CS264630B1 - Laminated sheet material and method of its production - Google Patents

Abstract

Currently, laminated sheet materials are treated in order to achieve optimal surface properties, mainly by applying various protective varnishes. However, from the point of view of the durability of the treatment and a more comprehensive solution of the properties of laminated sheet materials, it seems more advantageous to directly use more durable and high-quality covering layers - especially covering layers based on aliphatic polyurethanes, polyamides, polyglutamates, etc. The disadvantage of these solutions is, however, a significant increase in the price of the resulting sheet material. The solution, the essence of which is that the covering layer of laminated sheet materials is made of an acrylonitrile-butadiene-styrene copolymer, containing 25 to 50% by weight of the elastomeric component, which is in the form of particles with a size of 0.03 to 0.5 µm and the content of bound butadiene in it is 50 to 100% by weight. The remaining part of the elastomeric component is then formed by bound vinyl monomers (styrene, alphamethylstyrene, acrylonitrile or methyl methacrylate). The thermoplastic component of the copolymer, contained in an amount of 75 to 50% by weight, is formed by a styrene-acrylonitrile copolymer in a weight ratio of 85:15 to 55:45, the molecular weight of which, determined viscometrically, is 70,000 to 700,000. Furthermore, the solution also relates to a method of producing this laminated sheet material.

Description

The invention relates to a laminated sheet material intended primarily for clothing, haberdashery and upholstery applications. Furthermore, the invention also relates to a method of producing this laminated sheet material.

Laminated flat materials, both homogeneous and lightweight, based on polyvinyl chloride, with or without a textile layer, are used in many sectors of the consumer industry as a substitute for scarce natural leather. They are widely used, especially in the automotive industry for seat covers, in the haberdashery sector and in the clothing and footwear industry for undemanding applications, they do not require hygienic properties. The disadvantageous surface properties of these materials - especially sticky, dirty and unpleasant to the touch surface - are solved in many ways, but basically by applying protective varnishes based on nitrocellulose, cellulose acetobutyrate, polymethyl methacrylate, polyurethane or polyamides. Soft, elastic materials with a central lightweight polyvinyl chloride layer and a covering layer based on aliphatic polyurethanes have proven to be very advantageous for processing in the haberdashery, upholstery and clothing industries, which ensure a pleasant touch, satisfactory abrasion resistance and sufficient resistance to plasticizer migration. Other well-known applications consist of a combination of various covering layers - based on aliphatic polyurethanes, polyamides, polyglutamates and an adhesive layer of polyurethane or polyacrylate on textile substrates. The use of these materials and their processing in the form of a solution in organic solvents or water dispersions allows achieving, in particular, a low surface weight of the material, excellent organoleptic properties, resistance to abrasion and good properties in a wide range of temperatures. Due to these properties, the aforementioned laminated materials find advantageous application in the clothing industry, in haberdashery and in the footwear industry - especially for light types of footwear.

The main drawback that prevents the wider spread of these materials is generally the high economic cost of production, as a result of which these types of materials, in some variants, are even close to natural leather in price.

In accordance with this deficiency of the prior art, the purpose of the invention is therefore to create a soft laminated material of a different composition, which will allow to achieve a significant reduction in production costs while maintaining or even improving the useful properties of the final products. The problem is solved by a laminated sheet material, the essence of the invention being that the cover layer of this material is formed from an acrylonitrile-butadiene-styrene copolymer, containing 25 to 50% by weight, preferably 30 to 40% by weight, of an elastomeric component which is in the form of particles with a size of 0.03 to 0.5 µm, preferably 0.5 to 0.1 µm, and the content of bound butadiene therein is 50 to 100% by weight, preferably 65 to 95% by weight. The remaining part of the elastomeric component then consists of bound vinyl monomers from the group of styrene, alphamethylstyrene, acrylonitrile, methyl methacrylate. The thermoplastic component of the copolymer, contained in an amount of 75 to 50% by weight, preferably 70 to 60% by weight, is formed by a styrene-acrylonitrile copolymer in a weight ratio of 85:15 to 55:45, preferably 80:20 to 70:30, the molecular weight of which, determined by viscometry, is 70,000 to 70,000, preferably 100,000 to 300,000. Due to the generally lower light stability and weather resistance of the acrylonitrile-butadiene-styrene copolymer, a synergistic mixture of antioxidants based on substituted phenols, ultraviolet absorbers based on benzotriazoles and antioxidants of the sterically hindered amine type (HALS) can be used in more demanding applications (especially for clothing materials) in an amount of 0.5 to 10.0% by weight - based on the weight of the copolymer acrylonitrile-butadiene-styrene.

The essence of the method for producing a laminated sheet material according to the invention consists in applying the acrylonitrile-butadiene-styrene copolymer to a temporary separation substrate in the form of a solution in organic solvents or in the form of an aqueous dispersion, the coating thus obtained is dried at temperatures of 70 to 150 °C and then further layers of sheet material are gradually applied, and finally a base fabric is laminated to the adhesive layer.

The layered sheet material according to the invention is soft and elastic, characterized by high surface resistance to abrasion, has excellent tactile properties and, due to lower production costs (in comparison with previously known materials of similar nature), is suitable for applications in practically all fields processing synthetic leather.

I

The following examples serve to further clarify the nature of the invention:

Example 1

Acrylonitrile-butadiene-styrene with the following composition was used to prepare the solution for the coating:

total content of the elastomeric component content of bound butadiene in the elastomeric component content of styrene in the elastomeric component particle size of the elastomeric component the thermoplastic component consists of a styrene-acrylonitrile copolymer with a weight ratio of monomer units of 72:28 and a molecular weight of 120,000% by weight 90% by weight 10% by weight

0.1 _of the µm content of antioxidants based on substituted bis-phenols is 1.4% by weight (based on the acrylonitrile-butadiene-styrene copolymer).

A solution of the copolymer acrylonitrile-butadiene-styrene with a concentration of 10% by weight was prepared on a high-speed mixer at 1,000 rpm by dissolving the powder or crushed copolymer in a mixture of solvents toluene - acetone in a ratio of 3:1, with the addition of 1% by weight of the pigment premix in the paint (based on the weight of the mixture) and further 1.0% by weight of 2,2'-hydroxy-5-methylphenylbenzotriazole (Tinuvin P, and 1.0% by weight of bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770), based on the weight of the copolymer acrylonitrile-butadiene-styrene. A lightened polyvinyl chloride paste for the center layer was further prepared in a conventional manner (on a Papenmeier high-speed mixer at 500 rpm) with the following composition:

Polyvinyl chloride (Slovinyl EP 702) 100 wt., . parts emulsion paste, K value =70 dioctyl phthalate 100 wt. parts Azodicarbonamide (Genitron AC 4) 3 wt. parts brown pigment premix 20 wt. parts barium or zinc salts higher fatty acids 3 wt. parts The patterned paper separator pad was in quantity 100 g/m2

solution of the copolymer acrylonitrile-butadiene-styrene. After drying this layer at 80 to 100 °C, a middle layer of expandable polyvinyl chloride paste was applied in an amount of 180 g/m2, which was pregelatinized at 150 °C. Fabric was then laminated to the next layer - the lamination layer (in an amount of 80 g/m2). After expansion of the entire formation at temperatures of 180 to 190 °C and cooling, the laminated material was separated from the backing.

The obtained material had the following parameters and properties:

a) thickness b) weight per unit area 0.9 mm 0.350 kg/ ^m2 c) abrasion resistance according to 1,000 cycles at a load of 0.045 MPa Rowboat (ČSN 64 7031) in dry and wet conditions d) touch dry, non-sticky e) resistance to repeated after 50 kc (kilocycles) bending on a Bally flexometer 4/4 (ČSN 64 7029)

The material is suitable for processing in the field of light haberdashery - for handbags, suitcases and for furniture upholstery.

Acrylonitrile-butadiene-styrene with the composition was used to prepare the solution for the coating.

Example: total elastomeric component content 45 wt.%.

butadiene content bound in the elastomer component 70% by weight.

styrene content in the elastomer component 30% by weight.

the particle size of the elastomer component is 0.5 µm the thermoplastic component consists of a styrene-acrylonitrile copolymer with a weight ratio of monomer units of 78:22 and a molecular weight of 250,000 the content of an antioxidant based on substituted bis-phenols is 1.4% by weight (based on the acrylonitrile-butadiene-styrene copolymer).

A solution of acrylonitrile-butadiene-styrene copolymer with a concentration of 18% by weight was prepared on a high-speed mixer at 1 * Ό rpm by dissolving the copolymer in a toluene-acetone mixture in a 1:1 ratio, with the addition of 3% by weight of a brown pigment premix (based on the weight of the mixture) and further 3% by weight of 2(2*-hydroxy-5-methylphenyl)benzotriazole (Tinuvin P) and 3% by weight of bis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (Tinuvin 770), based on the weight of the acrylonitrile-butadiene-styrene copolymer.

A dispersion mixture for the adhesive layer was further prepared on a planetary mixer with the following composition:

aqueous dispersion of styrene-acrylate copolymer with a dry matter content of 45% by weight, with the composition butyl acrylate, styrene, acrylamide, N-butoxymethyl methacrylamide, acrylic acid (SOKRAT 4 924) melamine formaldehyde resin etherified with methanol, with a dry matter content of 65% (RESIN MH) polyacrylate thickener with the composition ethyl acrylate, methacrylic acid, with a dry matter content of 25% (SOKRAT 1 025) ammonia water with a concentration of 25%

100 parts by weight parts by weight parts by weight at pH 8 to 9

A layer of acrylonitrile-butadiene-styrene copolymer solution was applied to a paper separation pad in an amount of 130 g/m. After drying this layer at 80 to 100 °C, an adhesive layer based on an aqueous dispersion was applied in an amount of 100 g/m, into which a combed polyamide knit was laminated. After drying the entire structure at 100 to 130 °C and cooling, a leatherette material for clothing applications with excellent organoleptic properties was obtained. The material also meets the requirements for bending resistance according to Bally (150 kc) and abrasion resistance according to Veslice (2,000 cycles at a load of 0.045 MPa both dry and wet).

Example 3

A solution of the acrylonitrile-butadiene-styrene copolymer of the same composition was prepared using a similar procedure as in Example 2, with a concentration of 10% by weight in a mixture of solvents toluene-acetone in a ratio of 1:1, with the addition of 3% by weight of a brown pigment premix (based on the weight of the mixture) and the addition of 3% by weight of 2-(2'-hydroxy-5-methylphenyl)benzotriazole (Tinuvin P) and 3% by weight of bis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (Tinuvin 770) - based on the weight of the acrylonitrile-butadiene-styrene copolymer. The dispersion mixture for the adhesive layer was then prepared using the same procedure as in Example 2.

A layer of acrylonitrile-butadiene-styrene copolymer solution was applied to the patterned paper separation pad in an amount of 150 g/m, after drying at 80 to 100 °C, an adhesive layer of water dispersion with a surface weight of 100 g/m was then applied. A poromeric textile substrate was laminated to this layer, obtained in the previous production stage by impregnating the textile pad with a polyurethane solution and subsequent coagulation. After drying the entire formation at 100 to 130 C and cooling, a poromeric footwear material with excellent organoleptic properties was obtained, suitable primarily for women's footwear. The material meets very well the requirements for bending resistance according to Bally (100 kc) and abrasion resistance according to Veslic (2,000 cycles at a load of 0.045 MPa both dry and wet).

Example 4

The dispersion mixture for the covering layer was prepared using an aqueous dispersion of acrylonitrile-butadiene-styrene copolymer, with a dry matter content of 40%, with the following composition:

total content of the elastomeric component content of bound butadiene in the elastomeric component content of acrylonitrile in the elastomeric component particle size of the elastomeric component the thermoplastic component consists of a styrene-acrylonitrile copolymer with a weight ratio of monomer units of 80:20 and a molecular weight of 350,000 the content of an antioxidant based on substituted bis-phenols is 1.0 t wt. (based on the weight of the acrylonitrile-butadiene-styrene copolymer).

% wt. 80 i wt. 20 % wt. 0.2 jim

The dispersion mixture itself was then prepared in a slow-speed mixer according to the following recipe:

aqueous dispersion of acrylonitrile-butadiene-styrene copolymer (40% dry matter) 100 parts by weight casein dye black 5 parts by weight polyacrylate thickener with the composition ethyl acrylate-methacrylic acid with a dry matter content of 25% (SOKRAT 1 025) 2 parts by weight bis-(2,2,6,6-tetramethyl-4-piperidinyl)sebacate 1.2 parts by weight

2-(2-hydroxy-5-methylphenyl)benzotriazole 1.2 parts by weight

A dispersion mixture for the adhesive layer was prepared in a similar manner as in Example 2. The composition of the dispersion mixture and the procedure for preparing the synthetic leather were also identical to Example 2. The prepared leatherette material is suitable for clothing and upholstery applications; it meets very well the requirements for bending resistance according to Bally (150 kc) and abrasion resistance according to Veslice (2,000 cycles at a load of 0.045 MPa both dry and wet).

Claims (2)

SUBJECT OF THE INVENTION 1. Laminated sheet material composed of a polymer backing layer, a cellular layer, in particular based on polyvinyl chloride, an adhesive interlayer, in particular based on polyurethane and / or polyacrylate copolymers, and a backing textile layer, optionally only a backing polymer layer, adhesive interlayer and backing textile layer wherein the backing textile layer can also be a poromeric textile substrate, characterized in that the cover layer is formed of an acrylonitrile-butadiene-styrene copolymer containing from 25 to 50% by weight, preferably from 30 to 40% by weight, of an elastomeric component present in the copolymer in the form of particles having a particle size of 0.03 to 0.5 µm, preferably 0.05 to 0.1 µm, and the bound butadiene content in it is 50 to 100% by weight, preferably 65 to 95% by weight, the remainder being this elastomeric component consists of bound vinyl monomers from the group of styrene, alphamethylstyrene, acrylonitrile, methyl methacrylate and, furthermore, 75 to 50% by weight, preferably 70 to 60% by weight, 266430 of a component which is composed of a styrene-acrylonitrile copolymer in a weight ratio of 85:15 to 55:45, preferably 80:20 to 70:30, whose molecular weight determined viscosimetrically is 70,000 to 700,000, preferably 100,000 to 300,000, and further, that the above-specified acrylonitrile-butadiene-styrene copolymer contains 0.5-10.0% by weight of a synergistic mixture of antioxidants to increase light stability and atmospheric resistance based on substituted phenols, ultraviolet absorbers based on benztriazoles and spherically hindered amine (HALS) antioxidants. 2. A method according to claim 1, wherein the acrylonitrile-butadiene-styrene copolymer is applied to a temporary separation substrate in the form of a solution in organic solvents or in the form of an aqueous dispersion, and the coating thus obtained is dried at temperatures of 70-150 ° C. and then further layers of the sheet material are successively applied, and the backing is then laminated to the adhesive interlayer.