CS219356B1 - Flat multilayer material with ammeliorated sorption properties and method of making the same - Google Patents

Abstract

Flat multilayer material with improved absorption properties, intended for applications especially in footwear, clothing, haberdashery and the furniture industry and method production. The material is made of layers based on natural or synthetic polymers in fabric form, nonwoven fibrous layers, knitted fabrics, polymeric films of a particularly porous nature, or, if necessary, these deposited formations or impregnated elastomer blends or thermoplastic. At least one of layers of this sheet material 0.5 to 30% by weight, preferably 2 to 10% by weight; 12% of the metal electrolyte salts of metals I., II. and / or III. group of the periodic system. The method of making this material rests in that at least one of its layers is impregnates, eventually coating, with a solution or * polymer electrolyte dispersions, optionally mixtures thereof with a polymeric binder. During impregnation or after impregnation the electrolyte acts by inorganic solutions or organic metal salts of I., II. and/ / or III. groups of the periodic system, thereby forming salts of the polymer electrolyte directly in the sheet material.

Description

The invention solves a sheet material with improved sorption properties intended for processing especially in the footwear, clothing, haberdashery and furniture industries. It is a further object of the present invention to provide a method for producing such a material.

Materials based on natural, synthetic or modified polymers are widely used in various manufacturing industries, most commonly textile structures woven, nonwoven, knitted, knitted and other, optionally interconnected with a polymeric binder and in some cases provided with at least one polymeric cover layer. Materials for outerwear, materials for underlay, reinforcement or upper footwear materials, upholstery materials in the furniture industry and materials for the haberdashery industry are thus obtained. Recently, the production of impregnated fiber formations, artificial leather and poromers, mainly based on polyvinyl chloride and polyurethanes, has undergone great progress.

These materials are prepared using mainly the following technologies: impregnation and coating of textile formations with solutions, dispersions and pastes of polymers followed by drying, gelling, thermo-coagulation, coagulation with non-solvents, bonding by reactive polymeric systems, possibly with blocked reactive groups .

Most of these materials, especially those made entirely of synthetic polymers, do not achieve the necessary water sorption properties comparable to those of water; natural materials such as cotton and woolen fabrics or natural leather. ?

However, great efforts are being made to improve their utility properties, in particular the ability to reverse water vapor absorption and also to release them. This is evidenced by a number of known technical solutions dealing with this issue. It is known, for example, to improve the hygienic properties of sheets by adding silicic acid gels or bentonites which influence the formation of pores and thus the vapor permeability and water vapor sorption. A number of inventions are concerned with the application of polyacrylamides, their salts or copolymers having a very good water vapor absorption capacity. Polymers modified with the addition of polyalkylene oxides cross-linked with ionizing radiation are also used to produce sheet materials with improved sorption properties. To a large extent, differently treated collagen is utilized to enhance the water vapor abilities of sheet materials.

Recently, flat materials, mainly used in the footwear, clothing and furniture industries, where poly-JBk specific electrolytes have been applied as a sorption enhancing agent, are beginning to spread. An example of such materials is a polyurethane-based sheet-like structure capable of absorbing and permeating water-based bretons due to the uniform incorporation of solid particles of at least one swellable polymer in its structure. The swellable polymer is a modified carbohydrate, e.g., modified cellulose or starch. However, the use of polyelectrolytes as combination polymers for this purpose usually encounters a contradiction - polymers with high water sorption values are usually also water-soluble.

In this context, processes aiming at maintaining good sorption properties of polyelectrolytes while eliminating or at least limiting their solubility are useful. Many of these processes are already known from other fields - especially the production of sorption materials for medical products, such as db binder materials, tampons, diapers, etc. Limiting the solubility of alkali metal salts of carboxymethylcellulose can be achieved, for example, by heating these salts to 130 to 210 ° C. Another procedure is to conduct the etherification of the cellulose to a stage which does not yet allow the water-solubility of these polymers, but already gives the ability to absorb water vapor. Another way of limiting the solubility of hydrophilic swellable carbohydrates is by the action of ionizing radiation on the mixture of carbohydrate with powdered inert filler and water. Other possibilities of reducing the solubility of carboxymethylcellulose are its heating with acidic compounds, or the preparation of its alkali metal salt with a water-soluble fraction of less than 35%, or cross-linking with acrylamides. The principle composition and preparation of the ionic complex of anionic polyelectrolyte, in particular based on polyacrylates and their copolymers with other polyvalent metal polymers, is also known from the use for medical products and is applied here alone as a sorption material in the form of foils, fibers or powder. It is a water-swellable, water-insoluble material of a gelatinous nature, capable of absorbing up to 15times of water or other aqueous liquid - eg sweat, blood, urine.

Compared to the known flat synthetic materials mentioned above, it exhibits very good sorption properties, comparable to natural materials such as cotton and wool fabrics or natural leather, a multi-layer material according to the invention. It is a material of layers based on natural or synthetic polymers in the form of a fabric, non-woven fibrous layer, knitted fabric, knitted fabric, polymeric film, in particular of porous character, or these coated or impregnated elastomer or thermoplastic mixtures. At least one of the layers of said sheet material comprises 0.5 to 30 wt. %, preferably 2 to 12 wt. %, salts of polymer electrolyte with metals I., II. and / or III. groups of the periodic system.

The method for producing this multilayer sheet material is to impregnate or impregnate at least one of its layers. deposited with a solution or dispersion of a polymer electrolyte or a mixture thereof with a polymeric binder. During or after impregnation, the polymer electrolyte is treated with solutions of inorganic or organic metal salts of I., II. and / or III. groups of the periodic system. The residues of these salts after reaction with the polymer electrolyte and other salts present in the reactants are retained in the sheet material.

An advantage of the method of increasing the water sorption of the multilayer sheet materials produced according to the invention is, in comparison with the known methods, the possibility to control the solubility of the polyelectrolytes while maintaining or reducing the solubility. only a small decrease in their sorption properties. Salts present in the reactants or reaction-enhancing sorption properties still improve. Another advantage is the simple technology of production and does not require complex and expensive equipment.

The range of polymer electrolytes suitable for application to multilayer sheet materials is quite wide. In addition to natural polymers such as casein and gelatin, various modified natural polymers - in particular modified cellulose and starch derivatives - can be used for this purpose. The choice of a suitable polyelectrolyte depends on the desired properties of the final product, but mainly on the technical possibilities of its production and possibly the price. Modified cellulose ethers - especially carboxymethylcellulose - have a favorable position in this respect.

Of the polyvalent metal cations - in the sense of the definition of the object of the invention, metal II. and

III. In particular, aluminum and chromium cations are particularly preferred for their chemical properties and availability.

The metal content of the polyelectrolyte salts has been found to be in the range of 0.01 to 10% by weight. The amount of metal depends on the desired water-vapor-absorbing capacity of the polyelectrolyte, its degree of solubility, and also its molecular weight.

The way of conducting the reaction between the polymer electrolyte and polyvalent metal salts depends on the technology of production of the given multilayer sheet material - see individual practical examples. However, since the salts of polymer electrolytes with metals more than monovalent are either sparingly soluble or insoluble, it is preferred to carry out the reaction of the polyelectrolyte with these metal salts during or after impregnation or deposition of the polymer electrolyte or a mixture thereof. with a polymeric binder on the substrate. Since the inorganic, respectively. The organic salts present or formed in the synthesis of the salts of the polymer electrolyte have a favorable effect on improving the sorption properties of the sheet material, it is preferable to leave these salts in the material.

However, the presence of salts of polymer electrolyte in one of the layers of a multilayer sheet material also affects the physico-mechanical properties of the material - primarily increasing its dry stiffness. Therefore, according to the invention, the proportion of these salts in the sheet material is limited to a maximum of 30% by weight. %, preferably 2 to 12 wt. %. Due to the very good water vapor-absorbing capacity of the poly-electrolyte salts, which, for example, does not fall below 150% by weight of carboxymethylcellulose aluminum salts, this addition is sufficient to achieve sorption properties comparable to natural sheet materials such as leather, cellulose-based materials and the like.

The following practical examples serve to illustrate the invention in more detail, the first three of which are of particular importance in terms of comparing sorption properties, while the others show methods for producing and performing particular multi-layered sheet materials of various types.

Example 1

The needled fiber layer of 600 g / m ² polyester / polypropylene fiber blend was impregnated with a 16% solution of polyurethane in dimethylformamide in which 4% of sodium grade carboxymethylcellulose of technical grade was dispersed in a mixed solvent of dimethylformamide-water in a ratio of 1: 1 and 0. Of a 2% solution of potassium potassium sulphate in 10% water. The impregnated fibrous layer was coagulated in water and dried after drying the dimethylformamide at 90 ° C for 1 hour. It was then ground and chipped to a thickness of 1 mm. 0 50 mm wheels were punched out of the treated material for which the water vapor sorption at 30 ° C and 100% relative humidity was determined over a period of 8 hours. The result is shown in the table. The wheels were then washed in running water at 25 ° C for 1 hour and weight loss and water vapor sorption were determined. The results are also shown in the table.

Example 2

The fibrous layer identical to Example 1 was impregnated with a 20% polyurethane solution in dimethylformamide. After coagulation in water and washing, it was further impregnated by squeezing in a 5% solution of purified sodium carboxymethylcellulose to a content of ca 10% of this salt in the dry matter of the impregnated fiber layer. The wet impregnated fibrous layer was then immersed in a 0.5% potassium aluminum sulfate solution for 2 minutes and dried at 90 ° C for 1 hour after stripping off the excess solution. This was followed by grinding and

21S356 splitting to a thickness of 1 mm. It was further evaluated as in Example 1. Results - see table.

Example 3

It is identical to Example 2, but the fibrous layer impregnated with polyurethane was not impregnated with sodium carboxymethylcellulose solution and no further treatment with aluminum salt was performed. The sorption comparison is in the table.

TABLE

Example No. Content of polyelectro- Sorption of H2O lyte in material (%) (%)

Washing loss [%]

H2O sorption after washing (%)

1 4.72 10.3 3.17 9.2 2 10.55 18.2 25.59 13.4 3 0 0.6 0 0.5

Example 4

The mixer was mixed with the composition (in parts by weight):

poles vinyl chloride 100 benisylbutyl phthalate 40 dicotyliftalate 42 azodicarbonamide 3.5 organocomplex decomposition catalyst blowing agent 4 calcium carbonate 12 organotin stabilizer 1.5

This mixture was pre-plasticized at 115 ° C in a kneader, processed into a double roll at 125 ° C, and a 0.5 mm thick film was rolled on a four-roll roll at a roll temperature of 120-145 ° C. The film was then laminated at 165 ° C with a one-side combed knitted fabric on a 70:30 polyamide-cotton blend base and a polyvinyl chloride film without a blowing agent; the resulting layered material was expanded in an oven for 2 minutes at 195 ^° C. The material so produced was then sprayed from the reverse textile side with a 2% technical carboxymethylcellulose solution containing 0.1% potassium aluminum sulfate and dried at 110 ° C for a period of time. 10 minutes. The resulting multi-layer material can be used in shoe production and has an equilibrium water vapor sorption of 8 mg / cm ² .

Example 5

The prepolymer obtained by polyaddition of polypropylene glycol and 4,4 & apos ^; -diphenylmethane isocyanate containing 4.9% isocyanate groups, after dissolution in dimethylformamide to 60% solution, was extended with hydrazine hydrate until a viscosity of 2.8 Pa was reached. at 30 ° C. The resulting solution was then adjusted with the modification ingredients to the resulting composition;

Weight parts polyetherurethane 24 dimethylformamide 68.4 polypropylene oil 3.8 polyurethane dispersion 2.6 sulfonated phenol-formaldehyde resin 0.1

20% magnesium chloride solution 0.12 brown dye 0.98

The unilaterally combed polyamide fabric with a basis weight of 200 g / m ² was interconnected with this solution, which was then co-agglomerated unilaterally from the combed side with a 30% solution of dimethylformamide in water for 4 minutes. This was immediately followed by bilateral coagulation in the same bath for 6 minutes. After washing, the obtained material was roller coated with a fraction of a 6% solution of sodium carboxymethylcellulose in water, wiping off the excess solution with a metal damper under pressure. The so treated material containing 8% carboxymethylcellulose was passed over the surface of a 2% solution of aluminum sulfate in water and then dried at 110 ° C. The resulting soft velor poromer having a basis weight of 290 g / m ² had good abrasion resistance, a water vapor permeability of 25 mg / / cm ² / liod and a sorption of 9 mg / cm ² . The material is suitable for clothing, very soft footwear and upholstery.

Example 6

Double-sided combed fabric of 180 g / m ² fabric made of 70: 30 polyethylene terephthalate-cotton fiber blend was interlocked and overlaid on both sides with 8% dispersion of polybutylene adipate and 4,4'-diphenylmethane diisocyanate extended with 1,4-butanediol . The polymer dispersion in dimethylformamide contained 8% water, the viscosity was 230 mPa.s at 30 ° C. The thickness of the covering film was determined on both sides by a knife and a roller scraping so that it exceeded the length of the loose hair by 0.2 mm. The polymer was coagulated and washed from dimethylformamide by passing through a bath containing 90% water and 10% dimethylformamide. After squeezing, the coagulated formation was introduced into an impregnation bath of a 5% solution of sodium carboxymethylcellulose in water. The so impregnated body containing 8% carboxymethyloellulose sodium was immersed in a 3% aluminum sulfate solution for 3 minutes. After removing the excess solution, the material was compacted from the front side by ironing at 100 ° C and a pressure of 0.03 MPa, dried and ground down. The resulting material had a thickness of 0.75 mm, a basis weight of 295 g / m ² , a water vapor permeability of 18 mg / cm ² / hour. and sorption 12 mg / cm ² . After finishing the cheek surface _; A pigmented, finished polyurethane-based layer produced a soft synthetic leather with fine wrinkle on the cheek, suitable for application in clothing and upholstery.

Example-d7

The needled fiber layer of a blend of polypropylene, polyester and cellulose fibers weighing 160 g / m ² was impregnated with butadiene styrene latex containing 10% neutralized sodium carboxymethylcellulose in the latex dry matter at 20 ° C until saturation. The binder to fiber ratio was 50:50. The impregnated fiber layer was then dried at 110 ° C for 15 minutes, moistened with a 0.2% aluminum sulphate solution, dried again and vulcanized at 120 ° C. The material was then adjusted to a thickness of 1 mm. This impregnated fiber layer was laminated with the film described in Example 4, which was then expanded at 195 ° C for 2 min. The obtained material was surface treated. It showed good flexural properties and had a water vapor sorption of 11 mg / cm ² .

Example 8

A 0.2 mm thick solvent-free reactive mixture composed of 100 wt. parts of a 25% polyurethane solution, based on polycaprolactone, isophorone diisocyanate and ethylenediamine, in a toluene-iso10 propanol-methylethylketone mixture and a 1: 1: 1 ratio, and 8 wt. parts of a color batch containing 5 parts of a surfactant. The deposit was cured at 150 ° C for 2 minutes and then coated with a 0.2 mm thick, solvent-free thermoreactive mixture of 100 wt. parts of polypropylene glycol prepolymer, 2000 molecular weight, with toluene diisocyanate, 2 wt. parts by weight of ethylenediaminocarbamate, 3.5 wt. 30 parts by weight of aminoethylene ethanolaminocarbomate; parts by weight of a mixture of finely ground calcium carbonate and 15 wt. parts of a color batch.

This layer was cured at 125 ° C for 5 minutes. A laminate layer of the same composition 0 'of 0.25 mm thickness was then applied to its surface, into which a non-woven fibrous layer of thickness of 0.85 mm, impregnated with polyurethane, was immediately laminated. After curing the laminated layer at 110 ° C for 8 minutes, a 6% solution of sodium carboxymethylcellulose in water was fractionated on the resulting material by fractionation; the excess solution was stripped off by a metal damper. A 2% solution of aluminum sulphate in water was then also used. After drying of the material at 110 ^° C, the entire formation was separated from the paper separation pad. The obtained material, intended mainly for shoe production, showed good flexural properties and water vapor sorption of 7 mg / cm ² / hour. Example 9

A fiber layer identical to Example 1 was impregnated with a 16% solution of polyurethane in dimethylformamide. After coagulation in water and washing of dimethylformamide, it was saturated by repeated squeezing below the level of a 4% aqueous solution of purified sodium carboxymethylcellulose. After stripping off the excess solution, it was then immersed in a 1% zinc acetate solution, which was acidified with acetic acid to pH ca 3. After re-stripping, the treated fiber layer was dried at 90 ° C and split to 1 mm by splitting. It was further evaluated as in Example 1.

The prepared material contained 3.8% cellulose polyelectrolyte. Sorption of water vapor

15.2%. The polyelectrolyte loss by washing with water was 31.6% and the water vapor sorption after washing was 11.4%.

Claims (6)

SUBJECT 1. Flat multi-layer material with improved sorption properties, in particular for footwear, clothing, haberdashery and furniture applications, of layers based on natural or synthetic polymers in the form of fabric, non-woven fibrous layer, knitted fabrics, plaited fabrics, coated or impregnated with a mixture of elastomer or thermoplastic, characterized in that at least one layer thereof comprises salts of polymer electrolyte with metals of I., II. and / or III. groups of the periodic system; the proportion of these salts in the layer is 0.5 to 30%, preferably 2 to 12%. 2. The sheet of claim 1 wherein the polymer electrolyte is a modified cellulose ether. 3. The planar multilayer material according to claim 1, wherein the metal content of the salts of the polymer electrolyte is 0.01 to 10 percent by weight. 4. A method according to claim 1, wherein at least one of the sheets is impregnated or deposited with a melt or dispersion of a polymer electrolyte or a mixture thereof with a polymeric binder, and during or after impregnation. this * polymer electrolyte acts with solutions of inorganic or organic metal salts I. II. and / or III. groups of the periodic system, the residues of these salts and other salts present in the reactants are left in the sheet material. 5. Process according to claim 4, characterized in that after the coagulation, the fibrous layer impregnated with the polyurethane solution is again impregnated with a solution of a soluble cellulose ether salt, the water solubility of which is simultaneously or additionally limited by reaction with metal salts I, II. and / or III. groups of the periodic system. 6. A method according to claim 4, wherein the fibrous layer is impregnated with a latex of a polymer containing a cellulose ether ether salt of a Group I metal of the Periodic System, after pre-drying the metal salt solution II is applied to its surface. and / or III. group of the periodic system, and drying is followed by a final heat treatment - for example vulcanization.