrylonitrile — methacrylic acid. [Perbunan N 3405 M-Dispersion ,. which it contains

2.5 · parts of oxide. titanium · calculated solids content yr ^]) ^first In this way, a completely uniform uniform impregnation of the web is possible.

·. By repelling the water and oil of the treated webs, a fiber separation is achieved with tear strength values of 8 and 10 kg / mm / mm respectively. IUP & Fleece are · suitable carrier materials for · further · processing into a flexible material · replacing · leather that resembles a thicker beef. boxing.

136447

14

Pjříkřa®, 4h: '

Especially uniform. The surface of the fiber by the coating means is achieved by using a crosslinkable polymer with perfluorinated aliphatic lateral. Groups under the present. use, carrier polymer based on melamine formaldehyde precondensate. (e.g., Arkofix NM of Farbenwerke Hoechst AG).

The fibrous web of Example 1 is impregnated in a bath conditioner containing 100 g of Arkofix NM, 10 g of magnesium chloride (MgCl2) and 30 g of crosslinkable polymer with perfluorinated per liter of water. aliphatic side groups (e.g. QleogAtibM. · FC 218 :). Then it is: · crushed and dried, it is: 3 minutes at 12Ц1% ... Then it is exposed: 2 minutes in a drier with a tensioning frame at 150%, · condenses the precondensate and crosslinks with a cross-linking polymer containing aliphatic perfluorinated side chains.

Example 5.

The fibrous web of Example 1 is impregnated in a liquid containing 80 µg of ureaolormaldehyde precondensate (Arkofix NHL from Farbenfabriken, Hoechst AG) per liter of water, 30 g of a cross-linked polymer-based product with perforated side aliphatic chains (e.g. Oleaphobol P 68). by Chem; Fabrik Fersee) as well as 8 g of ammonium chloride;

After impregnation, the fleece is squeezed. dried for 5 minutes at 120 ° C and exposed to 150% for 2 minutes in a tension frame dryer, condensing the urea-formaldehyde precondensate and crosslinking with a crosslinkable polymer with perforated side chains. The fleece has water-repellent and oil-repellent properties. Therefore, the fleece (impregnate) is expedient. wetting with a 50% aqueous butadiene-acrylonitrile-methacrylic acid polymer dispersion (P-erbunan NT-Dispersion by Fanbannfabricate Bayer) containing 2% of a wetting solution (e.g. 5 why titanium dioxide as filler, based on solid material, squeeze, coagulate at 40%, wash and at 150% ^: dry in a stretcher dryer. the mechanical properties correspond to the veal box.

The web has a tear strength of 8-9 kg / mm. The elastomer content of the web is 61%. based on the total weight of the web,

Example 6.

Fleece. ' Example 1 is treated as described in Example 3 and then impregnated with elastomeric dispersion and coagulated etc., but impregnated with a polyurethane solution (Caprolan, LemfSrder Kujntstoff GmbH), coagulated with water, etc. Thus, in this example, the defective dispersion treatment is performed and bound with a polyurethane solution.

Example 7 • Woven fleece of .50% polyester heat-shrinkable fibers and .5% polyamide fibers (staple length 30 mm, ti.tr 1, .3 dtex) ® density 0.10 g / cm 3 with dipped defective A dispersion containing 80 g / l of dimethyl polysicane (Primenlt SW from Farbenwerke HoecfKst. AG), bath ratio. 1:30, crushed, dried for 5 minutes at 120 ° C. and then processed. 2 minutes at 150 ° C in a stretcher frame dryer. '

Subsequently, the nonwoven is soaked with an aqueous 5.0% dispersion of a mixed polymer butadiene-acnylnitrile methacrylic acid (Perbuirani N '3405 M (Dispersion fy), Farbenfabriken,

Bayer, Leverkusen) having a solids content of 50% and an elastomer is thermally coagulated in a known manner and dried at 150 ° C.

A very flexible fleece with a binder content of 65%, which is high, is obtained. Flexibility and tear strength 7 kg / mm (according to 1UP ftj. ·. ···. ·.

Example 1 and d 8 '.

A spunbond web of 50% heat-shrinkable polyester fiber and 50% polyamide fiber (staple length 30 mm, titer 1.3 dtex) with a density of 0.26 g / cm 3 is dipped with an aqueous dispersion. containing 80 g / l of hydrogen methylpolysiloxane (Arkophob SN from Farbenwerke Hoechst AG) and 8 g / l of zirconium chloride catalyst (bath ratio Ί: 30), squeezed and dried at 120 ° C for 5 minutes. .on the fleece. for 3 minutes at 150 ° C. (warm air flow). This web with a known dispersion soaks an aqueous dispersion of butadiene-acrylonitrile-methacrylic acid mixed polymerate (Perbunan N 3405 N, solids content 50%) and the elastomer is thermally coagulated. :.

Complete separation is achieved, the fiber is elastomeric and the tear strength is 15 kg / mm (according to IUP '6). .

Binder content 54%. The fleece is suitable as a substrate for a synthetic veal box.

Example 9

Swirl fleece of 50% heat-shrinkable polyester fibers and 50% polyamide fibers, with a staple length of 30 mm and a tester of 1.3 dtex, with a basis weight of 2: 5.0 g /. / m2 and a fiber density of 0,14 g / cm ⁵ ; The needle punched 400 punctures / cm @ ² are processed in a tank containing an impregnating liquid containing per g of perhionethylene 30 g of phenol and 50 g of giyceninmonium stearate for 10 minutes at room temperature. Bath ratio. is 1: 30:

The nonwoven is then removed from the bath and rinsed with pure perchlorethylene in another bath, removed from the bath and then dried at 120 ° C for 30 seconds in a stretcher frame dryer. The web is then soaked in a bath which contains an aqueous 50% dispersion of butadiene-acrylonitrile-methacrylic acid mixed polymerate (Perbunan · N · 3405 · Farbenfabriken · Bayer) by applying a heat of 30 to 40 ° C on the web. The web which has been treated as described above is then dried in an oven at 16 ° C for 15 minutes. · Tear strength. · (According to IUP 8) · is 7 kg / mm (in the usual way · bonded webs have a tear strength of between 4 and 5 kg / mm).

Slipping is observed when torn. The elastomer on the fiber, on the other hand, is found to cause tear of the conventional elastomeric bond. The fleece is suitable as a carrier material for cowhide-type leatherette. .

Example · 10

As Example 9, but with the difference that the impregnating liquid used in the first stage of the web preparation process contains 10 g of phenol and 20 g of glycerin monostearate per liter of perchlorethylene.

Example 11, *

As Example 10, but with the difference that the impregnating liquid contains 15 g of phenol and 30 g of glycerin monostearate per liter of perchlorethylene.

Example 12 · '

As Example 10, but with the difference that the impregnating liquid contains na. . liter perchlorethylene 40 g phenol and 60 g glycerin monostearate.

Example 13. .

The fibrous web of Example 9 is treated with an impregnating liquid in the manner described therein containing 30 g of phenol per 1 liter of perchlorethylene and 10 g of glycerol monostearate. After treatment for 10 minutes, the web is rinsed in pure perchlorethylene and air dried at room temperature. The fleece exhibits a significant weight increase of up to 20% based on the unprocessed fiber, which can be attributed to the considerable swelling of the fibers. The cross-section of the polyamide fibers, the swelling agent and the solvent penetrates into the polyester fibers without the cross-section widening. · Does not change at room temperature. a state of swelling for a longer time.

The web treated as above is dipped in an aqueous dispersion in a known manner. mixed polymer based on · butadiene-acrylonitrile-acid · methacrylic (Perbunan · N 3405 M · f · Farbenfabriken Bayer) in a bath and then · · remove excess by squeezing and · coagulate · heat treatment 38 to 40 ° C, washed and then dried at 160 ° C for 15 minutes. In this drying process, the fiber swells. Swelling agents; respectively. the solvents · are pulled off the fibers, the bonded webs are very flexible and show a rolling and brittle behavior · like leather. The elastomer content is 60% based on the total weight of the web. The tensile strength according to IUP 8 is 8 kg / mm (box-, calf-type). · \ "

Example 14

According to Example 13, except that the impregnating liquid in the first stage of the preparation process contains 40 g of phenol and 15 glycerin monostearate per liter of perchlorethylene.

Example 15

As in Example 13, but with the difference that the impregnating liquid contains per liter of perchlorethylene 50 g of phenol and 20 g of glycerin monostearate.

Example 16

As in Example 13, but with the difference that the impregnating liquid contains 60 g of phenol in 30 g of perchlorethylene in 30 g of glycerol monostearate.

By varying the proportions of the impregnating liquid components, the fiber shifting properties of the binder change.

Example · 17

The spunbonded web of Example 1 is treated for 10 minutes in a liquid containing 50 g of phenol and 30 g of citric acid monostearyl ester in one liter of perchlorethylene.

It is then rinsed in pure perchlorethylene and treated for 3 minutes in a hot-air frame dryer with 150 ° C hot air.

The treated nonwoven is soaked in a known manner with a 50% aqueous dispersion of butadiene-acrylonitrile-methacrylic acid mixed polymerate (Perbunan N 3405 M), coagulated and dried in a tension frame dryer at 160 ° C for 15 minutes.

A flexible fleece having a tear strength of 7 kg / mm (according to IUP 8) is provided, which is a suitable substrate for cowhide-type leatherette. .

. \ ' ¹

EXAMPLE 18 The swirled fiber web of Example 1 is treated for 8 minutes with an impregnating liquid containing per liter of perchlorethylene 30 g per day. phenol and 50 g glycol monooleate.

It is then washed in pure perchloroethylene and exposed to a temperature of 150 ° C for 5 minutes in a tension frame dryer. The web is soaked with 50% aqueous dispersion of butadiene-acrylonitrile-acid mixed polymerate. methacrylic (Perbunan N3405M), squeezed, coagulated with heat 38-40 ° C, and dried at 160 ° C.

The tear strength is 7 kg / mm (according to IUP 8).

Claims (35)

1. A fiber web having leather-like properties based on synthetic fibers, in particular based on a 1: 1 mixture of polyamide and polyester fibers, optionally based on heat-shrinkable fibers, comprising a polymeric organic reinforcing material, characterized in that: comprising a polymeric elastic reinforcing material of 10 to 80% by weight, based on the total weight of the raw web, with a density of - 0.1 to 0.28 g / cm 3, a fiber thickness of 0.8 to 3 dtex, a tensile strength of at least 0.09 MPa, a tensile strength of at least 7 kg / mm and a tensile test at 10% elongation at a specified tensile stress of 0.27 MPa, with a synthetic coating on the fiber surface - in an amount of 2 to 20% per - the weight of the raw nonwoven having an adhesive strength against the surface of the fiber - preventing scrubbing - on the other hand, it has no adhesion to the elastic polymeric reinforcing material bordering the nonwoven penetrating coating - and yet surrounds the nonwoven fibers. 2. The fibrous web of claim 1 wherein the polymeric reinforcing agent is an elastomer. 3. Fiber fleece according to items 1. -a - 2, characterized in that the polymeric strengthening agent consists of polyurethane. 4; Fiber web according to Claims 1 and 2, characterized in that - the polymeric reinforcing agent consists of synthetic rubber. 5. The fibrous web of claim 1, wherein the polymeric strengthening agent comprises a mixed polymer of butadiene, acrylonitrile and methacrylic acid. 6. A fiber web as claimed in any one of Claims 1 to 5, characterized in that it has a proportion of reinforcing agent of from 30 to 65% by weight. 7. The fibrous web of claim 2 wherein the coating is octadecylethylene urea. 8. The fibrous web of claim 1, wherein the coating comprises dimethyl polysiloxane. 9. Fiber-web according to claim 8, characterized in that the coating consists of a cross-linkable silicone. 10. Fiber web according to claims 1-7, characterized in that the coating consists of a precondensate of melamine formaldehyde or urea-formaldehyde cross-linked polymers with perfluorinated aliphatic side chains. 11. Fiber fleece according to - points - 1 - to - 10, The coating composition is present in 5 to 5 layers. 15 -%, - based on the total weight of the web. 12. A method of preparing a fibrous web as claimed in any one of claims 1 to 11, wherein the web is treated with a solution or dispersion of a synthetic non-replaceable coating composition, an excess of processing. The bath is removed and the impregnated web is treated for 10 seconds to 10 minutes at a temperature of - 100-180 ° C, impregnated, the web is then treated with a solution or dispersion of the polymeric strengthening agent, the polymer precipitates and the web is dried. for 2 to 30 minutes at a temperature of 100 to 180 ° C. - - 13. A method according to claim 12, characterized in that the web is treated with a solution or dispersion consisting of liquid halogenated, aliphatic hydrocarbons, benzene compounds and a free phenolic OH group, and - a coating composition consisting of higher fatty acid serersesters and polyvalent aliphatic alcohols or - polyvalent -aliphatic carboxylic acids with long-chain aliphatic alcohols, wherein the amount of ester in the impregnating liquid exceeds the benzene compounds having a free phenolic OH group, or both present - in equal proportions, the fleece is then freed of excess impregnating liquid by washing with solvent and, if the ester component is predominant in the impregnating liquid, the benzene component having a free phenolic OH group - is left to act for 10 seconds to 10 minutes heat - 100 to 180 C and then impregnated on 'the web is allowed to act, or a liquid solution - dispersion polymer - zpevňoyacího elastic means, fixing means polymer was precipitated and dried fleece; for 2 až'30 minutes at 100 to 180 ° C. . 14. A process according to claim 12, characterized in that the nonwoven is treated with a bath consisting of liquid halogenated aliphatic hydrocarbons, benzene compounds with a free phenolic OH group, and a coating composition for nonwoven fibers composed of esters of higher fatty acids and polyvalent. aliphatic alcohols or polyhydric aliphatic-carboxylic acids with long-chain aliphatic alcohols, wherein the amount of the benzene compound having a free phenolic OH group predominates the amount of the coating agent, then the web is removed by rinsing 188447 ¹⁹ duction redundant impregnating liquid and dried at room temperature, then the impregnated material is treated with a liquid solution or dispersion of a polymeric elastic fixing means, and the precipitated elastomer web is 2 to 30 minutes and dried at 100 to 180 ° C. 15. The method of claim 12, wherein after impregnating the web and removing excess impregnating liquid, heat is applied for 10 seconds to 10 minutes, then the impregnated material is treated with a liquid solution or dispersion of polymeric reinforcing agent, the elastomer precipitates and the web is dried for 2 to 30 minutes at 100 to 180 ° C. 16. Method according to claim 12, 13 or 15, characterized in that after impregnation, the web is treated for 2 to 30 minutes at a temperature of 100 to 180 [deg.] C. 17. The method of claim 22, After the impregnation, the web is treated for 2 minutes at 150 ° C. ' 18. The method of claim 12 wherein the web is coated with a 6% aqueous silicone dispersion. 19. The method of claim 12, wherein the fleece is coated with a 5% aqueous dispersion of octadecylethylene urea. 20. The method of claim 12, wherein the web is coated with a 30% aqueous dispersion of a readable polymer with perfluorinated aliphatic side chains at a bath ratio of 1:20, 21. The method of claim 20, wherein the web is coated with an aqueous dispersion consisting of 80 g / l precursor of melamine formaldehyde and 30 g / l crosslinkable polymer with perfluorinated aliphatic side chains. . 22. The method of claim 20, wherein the web is coated with an aqueous dispersion consisting of 100 g / l of urea-formaldehyde precondensate and 30 g / l of cross-linkable polymer with aliphatic side chains. 23. The method of claim 12, wherein the web is coated to form a coating which is 2 to 20% by weight of the web without filler. 24. The method of claim 23, wherein the web is coated to form a coating which is 5 to 15% by weight of the web without filler. 25. The process of claim 13, wherein the amount of ester I in the impregnating liquid is greater than the amount of benzene compounds having a free phenolic OH group or both are present in equal parts. 26. The process of claim 14 wherein the amount of benzene compound having a free phenolic OH group in the impregnation liquid exceeds the amount of ester. 27. A process according to claim 13, wherein the impregnating bath comprises a liquid chlorinated aliphatic hydrocarbon, phenol and glycerin monostearate. 28. A method as claimed in any one of claims 13 to 15, 25 and 26 wherein the web is impregnated with a liquid consisting of a liquid chlorinated aliphatic hydrocarbon, phenols; as well as citric acid monostearyl ester. 29. The method of items 13 to 15, 25 and 26, characterized in that; The method of claim 1 wherein the web is impregnated with a liquid consisting of a liquid chlorinated aliphatic hydrocarbon, phenol and glycertine monooleate. 30. The method of claims 13 to 15, 25 and 26 wherein the web is impregnated with a liquid consisting of a liquid chlorinated aliphatic hydrocarbon, phenol, and glycerine distearate. 31. The process of claims 13 to 15, 25 and 26 wherein the web is impregnated with a liquid consisting of a liquid chlorinated aliphatic hydrocarbon, phenol and erythrltmonopalmitate. 32. A method according to any one of claims 13 to 15, 25 and 26, characterized in that the web is impregnated with a liquid consisting of a liquid chlorinated aliphatic hydrocarbon, phenol and sorbitmonostearate. 33. The process of claims 13 to 15, 21 and 22 wherein the web is impregnated with a liquid consisting of a liquid chlorinated aliphatic hydrocarbon, phenol, and sorbitol di-stearate. 34. The method of claims 13-15, 21 and 22, wherein the web is impregnated with a liquid in which the liquid chlorinated hydrocarbon is saturated. 35. The process of claims 13-15, 21, 22-30, wherein the web is impregnated with a liquid in which the liquid chlorinated hydrocarbon is perchlorethylene.