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Title:
A METHOD FOR MANUFACTURING COATED FABRICS USING WATER-BASED OR SOLVENT-FREE, VOC-FREE POLYURETHANES AND A FABRIC OBTAINED USING THIS METHOD
Document Type and Number:
WIPO Patent Application WO/2022/039607
Kind Code:
A1
Abstract:
This invention relates to a method for manufacturing polyurethane-coated fabrics, hereinafter referred to as the PU-coated fabrics, comprising a stage of coating a substrate - a PU-modified knitted fabric, characterised in that it comprises the following subsequent processes: - preparing a PU-W paste composition - a top layer or the face; - preparing a chemically-foamed PU-S paste composition - a second layer providing thickness and flexibility; - preparing a PU-L paste composition - a third layer bonding the PU-W+PU-S layer with the substrate (knitted fabric); - coating, i.e. applying the pastes on a release paper; - further processing. The invention also covers a PU-coated fabric characterised in that it comprises a substrate - a cotton knitted fabric in the amount of 69.6 to 71.7% wt, coated with three layers of polyurethane: 7.6 to 7.0% wt. PU- W; 16.3 to 15.4% wt. PU-S and 6.5 to 5.9% wt. PU-L, and the invention also covers said fabrics manufactured using the disclosed process.

Inventors:
KRAWCZUK MONIKA (PL)
KRZYWONOS RITA (PL)
Application Number:
PCT/PL2021/000002
Publication Date:
February 24, 2022
Filing Date:
January 11, 2021
Export Citation:
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Assignee:
SANWIL POLSKA SP Z O O (PL)
International Classes:
D06N3/14; B32B27/40; D06P5/24
Foreign References:
CN107151920A2017-09-12
CN104762825A2015-07-08
CN103498344A2014-01-08
Attorney, Agent or Firm:
SZYCHULSKA-HAWRANEK, Izabela (PL)
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Claims:
Claims A method for manufacturing polyurethane-coated fabrics, hereinafter referred to as the PU-coated fabrics, comprising a stage of coating a substrate - a PU-modified knitted fabric, characterised in that it further comprises the following subsequent processes:

- preparing a PU-W paste composition - a top layer or the face;

- preparing a chemically-foamed PU-S paste composition - a second layer providing thickness and flexibility;

- preparing a PU-L paste composition - a third layer bonding the PU-W+PU-S layer with the substrate (knitted fabric);

- coating, i.e. applying the pastes on a release paper;

- further processing. The method according to claim 1, wherein at the stage of preparing the PU-W paste composition, an aqueous polyurethane solution, preferably aliphatic polycarbonate-based, preferably with the following parameters:

- concentration 30%;

- viscosity 100 mPas;

- elongation at break 375%;

- elongation modulus in 100% - 6 MPa

- softening point 195°C

- tensile strength 35 MPa in the amount of 82.4 to 83.3% wt. is mixed with a surfactant, preferably 100% concentration and viscosity 25 mPas in the amount of 0.2 to 0.3% wt., a rheology modifier, pH 8 and viscosity 5.4 mPas in the amount of 2.0 to 1.5% wt., a cross-linking agent, preferably polycarbonate-based, viscosity 250 mPas in the amount of 3.5 to 3.3% wt., a defoaming agent, preferably silicone-free, viscosity 700 mPas in the amount of 3.5 to 3.3% wt., an adhesion modifier to reduce squeaking, viscosity 3 mPas and pH 5 in the amount of 4.9 to 5.0% wt., an adhesion modifier to improve abrasion resistance, preferably silicone- based, viscosity 150 mPas in the amount of 3.5 to 3.3% wt., the obtained mixture is stirred using an industrial mixer with dispersion blades for 15 minutes until all the components are combined, and the mixture is dyed to a specific colour, deaerated and conditioned for 24 hours, after which a polycarbonate-based cross-linking agent in the amount of 3.5 to 3.3% wt. is added immediately before coating. The method according to claim 1, wherein:

- at the first stage of preparing the PU-S paste, a mixture of pigments in the amount of 1.4 to 0.8% wt. and a pigment dispersing agent in the amount of 3.5 to 3.0% wt., a cross-lining agent, preferable blocking aromatic isocyanate-based in the amount of 4.5 to 4.0% wt. is prepared, wherein the mixture of pigments is added to the weighted dispersing agent and mixed at low speed in a mixer with dispersion blades for 10 to 15 minutes, the cross-linking agent is added and mixed for 5 to 10 minutes, and the obtained mixture is strained and conditioned for 8 hours,

- at the second stage of preparing the PU-S paste, an aqueous polyurethane solution, preferably aromatic, concentration 93 to 97% and viscosity 50,000 to 100,000 mPas in the amount of 82.5 to 84.6% wt. is mixed with a catalyst, preferably aliphatic isocyanate-based in the amount of 1.8 to 1.3% wt.; a silicone in the amount of 1.4 to 1.1% wt.; a fire retardant, preferably chlorine phosphate-based, liquid, low fogging in the amount of 4.9 to 5.2% wt., all components are mixed using an industrial paddle mixer for 10 minutes, and the mixture of pigments with the dispersing and cross-linking agent prepared in the first stage is added to said paste, mixed for 10 to 15 minutes and deaerated; the paste is not conditioned at this stage. The method according to claim 1, wherein at the day the paste is to be used for coating, a PU-L paste composition is prepared, wherein an aqueous polyurethane solution, preferably polyether-based, pH 6.5 to 7.5, concentration 48 to 52% in the amount of 49 to 51% wt. is mixed with an aqueous polyurethane solution, preferably polyether-based with pH 7 to 8 and concentration 38 to 42% in the amount of 50 to 48% wt., and immediately before coating, a cross-linking agent in the amount of 1 to 0.1% wt. is added to the mixture of two polyurethanes. The method according to claim 1, wherein at the stage of coating a substrate with the PU-W polyurethane paste, the PU-W paste with a viscosity of 100±10 mPas is poured over a release paper, preferably with acrylic coating at the head no. I of the coating machine operating at a linear speed of 9±1 m/min, and the paste applied on the release paper with a basis weight of 30 to 35 g/m2, being a top layer of the fabric is passed through the first heating tunnel, where the top layer paste is cross-linked at 90-100-110°C; the paper with the top layer is passed through a cooling unit to reduce its temperature, and the paper with the top layer is transferred to the head no. II of the coating machine, where the second PU-S layer with a basis weight of 65 to 75 g/m2 is applied and passed through the second heating tunnel where the PU-S paste is cross-linked and foamed at 150-170-180°C, passed through the cooling unit to reduce its temperature and transferred to the coating head no. Ill where the third laminate PU/L layer with a basis weight of 25 to 30 g/m2 is applied and attached to the substrate, the substrate is pressed by a laminating roller, and the paper with three polyurethane layers and the substrate is passed through the third heating tunnel, where it is cross-linked at 110-130-140-150°C, and the obtained product with a basis weight of 440±20 g/m2 and a thickness of 0.8±0.1 mm is passed through a cooling unit and delaminated, i.e. the coated fabric is separated from the release paper. A PU-coated fabric characterised in that it comprises a substrate - a cotton knitted fabric in the amount of 69.6 to 71.7% wt., coated with three layers of polyurethane: 7.6 to 7.0% wt. PU-W; 16.3 to 15.4% wt. PU-S and 6.5 to 5.9% wt. PU-L. The fabric according to claim 6 characterised in that it is manufactured using the process according to claim 1.

AMENDED CLAIMS received by the International Bureau on 16 August 2021 (16.8.2021) A method for manufacturing polyurethane-coated fabrics, hereinafter referred to as the PU-coated fabrics, comprising a stage of coating a substrate - a PU-modified knitted fabric, characterised in that it further comprises the following subsequent processes: a) preparing a PU-W paste composition - a top layer or the face, wherein at the stage of preparing the PU-W paste composition, an aqueous polyurethane solution, preferably aliphatic polycarbonate-based, preferably with the following parameters:

- concentration 30%;

- viscosity 100 mPas;

- elongation at break 375%;

- elongation modulus in 100% - 6 MPa

- softening point 195’C

- tensile strength 35 MPa in the amount of 82.4 to 83.3% wt. is mixed with a surfactant, preferably 100% concentration and viscosity 25 mPas in the amount of 0.2 to 0.3% wt., a rheology modifier, pH 8 and viscosity 5.4 mPas in the amount of 2.0 to 1.5% wt., a cross-linking agent, preferably polycarbonate-based, viscosity 250 mPas in the amount of 3.5 to 3.3% wt., a defoaming agent, preferably silicone-free, viscosity 700 mPas in the amount of 3.5 to 3.3% wt., an adhesion modifier to reduce squeaking, viscosity 3 mPas and pH 5 in the amount of 4.9 to 5.0% wt., an adhesion modifier to improve abrasion resistance, preferably silicone- based, viscosity 150 mPas in the amount of 3.5 to 3.3% wt., the obtained mixture is stirred using an industrial mixer with dispersion blades for 15 minutes until all the components are combined, and the mixture is dyed to a specific colour, deaerated and conditioned for 24 hours, after which a polycarbonate-based cross-linking agent in the amount of 3.5 to 3.3% wt. is added immediately before coating. b) preparing a chemically-foamed PU-S paste composition - a second layer providing thickness and flexibility, wherein:

- at the first stage of preparing the PU-S paste, a mixture of pigments in the amount of 1.4 to 0.8% wt. and a pigment dispersing agent in the amount of 3.5 to 3.0% wt., a cross-lining agent, preferable blocking aromatic isocyanate-based in the amount of 4.5 to 4.0% wt. is prepared, wherein the mixture of pigments is added to the weighted dispersing agent and mixed at low speed in a mixer with dispersion blades for 10 to 15 minutes, the cross-linking agent is added and mixed for 5 to 10 minutes, and the obtained mixture is strained and conditioned for 8 hours,

- at the second stage of preparing the PU-S paste, an aqueous polyurethane solution, preferably aromatic, concentration 93 to 97% and viscosity 50,000 to 100,000 mPas in the amount of 82.5 to 84.6% wt. is mixed with a catalyst, preferably aliphatic isocyanate-based in the amount of 1.8 to 1.3% wt.; a silicone in the amount of 1.4 to 1.1% wt.; a fire retardant, preferably chlorine phosphate-based, liquid, low fogging in the amount of 4.9 to 5.2% wt., all components are mixed using an industrial paddle mixer for 10 minutes, and the mixture of pigments with the dispersing and cross-linking agent prepared in the first stage is added to said paste, mixed for 10 to 15 minutes and deaerated; the paste is not conditioned at this stage;

17

AMENDED SHEET (ARTICLE 19) c) preparing a PU-L paste composition - a third layer bonding the PU-W+PU-S layer with the substrate (knitted fabric), wherein at the day the paste is to be used for coating, a PU-L paste composition is prepared, wherein an aqueous polyurethane solution, preferably polyether-based, pH 6.5 to 7.5, concentration 48 to 52% in the amount of 49 to 51% wt. is mixed with an aqueous polyurethane solution, preferably polyether-based with pH 7 to 8 and concentration 38 to 42% in the amount of 50 to 48% wt., and immediately before coating, a cross-linking agent in the amount of 1 to 0.1% wt. is added to the mixture of two polyurethanes; d) coating, i.e. applying the pastes on a release paper, wherein at the stage of coating a substrate with the PU-W polyurethane paste, the PU-W paste with a viscosity of 100+10 mPas is poured over a release paper, preferably with acrylic coating at the head no. I of the coating machine operating at a linear speed of 9±1 m/min, and the paste applied on the release paper with a basis weight of 30 to 35 g/m2, being a top layer of the fabric is passed through the first heating tunnel, where the top layer paste is crosslinked at 90-100-110°C; the paper with the top layer is passed through a cooling unit to reduce its temperature, and the paper with the top layer is transferred to the head no. )l of the coating machine, where the second PU-S layer with a basis weight of 65 to 75 g/m2 is applied and passed through the second heating tunnel where the PU-S paste is cross-linked and foamed at 150-170-180°C, passed through the cooling unit to reduce its temperature and transferred to the coating head no. Ill where the third laminate PU/L layer with a basis weight of 25 to 30 g/m2 is applied and attached to the substrate, the substrate is pressed by a laminating roller, and the paper with three polyurethane layers and the substrate is passed through the third heating tunnel, where it is cross-linked at 110-130-140-150°C, and the obtained product with a basis weight of 440±20 g/m2 and a thickness of 0.8+0.1 mm is passed through a cooling unit and delaminated, i.e. the coated fabric is separated from the release paper; e) further processing. A PU-coated fabric characterised in that it is manufactured using the process according to claim 1 and that it comprises a substrate - a cotton knitted fabric in the amount of 69.6 to 71.7% wt., coated with three layers of polyurethane: 7.6 to 7.0% wt. PU-W; 16.3 to 15.4% wt. PU-S and 6.5 to 5.9% wt. PU-L.

18

AMENDED SHEET (ARTICLE 19)

Description:
A method for manufacturing coated fabrics using water-based or solvent-free, VOC-free polyurethanes and a fabric obtained using this method

The present invention relates to a method for manufacturing coated fabrics using water-based or solvent-free, VOC-free polyurethanes and a fabric obtained using this method, in particular, for use in the automotive industry.

Background and current problems

The automotive and transport industry, globally the largest consumer of coated fabrics, more and more often demand "safe materials" i.e. materials that do not contain any toxic VOCs, show excellent fire-retardant properties and do not release toxic gas during combustion, e.g. fire. Currently, in the automotive industry, the most commonly used fabrics are based on plasticised PVCs with different additives reducing or retarding flammability, i.e. fire retardants. The fabric properties, including its flammability and toxic properties, depend on its individual components, and in case of coated upholstery fabrics, also on a substrate used - a knitted or woven fabric. The modifiers used may improve some parameters and affect others, as is the case with the PVC- based fabric, which as a polymer shows a high oxygen index and is considered non-flammable, whereas the addition of a plasticiser improves its processing and mechanical properties but reduces its flammability from class VO to class V2. For upholstery fabrics used in vehicles, the most important properties include: flammability, fire propagation rate, thermal energy release rate and rate of emission of toxic combustion products. Nowadays, the focus is on the thermal energy release rate and the amount and type of released toxic products of combustion and pyrolysis. Flame retardants in the PVC-based fabric will provide protection until the composition is combusted, at which point they contribute to the release of toxic gases. The only solution is to develop a composition based on plastics and modifiers without any toxic components and not releasing any toxic gases as a result or thermal decomposition or combustion. Fire safety depends on fabric properties: flammability, smoke production and toxicity of thermal decomposition and combustion products of those fabrics, heat release rate and flame propagation at the surface.

The authors have met the requirements by using green polyurethanes with water-based solvents and a composition of green modifiers.

The purpose of the invention is to develop a technology for manufacturing fabrics using water-based polyurethanes with additives while maintaining basic physical and mechanical parameters, i.e. abrasion resistance, fire retardancy as per the railway standards, tensile strength, tear resistance and improving some parameters, i.e. reducing the basis weight while maintaining product thickness and eliminating toxic VOCs to the limit of detection.

Summary

The invention in its first aspect comprises a method for manufacturing polyurethane-coated fabrics, hereinafter referred to as PU-coated fabrics, including a stage of coating a substrate - a PU-modified knitted fabric, characterised in that it comprises the following subsequent stages:

- preparing a PU-W paste composition - a top layer or the face;

- preparing a chemically-foamed PU-S paste composition - a second layer providing thickness and flexibility; - preparing a PU-L paste composition - a third layer bonding the PU-W+PU-S layer with the substrate (knitted fabric);

- coating, i.e. applying the pastes on a release paper;

- further processing.

At the stage of preparing the PU-W paste composition, an aqueous polyurethane solution, preferably aliphatic polycarbonate-based, with the following parameters:

- concentration 30%;

- viscosity 100 mPas;

- elongation at break 375%;

- elongation modulus in 100% - 6 MPa

- softening point 195°C

- tensile strength 35 MPa in the amount of 82.4 to 83.3% wt. is mixed with a surfactant, preferably concentration 100%, viscosity 25 mPas in the amount of 0.2 to 0.3% wt., a rheology modifier, pH 8 and 5.4 mPas in the amount of 2.0 -1.5% wt., a crosslinking agent, preferably polycarbonate-based, viscosity 250 mPas in the amount of 3.5 - 3.3% wt., defoaming agent, preferably silicone-free, viscosity 700 mPas in the amount of 3.5 -3.3% wt., adhesion modifier to reduce squeaking, viscosity 3 mPas and pH 5 in the amount of 4.9 - 5.0% wt., adhesion modifier to improve abrasion resistance, preferably silicone-based, viscosity 150 mPas in the amount of 3.5 - 3.3% wt. The composition is mixed in an industrial mixerwith dispersion blades for approx. 10-15 minutes until all components are combined. The mixture is dyed to a selected colour, deaerated and conditioned for 24 hours. A polycarbonate-based crosslinking agent in the amount of 3.5 - 3.3% wt. is added immediately before coating.

Simultaneously, a PU-S paste for chemical foaming is prepared. In the first stage of preparing the PU-S paste composition, a mixture of pigments in the amount of 1.4 to 0.8% wt. and a dispersing agent in the amount of 3.5 to 3.0% wt., a cross-linking agent in the amount of 4.5 to 4.0% wt., preferably aromatic isocyanate-based, blocking is prepared. The mixture of pigments is added to the weighted amount of the dispersing agent and stirred at low speed in a mixer with dispersion blades for approx. 10 to 15 minutes, after which the cross-linking agent is added and stirred for approx. 5 to 10 minutes. The mixture is strained and conditioned for 8 hours. In the second stage of preparing the PU-S paste composition, an aqueous solution of polyurethane, preferably aromatic, concentration 93 to 97%; viscosity 50,000 - 100,000 mPas in the amount of 82.5 to 84.6% wt. is mixed with a catalyst, preferably aliphatic isocyanate-based in the amount of 1.8 to 1.3% wt.; a silicone in the amount of 1.4 to 1.1% wt., and a flame retardant, preferably chlorine phosphate-based, liquid, low fogging in the amount of 4.9 to 5.2% wt. The components are stirred in an industrial paddle mixer for approx. 10 minutes. A mixture of pigments, dispersing agent and cross-linking agent prepared in the first stage is added to the paste, stirred for approx. 10 to 15 minutes and deaerated. The obtained paste composition is not conditioned and must be used within 5 hours.

The PU-L paste composition is prepared on the day of coating by mixing an aqueous polyurethane solution, preferably polyether, pH 6.5 to 7.5; concentration 48 to 52% in the amount of 49 to 51% wt. and an aqueous polyurethane solution, preferably polyether, pH 7 to 8; concentration 38 to 42% in the amount of 50 - 48 % wt., after which a cross-linking agent in the amount of 1 to 0.1% wt. is added to the mixture of two polyurethanes immediately before coating.

At the stage of substrate coating with PU-W paste composition, the PU-W paste at 100±10 mPas viscosity is poured over a release paper, preferably with acrylic coating, at the head no. I of a coating machine operating at a linear speed of 9±1 m/min. The paste poured over the release paper with a basis weight of 30 to 35 g/m 2 used as the top layer (face) of the fabric is passed through the first heating tunnel where it is cross-linked at 90-100-110°C, and the paper with the top layer is cooled by passing it through the first cooling unit and transferred to the head no. II of the coating machine where the second PU-S layer with a basis weight of 65 to 75 g/m 2 is applied and passed through the second heating tunnel, where it is cross-linked at 150-170-180°C and foamed; the fabric is cooled in the second cooling unit and transferred to the head no. Ill of the coating machine, where the third laminate PU/L layer with a basis weight of 25 - 30 g/m 2 is applied and attached to the substrate. The substrate is pressed by the laminating roller, and the paper with three polyurethane layers and the substrate is passed through the third heating tunnel, where final cross-linking takes place at 110-130-140-150°C. The product with a basis weight of 440±20 g/m 2 and the thickness of 0.8±0.1 mm is passed through a series of coolers and delaminated, i.e. the coated fabric is separated from the release paper.

In the second aspect, the invention comprises a PU-coated fabric including a substrate - a cotton knitted fabric in the amount of 69.6 - 71.7% wt., coated with three layers of polyurethane: 7.6 to 7.0% wt. PU-

W; 16.3 to 15.4% wt. PU-S and 6.5 to 5.9% wt. PU-L, characterised by better physical and mechanical parameters than the fabrics dedicated for the automotive industry, fire retardant as per the railway standards, and containing no toxic VOCs.

The fabric according to this aspect is manufactured using the process according to the first aspect.

Benefits

The invention has many benefits compared to the solutions known from the art. The method according to the invention reduces the basis weight of the product by using PU-S while maintaining its thickness, flexibility, physical and mechanical parameters, i.e. abrasion resistance, tear resistance or tensile strength. Previously, thick fabrics were only available using chemically-foamed PVC pastes characterised by high emission of toxic gases during combustion which did not conform to PN-EN 45545-2+Al:2015 R2 requirements. Using eco-friendly polyurethanes with water as a solvent, a fabric was obtained that meet the ecological aspects and which does not emit toxic gases as a result of combustion, e.g. during a fire. Previously, coated fabrics with a thickness > 0.7 mm could be manufactured using a coating technology with plasticised PVC, in which the second and the third layer comprise a foamed PVC paste. The fabrics show high basis weight at the thickness > 0.7 mm and high toxicity of gases produced as a result of combustion, e.g. during a fire, and very high smoke production, which is a key factor in fire emergencies, and an important factor to consider for fabrics used in the automotive industry.

Detailed description

The invention is presented below in a detailed description of selected embodiments without any limitations to the scope of protection of the patent.

In the experimental stages, for experimental and comparative purposes, two types of substrate were used: woven and knitted fabric and two types of PU-S paste - the first intended for chemical foaming - PU-S/1 and the second for comparison, intended for mechanical foaming - PU-S/2 were used.

Table 1. Textile substrate parameters.

Preparation of the top layer PU-W paste At this stage, water-based eco-friendly raw materials free from hazardous solvents were used. A key concern was to select a suitable polyurethane type and additives. The following polyurethanes were used in the experimental tests: aliphatic polycarbonate-based, aromatic polycarbonate-based, aliphatic polyester-based, aromatic polyester-based, aliphatic polyether-based and aromatic polyether-based. All polyurethanes were free from hazardous solvents and were intended for coating at 100 - 180°C. For all polyurethanes, the tests were carried out at different concentration, i.e. dry solid content: 10 to 15%, 15 to 20%, 20 to 25%, 25 to 30%, 30 to 35%, 35 to 40%, 40 to 45%, 45 to 50%, 50 to 55%, 55 to 60%, 60 to 65%, 65 to 70%, 70 to 75%, 75 to 80%, 80 to 85%, 85 to 90%, 90 to 95%, 95 to 100%. Different modifiers were added to each polyurethane in different amounts:

- surfactant to improve spreadability of the polyurethane mixture. This raw material does not contain solvents, has low VOC content and a viscosity of 25 mPas at 100% concentration. Added amount: 0 to 1 g per 100 g polyurethane.

- rheology modifier for aqueous polyurethane solutions, viscosity 5.4 mPas and pH 8. Added amount: 0 to 3 g per 100 g polyurethane.

- silicone-free defoaming agent to eliminate foam formed during stirring. Added amount: 0 to 8 g per 100 g polyurethane.

- adhesion modifier to reduce squeaking, improve slippage and stain resistance. Viscosity 3 mPas and pH 5. Added amount: 0 to 8 g per 100 g polyurethane.

- adhesion modifier to improve abrasion resistance, viscosity 150 mPas. Added amount: 0 to 5 g per 100 g polyurethane

- cross-linking agent, polycarbonate-based, solvent-free for cross-linking the polymer. Viscosity 250 mPas, no VOC content. Added amount: 0 to 8 g per 100 g polyurethane.

The compositions were subjected to rheology testing, i.e. viscosity measurements, the coating tests were carried out using the selected release paper, and based on the tests, a suitable polyurethane, its concentration and suitable additives providing the required rheology to guarantee good spreadability on the release paper and no surface defects, e.g. cratering and suitable abrasion resistance, stain resistance and no squeaking in contact with the face surface were selected. Table 2 shows the composition of the obtained mixture.

Table 2. PU-W paste composition

At this stage, a method of mixing the components, i.e. the PU-W paste was improved. The mixture components, apart from the cross-linking agent were added in sequence (see Table 2) and mixed using a mixer with dispersion blades for approx. 15 minutes, dyed white, deaerated and conditioned for 24 hours. Immediately before coating, a suitable amount of the cross-linking agent was added, see Table 2. Preparing the foamed PU-S paste

At this stage, two types of solvent-free polyurethanes were used for comparison, for chemical and mechanical foaming.

The chemical foaming tests included aqueous polyurethane solutions for transfer coating at temperatures between 100 to 180°C: aromatic polyether-based, aliphatic polyether-based, aliphatic polyester- based, aromatic polyester-based. Each polyurethane was used in the concentration range from 93 to 97% and from 97 to 100%. A suitable amount of additives was added to each polyurethane:

- aliphatic isocyanate-based catalyst; 0 to 5 g per 100 g polyurethane;

- silicone to improve spreadability; concentration 98±2%, 0 to 5 g per 100 g polyurethane;

- chlorine phosphate-based flame retardant, liquid, low volatile, low fogging; 0 to 10 g per 100 g polyurethane;

- pigment dispersing agent to reduce viscosity for improved pigment distribution in the paste; 0 to 6 g per 100 g polyurethane;

- blocking aromatic isocyanate-based cross-linking agent; 0 to 10 g per 100 g polyurethane.

A PU-S/1 paste mixing method was improved at this stage. At the first stage, a suitable amount of the dispersing agent was added to a container, followed by the pigment composition and stirred at low speed for approx. 15 minutes, until combined. A cross-linking agent was added and stirred for approx. 10 minutes. The premix was strained on the strainer and conditioned for 8 hours. At the next stage, a base was prepared, i.e. the polyurethane was mixed with a catalyst, silicone and flame retardant using a paddle mixer for approx. 10 minutes, and the paste, i.e. the base prepared in the second stage was mixed with the premix prepared in the first stage, stirred using a paddle mixer for approx. 15 minutes and deaerated. Table 3 shows the composition of PU-S/1 paste.

Table 3 Composition of the PU-S/1 paste

The polyurethanes with pH 8-9 for transfer coating at 100 to 180°C were used in the mechanical foaming tests in the following concentration ranges (dry weight): 40 to 51%; 52 to 61%; 62 to 70%. The foaming process involved foaming, i.e. generating the foam in a special unit. The tests allowed to obtain pastes with 300 to 800 g/m 2 foaming rate. The most optimum foaming rate was determined at 300 g/m 2 at which the foam showed closed pores and the highest flexible, however, a comparison of obtained foam with the chemically foamed PU- S/1 paste showed that the mechanically foamed polyurethane does not show a 'memory' effect and does not return to its initial shape when compressed. At this stage, the optimum foaming process temperatures and the coating line speed were determined. The obtained paste was designated as PU-S/2. The line test parameters:

- temperature 150/170/180°C

- speed 9±1 m/min.

Table 4 Composition of the PU-S/2 paste

Preparing the laminate PU-L paste

Four polyurethane types were used at this stage:

- aqueous polyether-based laminate polyurethane pH 6.5 to 7.5

- aqueous polyester-based laminate polyurethane pH 6.5 to 7.5

- aqueous polyester-based laminate polyurethane pH 7 to 8

- aqueous polyether-based laminate polyurethane pH 7 to 8

The polyurethane type or composition of different polyurethanes, concentrations and suitable crosslinking agent were selected to ensure the required adhesion between the foamed layer and the substrate.

A single composition/laminate PU-L paste was selected (composition, see Table 5).

Table 5 Composition of the laminate PU-L paste

Manufacturing stages according to the invention

The manufacturing method according to the invention comprises the following stages:

- preparing the top layer PU-W paste;

- preparing the chemically-foamed PU-S/1 paste and the mechanically-foamed PU-S/2 paste for comparison;

- preparing the laminate PU-L paste;

- coating the substrate with three layers PU-W+ PU-S/l+PU/L and PU-W/+PU-S/2+PU-L;

- further processing. Preparing the top layer PU-W paste

The raw materials according to the embodiment (see Table 2) were added to a vacuum dispersion mixer in the following order: 30% water-based aliphatic polycarbonate-based polyurethane, surfactant, rheology modifier, defoaming agent, adhesion modifier to reduce squeaking, adhesion modifier to improve abrasion resistance and stirred for 15 minutes. The obtained paste was dyed white, strained in a vacuum strainer with a 0.3 mm mesh size, deaerated and conditioned for 24 hours. A required amount of cross-linking agent was added 30 minutes before coating, stirred for 5 minutes and deaerated.

Preparing the chemically-foamed PU-S/1 and mechanically-foamed PU-S/2 paste

- preparing the PU-S/1 paste for chemical foaming

A weighted amount of the dispersing agent and the pigment composition (Table 3) was added to a mixer with dispersion blades and stirred for 15 minutes, until combined. A cross-linking agent was added to the mixture and stirred for 10 minutes. For the amount of cross-linking agent used, see Table 3. The pre-mixture was strained (0.3 mm mesh size) and conditioned for 8 hours. A polyurethane, catalyst, silicone and fire retardant (Table 3) were added to a paddle mixer and stirred for 10 minutes until combined. The pre-mixture was added to the base paste prepared at the previous stage, mixed using the paddle stirrer for 15 minutes and deaerated.

- preparing the PU-S/2 paste for mechanical foaming

The raw materials according to the embodiment (see Table 4) were added to a paddle mixer, stirred for 15 minutes and deaerated. The obtained paste was foamed on the line during coating using a special foaming unit.

Preparing the laminate PU-L paste

The raw materials according to the embodiment (see Table 5) were added to a paddle mixer, stirred for 15 minutes and deaerated.

Coating the substrate with three layers PU-W+ PU-S/l+PU-L and PU-W/+PU-S/2+PU-L

A release paper with the goat skin texture and two types of textile substrates: cotton/PES woven fabric and cotton knitted fabric were used. Four coating tests were carried out for comparison:

Test no. I: using PU-W pastes; PU-S/1; PU-L substrate: cotton/PES woven fabric

Test no. II: using PU-W pastes; PU-S/1; PU-L substrate: cotton knitted fabric

Test no. Ill: using PU-W pastes; PU-S/2; PU-L substrate: cotton/PES woven fabric Test no. IV: using PU-W pastes; PU-S/2; PU-L substrate: cotton knitted fabric

Test no. I

A PU-W paste with a viscosity of 100±10 mPas was poured over a release paper with acrylic coating at the head no. I of the coating machine operating at a linear speed of 9±1 m/min, controlling the head clearance to ensure that the required amount of paste is applied. The paste poured over the release paper with a basis weight 30 to 35 g/m 2 , used as a top coat was passed through the first heating tunnel, where the top layer was cross-linked at 90-100-110°C, and the coated paper was passed through a cooling unit to reduce its temperature. The paper with the top layer was transferred to the head no. 2 of the coating machine where the second PU-S/1 layer was applied, basis weight 195 - 205 g/m 2 , and transferred to the heating tunnel where the PU-S/1 paste was cross-linked and foamed at 150-170-180°C, passed through the cooling unit and transferred to the head no. 3, where the third laminate PU-L layer with a basis weight of 25 to 30 g/m 2 was applied and attached to a substrate, in this case a 44/56% cotton/PES woven fabric with a basis weight of 170±10 g/m 2 . The substrate was pressed by a laminating roller and along with the paper and three polyurethane layers passed through the third heating tunnel where final cross-linking took place at 110-130-140-150°C. The product with a basis weight of 430±20 g/m 2 and a thickness of 0.8±0.1 mm was passed through the cooling unit and delaminated, i.e. the coated fabric was separated from the release paper.

Test no. II

A PU-W paste with a viscosity of 100±10 mPas was poured over a release paper with acrylic coating at the head no. I of the coating machine operating at a linear speed of 9±1 m/min, controlling the head clearance to ensure that the required amount of paste is applied. The paste poured over the release paper with a basis weight 30 to 35 g/m 2 , used as a top coat was passed through the first heating tunnel, where the top layer was cross-linked at 90-100-110°C, and the coated paper was passed through a cooling unit to reduce its temperature. The paper with the top layer was transferred to the head no. 2 of the coating machine where the second PU-S/1 layer with a basis weight of 65 to 75 g/m 2 was applied and passed through the second heating tunnel where the PU-S/1 paste was cross-linked and foamed at 150-170-180°C, passed through a cooling unit to reduce its temperature and transferred to the head no. 3, where the third laminate PU-L layer with a basis weight of 25 to 30 g/m 2 was applied and attached to a substrate, in this case a 100% cotton knitted fabric with a basis weight of 310±10 g/m 2 . The substrate was pressed by a laminating roller and, along with the paper and three polyurethane layers, passed through the third heating tunnel where final cross-linking took place at 110-130-140-150°C. The product with a basis weight of 430±25 g/m 2 and a thickness of 0.8±0.1 mm was passed through the cooling unit and delaminated, i.e. the coated fabric was separated from the release paper.

Test no. Ill

A PU-W paste with a viscosity of 100±10 mPas was poured over a release paper with acrylic coating at the head no. I of the coating machine operating at a linear speed of 9±1 m/min, controlling the head clearance to ensure that the required amount of paste is applied. The paste poured over the release paper with a basis weight 30 to 35 g/m 2 , used as a top coat was passed through the first heating tunnel, where the top layer was cross-linked at 90-100-110°C, and the coated paper was passed through a cooling unit to reduce its temperature. The paper with the top layer was transferred to the head no. II of the coating machine, where the second PU-S/2 layer was applied using a pump and foamed using a mechanical foaming unit. The applied PU-S/2 layer had a basis weight of 195 to 205 g/m 2 and a foaming rate of 300 g/m 2 . The fabric was passed through the second heating tunnel, where the PU-S/2 paste was cross-linked and foamed at 150-170-180°C, passed through a cooling system to reduce its temperature and transferred to the laminating head no. 3 where the third laminate PU-L layer with a basis weight of 25 to 30 g/m 2 was applied and attached to a substrate, in this case a 44/56% cotton/PES woven fabric with a basis weight of 170±10 g/m 2 . The substrate was pressed by a laminating roller and, along with the paper and three polyurethane layers, passed through the third heating tunnel where final cross-linking took place at 110-130- 140-150°C. The product with a basis weight of 430±25 g/m 2 and a thickness of 0.8±0.1 mm was passed through the cooling unit and delaminated, i.e. the coated fabric was separated from the release paper.

Test no. IV

A PU-W paste with a viscosity of 100±10 mPas was poured over a release paper with acrylic coating at the head no. I of the coating machine operating at a linear speed of 9±1 m/min, controlling the head clearance to ensure that the required amount of paste is applied. The paste poured over the release paper with a basis weight 30 to 35 g/m 2 , used as a top coat was passed through the first heating tunnel, where the top layer was cross-linked at 90-100-110°C, and the coated paper was passed through a cooling unit to reduce its temperature. The paper with the top layer was transferred to the head no. II of the coating machine, where the second PU-S/2 layer was applied using a pump and foamed using a mechanical foaming unit. The applied PU-S/2 layer had a basis weight of 65 to 75 g/m 2 and a foaming rate of 300 g/m 2 . The fabric was passed through the second heating tunnel, where the PU-S/2 paste was cross-linked and foamed at 150-170-180°C, passed through a cooling system to reduce its temperature and transferred to the laminating head no. 3 where the third laminate PU-L layer with a basis weight of 25 to 30 g/m 2 was applied and attached to a substrate, in this case a 100% cotton knitted fabric with a basis weight of 310±10 g/m 2 . The substrate was pressed by a laminating roller and along with the paper and three polyurethane layers passed through the third heating tunnel where final cross-linking took place at 110-130- 140-150°C. The product with a basis weight of 430±25 g/m 2 and a thickness of 0.8±0.1 mm was passed through the cooling unit and delaminated, i.e. the coated fabric was separated from the release paper.

Table 6 Physical and chemical parameters of the fabric according to the invention - Test no. 1

Table 7 Physical and chemical parameters of the fabric according to the invention - Test no. II

Table no. 8. Physical and chemical parameters of the fabric according to the invention - Test no. Ill

Table no. 9. Physical and mechanical parameters of the fabric according to the invention - Test no. IV Conclusions: Based on the test results for samples no. I, II, III and IV, sample no. II meet the technological requirements laid out in the introduction. For comparison, the PU-S/2 paste used on the second coating blade in test no. Ill and IV, i.e. the paste for mechanical foaming did not achieve the required resistance to light and ageing. As a result of 200 hour xenon lamp irradiation, emitting a light at 42 W/m 2 and intensity adjustable from 300 to 400 nm, at 40% humidity and 30,000 kJ/m 2 dose, the fabric underwent a significant degradation. Both the colour and the structure of the sample has changed (cracking, coating delamination). In all four solutions, the same top layer PU-W paste and the same laminate PU-L paste were used, and the analysis of the test results for all four solutions shows that the paste used in the second layer of the fabric, i.e. the PU-S paste, significantly affects the ageing process of the fabric according to the invention. An analysis of combustibility of all four solutions shows difference in combustibility when using the cotton/PES woven fabric without fire retardant. This substrate did not meet the standard requirements for combustibility.