RU2412625C1 - Combined multi-layer material - Google Patents

Abstract

FIELD: personal use articles. ^ SUBSTANCE: invention relates to special-purpose materials for sewing clothes and relates to combined multi-layer material. Design of combined multi-layer material includes upper woven layer, diffusion layer, polymer membrane and lower knitted layer. Polymer membrane is formed on upper woven layer by coagulation of composition including solution of PEU in dimethylformamide, non-ionogenic surfactant, microcrystalline cellulose with subsequent coagulation, washing with simultaneous process of diffusion of polyurethane composition into structure of woven layer for the depth of 16.7-30,0% of woven layer thickness to form diffused layer, drying, application of adhesive layer at the side of membrane, duplication with knitted base at speed of technological process of 2.0-7.0 m/min with ratio of layers of finished combined multi-layer material making 0.49-0.65:0.10-0.19:0.25-0.32. ^ EFFECT: invention makes it possible to develop material, having high complex of consumer properties. ^ 1 dwg, 7 tbl

Description

The present invention relates to the design of a combined multilayer material for sewing various clothes intended for equipping power structures, professional clothes associated with extreme operating conditions, sports and tourism and having a high range of consumer properties.

Multilayer materials are known, including the outer, intermediate and inner layers, where the outer layer is a fabric for the top of the product, the inner is a bulk insulation having hydrophilic fibers and having hygienic properties, and the intermediate is a layer of adhesive material (Patents of the Russian Federation No. 2004167, 2004168, 2004169, 2004170, 2004171).

The disadvantage of these designs is the low hygiene and special properties that determine the functional characteristics of the materials (lack of sufficient watertightness under the influence of precipitation, or lack of vapor permeability, which causes discomfort when wearing outerwear due to the lack of moisture (sweat) from the inside of the clothing), and also the duration of the technological process of making clothes due to the additional operation of fastening the package by means of adhesive compounds and their limited use.

Known design of the combined material (RF Patent No. 2275158), one of the elements of which is a polymer membrane, impervious to water, but transmitting steam.

However, the specified design of the multilayer material is laborious and not technologically advanced.

The closest technical solution for creating the design of a combined multilayer material for clothing with a complex of physico-mechanical and hygienic properties is a multilayer combined material according to the patent of the Russian Federation No. 2167702.

The design of the specified combined multilayer material is based on the use of a polytetrafluoroethylene (PTFE) polymer membrane, including an outer upper woven layer of polyester fiber with a water-repellent fluorocarbon finish, a lower layer of synthetic knitted fabric, between which is a laminate made of hydrophobic PTFE with biaxially oriented hydroformed microporous adhesive) with reactive isocyanate groups of at least three in the molecular chain ly, the upper fabric layer connected gravure printing method (overlap) dot adhesive pattern with a hydrophobic PTFE membrane, and the lower layer of knitted fabric is connected with duplication of the hydrophilic polyurethane coating applied to the back side of the membrane.

The advantages of this combined multilayer material in comparison with the currently known domestic and foreign combined laminated materials for clothes are obvious and provide high strength, water resistance and, most importantly, hygienic properties of the clothing material.

However, the technological process of obtaining the main element of the combined multilayer material — the PTFE membrane — is technologically complicated and multi-operational (see Table 1) and, in addition, this membrane requires additional protection, because on products of PTFE used according to the prototype, a film of salts is formed upon contact with salt water (sweat) (Handbook of plastics edited by V.M. Kataev et al., t.1, p.129, M .: Chemistry, 1975 g), which during operation can lead to loss of functionality of the membrane as the main element of the combined multilayer material.

Analysis of table 2 of the known technical solution for the prototype showed that the design of the combined multilayer material is limited, since with the upper woven layer 0.35 mm thick, 0.03 mm membrane, PES adhesive 0.01-0.02 mm, knitwear 0.21 -0.23 mm we get the ratio of the layers with a total thickness of the combined multilayer material of 0.6-0.61 mm, respectively: 0.57-0.58: 0.05-0.05: 0.017-0.033: 0.34-0, 35, which, due to a narrow range of layer ratios, limits variation to the main structural elements (thicknesses of woven layers and membrane thickness) and, as COROLLARY, does not allow to expand the range of clothing materials.

The technical task of the invention is to develop a combined multilayer material with a reduced cost due to lower energy costs and technological operations when obtaining the main element of the combined multilayer material - a polymer membrane while increasing its hygiene indicators, physico-mechanical properties and expanding the range of clothing materials.

The problem is solved in that in a combined multilayer material including an upper woven layer, a laminate of a polymer membrane and a hydrophilic polymer coating and a lower knitted layer, a polymer membrane with a thickness of 0.08-0.12 mm is formed by a knife blade with a gap of 0.15-0 , 20 mm at a process speed of 2.0-7.0 m / min on the upper woven layer with a thickness of 0.310 and 0.518 mm from a solution of a composition based on polyether urethane (PEU) of the Vitur-0512 brand (TU 6-55-221-1085- 2003) in an amount of 80,0-150,0 g / m ² (dry basis), prepared by catalytic reaction of polyethylen enbutylene glycol adipate, ethylene glycol and 4,4'-diphenylmethane diisocyanate in dimethylformamide with a dry matter content of 25.0-60.0 wt.%, dynamic viscosity at 25 ° C and 80 ° C, respectively 30.0-60.0 and 8, 0-15.0 Pa · s, including nonionic surfactant in an amount of 0.3-1.0 wt.%, Microcrystalline cellulose with a particle size of 20.0-40.0 μm in an amount of 2.0-20.0 wt.% (TU 7505-706-55-90) and dimethylformamide in an amount of 19.0-45.4 wt.% (GOST 20289-74), followed by immersion of the material in a coagulation bath containing a mixture of 20.0-40, 0 wt.% Dimethylformamide and 8 0.0-60.0 wt.% Water with a temperature of 40-50 ° C, washing in a washing bath with water at a temperature of 50 ° C until the content of dimethylformamide in it is not more than 3.0 wt.%, With the simultaneous formation of a diffusion layer on based on a coagulated polyester urethane composition in the structure of the woven layer with a thickness of 16.7-30.0% of the thickness of the woven layer, drying the material at 110-160 ° C, applying the adhesive layer in the form of a spot irregular coating based on ethylene vinyl acetate with temperature to the finished material from the membrane side melting point 70 ° C in an amount of 15.0 g / m ² yl polyamide powder with a melting point of 116-118 ° C in an amount of 20 g / m ² or powdered polyamide having a melting temperature of 125 ° C, doubling with knitted foundation with a thickness of 0.20-0.22 mm at a ratio of the combined layers of the laminate: 0 49: 0.19: 0.32; 0.62: 0.13: 0.25 and 0.65: 0.10: 0.25, respectively, with a thickness of 0.63, 0.798 and 0.888.

The woven layers according to the examples are pile fabrics with a pile density of 40.0-60.0% of the surface area of the fabric, pre-treated with a water repellent agent based on an emulsion of siloxane copolymers in a 2% solution of polyvinyl alcohol in an amount of 0.10-0.15 wt. % by weight of material. The mechanism of hydrophobization of textile materials is considered in the book by N.F. Orlov et al. “Organosilicon compounds in the textile and light industry”, “Light Industry”, Moscow, 1966, pp. 63-70, “Encyclopedia of Polymers”, “Soviet Encyclopedia ", M., 1977, v. 1, pp. 625-632.

The choice of polyether urethanes to create a membrane layer in a multilayer material is primarily due to their physicochemical properties and the ability to form structures with developed porosity.

We found that the polyurethane membrane polymer layer can be in the form of a microporous or monolithic film. For microporous coatings, hydrophobic or slightly hydrophilic polyurethanes are used; vapor permeability in this case is determined by their structure. An important role is played by pore diffusion permeability, and the solution to the problem of providing the necessary vapor permeability is to create a certain value of through porosity.

The permeability of monolithic polymer layers is due to intermolecular spaces. Vapor penetration is facilitated by the use of a polymer whose macromolecules have a sufficient amount of hydrophilic groups, such as —OH, —COOH or —NH ₂ , which can form labile hydrogen bonds with water vapor molecules. In this case, the mechanism of passage of water vapor consists of three stages: absorption by hydrophilic functional groups, diffusion through intermolecular voids, and desorption from the external surface. The rate of passage of water vapor through these layers is inversely proportional to their thickness. Therefore, the coating should be of sufficient thickness and there should be no defects leading to water permeability, and on the other hand, it should be thin enough to maintain a certain degree of permeability to water vapor.

The functioning of such systems is based on a large difference in the size of the vapor molecules (about 0.0004 microns) and raindrops, the diameter of which is about 100 microns.

To obtain a membrane polymer layer in a multilayer composite material with high permeability with respect to water vapor, nonionic surfactants and fibrous hydrophilic fillers were additionally introduced into the polymer composition at certain ratios.

The introduction of nonionic surfactants due to their good adsorption at the phase boundary and on the surface of structural elements promotes the formation of a uniform porous structure. The introduction of hydrophilic fibrous fillers in the form of microcrystalline cellulose, on the one hand, increases the hydrophilicity of the membrane polymer layer, on the other hand, located in the pores of the structure, they keep the pores from completely closing during shrinkage due to relaxation processes, and thereby also contribute to the formation of a uniform through microporous structure.

The introduction of nonionic surfactants and hydrophilic fillers into the composition of the polymer composition made it possible to create a polymer microporous membrane layer (pore number 10 ⁷ / cm ³ , pore size 1-5 μm), which allows water molecules to penetrate in the vapor state and not to let drop moisture pass, i.e. providing a high level of vapor permeability and water tightness with high strength and durability of the multilayer composite material.

The hot-melt coating was applied at the installation with a chromed engraving shaft at a shaft temperature of 70.0-120.0 ° С and spot irregular coating was applied with 10.0-20.0 g / m ² applied, and duplication was carried out on a duplicate calender at a pressure of 0 7-1.5 kg / cm ² .

Finished combined multilayer materials at apparent density have:

upper woven layer 0.46-0.50 g / cm ³ membrane 0.60-0.65 g / cm ³ bottom knit layer 0.3-0.34 g / cm ³ total density combined materials 0.44-0.46 g / cm ³ breathability, cm ³ / cm ² · s 0.83-0.84

The drawing shows a design diagram of a combined multilayer material (section).

Table 2 shows the comparative characteristics (indicators) of combined multilayer materials in comparison with the material obtained by a known technical solution.

According to the invention used:

1. Tufted and hydrophobized textile bases:

Fabric composition: viscose - 33%, polyester - 67%, art.32-11 TU 858-5505-2000, twill.

Composition fabrics: cotton - 51%, polyester - 49%.

Composition fabrics: polyester - 100%, GOST 28486-90.

Knitwear (lining - 3rd layer) - GOST 28554-90, art. 1544076, 1544168.

To conduct experiments on optimizing the designs of combined multilayer materials and expanding the range of clothing materials with high consumer properties, we used a different assortment of newly developed textile foundations, which are fabrics made of cotton polyester, viscose-polyester and synthetic yarns introduced by the domestic industry to replace imported fabrics. Physico-mechanical properties of tissues are shown in table 3.

Table 4 shows the hygienic characteristics of the tissues.

2. Solutions of polyester urethanes manufactured by the industry on the basis of various diisocyanates, simple and complex oligoesters and glycols, the dependence of the properties of which are given on their structure are given in the Encyclopedia of Polymers, M .: Soviet Encyclopedia, 1977, v.3, p.63- 70 and in the monograph by J.H. Saunders, K.K. Frisch, "Chemistry of Polyurethanes", M .: "Chemistry", 1968, p. 324-427.

3. Nonionic hydrocarbon surfactants, aqueous solutions which reduce the surface tension of water to 28-30 erg / cm ² ("Encyclopedia of Polymers", M .: "Soviet Encyclopedia", 1977, v.2, s.666-678) .

4. Powdered thermoplastics for duplication of the knitted layer - a copolymer of ethylene with vinyl acetate (15 wt.% Vinyl acetate) with a dispersion of 80-200 microns, bulk density of 0.32 g / cm ³ , melting point 70-80 ° C and a melt viscosity of 28 cPa;

- a copolymer of vinyl acetate with ethylene in a ratio of 28:72 with a melt flow rate (MFR), g / 10 min at 120 and 145 ° C, respectively 2.0 and 30.0, with a dispersion of 200-400 microns, a melting point of 90 ° C and bulk density of 0.35 g / cm ³ ;

- polyamide powder with a dispersion of 80-200 microns, bulk density of 0.53 g / cm ³ and a melting point of 116-118 ° C;

- powdered polyamides with a bulk density of 0.45-056 g / cm ³ , a dispersion of 60-200 microns and a melting point of 105-125 ° C.

The proposed design of the combined multilayer material is realized due to the fact that when the woven layer moves on a hard alluvial table with the speed and the gap between the woven layer and the knife blade specified by this technical solution, the PES composition partially penetrates the structure of the woven layer mainly due to the diffusion process, which continues in a coagulation bath in a solvent-non-solvent medium while coagulating it in the form of a transitional diffusion layer in the structure of the woven material and the membrane.

The diffusion process ends when the content of dimethylformamide in the wash bath is less than 12.0 wt.% And is finally formed and fixed in the structure of the woven layer during the drying process, resulting in the formation of a combined multilayer material and a transition diffusion layer is formed that passes into the membrane.

The diffusion process does not have a clear boundary of the propagation front. The penetration depth of the PES layer into the thickness of the woven layer was determined by sections of laminates from 10 samples of each fabric. It was found that with a membrane thickness of 0.08 mm, the thickness of the diffusion layer in the tissues used (thickness 0.31-0.548 mm) is 0.052-0.090 mm, with 0.1 mm it is 0.08-0.137 mm, and with 0.12 mm - 0.09-0.164 mm (16.7-30.0%). Thus, in the process of obtaining a combined multilayer material, the membrane is fixed in thickness.

The drawing shows a design diagram of a combined multilayer material (section), including a woven layer (1), a layer of a coagulated in the thickness of the woven material PES composition (1a), passing into the membrane layer (2) and knitwear (3).

The fibers of the textile base and the PES of the diffusion layer form a tight weave having a fine-fiber porous structure, which, in all likelihood, provides high hygienic characteristics of the combined multilayer material by maintaining a constant partial vapor pressure (the process of vapor condensation through the thickness of the combined multilayer material is slowed down or absent) from inner clothing space and strength characteristics due to the properties of the diffusion layer.

The cost of the proposed combined multilayer material is significantly lower than known.

The test of the combined multilayer material was carried out according to the indicators:

"Breaking load" GOST 17316-71 "Tear Resistance" GOST 17074-71 "Rigidity" GOST 8977-74 "Resistance to repeated bending" GOST 8978-75 "Breathability" GOST 8973-77 "Permeability" GOST 22944-78 "Vapor permeability" GOST 22900-78 “Hygroscopicity and moisture loss” GOST 8971-78 Clothing fabrics: "Gap and elongation" GOST 3813-72 "Tearing load" GOST 17922-72 For technical fabrics, respectively GOST 29104.4.91 and GOST 29104.5.91 "Abrasion Resistance" GOST 18976-73 "Water Resistance" GOST 3816-81

Table 1. The main operations of technological processes and modes of their execution Famous Proposed Technological operation Modes Technological operation Modes Temperature ° C Time min Pressure, kg / cm ² Temperature ° C Speed m / min Tape extrusion Energy intensive process 100-200 Drawing on the upper woven layer of the polyester-urethane composition 20-25 2-7 Sintering tape 327-342 1-3 - Coagulation 40-50 2-7 Longitudinal hood 200-300 - - Flushing fifty 2-7 Thinning 200-300 - - Drying 110-160 2-7 Reeling - - - Duplication 70-125 2-7 Temperature control 250-327 40-60 - Transverse hood - - 6-12 Heat setting 332-340 10-20 - Grease removal 40-80 - - Drying 110-130 20-60 -

Table 4 Indicators of tissue hygiene №№ Indicators Hygroscopicity,% Moisture recovery,% Vapor permeability, g / m ² days Water permeability, cm / h one 2 3 four 5 one 2.1 1.7 1150 instantly 2 4.7 3,7 1054 " 3 2.0 1.55 993.6 " four 5.2 4.1 985 " 5 3.6 2.7 760 " 6 5.2 4.6 777.6 " 7 4.4 3.8 691 " 8 1.37 0.99 726 " 9 7.8 7.1 760 " 10 5.8 5.2 786 " eleven 7.4 6.3 786 " 12 7.4 6.6 786 "

The main indicators and the ratios of the layers of combined multilayer materials were determined, including the above woven layers, PES membranes and knitwear as the lining, which are presented below (Table 5-7). Knitwear was duplicated with a laminate using powdered thermoplastics with a melting point of 70-125 ° C (see page 8 of the description).

Table 5 Designs of the proposed combined multilayer materials and their main elements №№ Thickness mm Layer ratio the cloth membrane knitwear composite laminate one 0.31 0.12 0.20 0.63 0.49: 0.19: 0.32 2 0.33 0.10 0.20 0.63 0.52: 0.16: 0.32 3 0.35 0.08 0.20 0.63 0.55: 0.13: 0.32 four 0.35 0.10 0.21 0.66 0.53: 0.15: 0.32 5 0.378 0.08 0.21 0.66 0.57: 0.12: 0.31 6 0.378 0.10 0.20 0.678 0.56: 0.15: 0.29 7 0.378 0.12 0.21 0.708 0.53: 0.17: 0.30 8 0.428 0.08 0.20 0.718 0.60: 0.11: 0.29 9 0.428 0.08 0.22 0.728 0.59: 0.11: 0.30 10 0.428 0.12 0.21 0.758 0.56: 0.16: 0.28 eleven 0.474 0.08 0.21 0.764 0.62: 0.11: 0.27 12 0.474 0.10 0.21 0.784 0.60: 0.13: 0.27 13 0.518 0.08 0.20 0.798 0.65: 0.10: 0.25 fourteen 0.474 0.12 0.21 0.804 0.59: 0.15: 0.26 fifteen 0.526 0.08 0.22 0.826 0.64: 0.10: 0.26 16 0.518 0.10 0.21 0.828 0.63: 0.12: 0.25 17 0.526 0.10 0.21 0.836 0.63: 0.12: 0.25 eighteen 0.548 0.08 0.22 0.848 0.64: 0.10: 0.26 19 0.548 0.12 0.22 0.888 0.62: 0.13: 0.25

Table 6 Indicators of the functional properties of combined multilayer materials №№ Indicators Hygroscopicity,% Moisture recovery,% Vapor permeability, g / m ² days Water permeability, cm / h GOST 22944-78 one 2 3 four 5 one 5.3 4.8 680 0 2 6.6 5.7 680 0 3 5,4 4.8 670 0 four 5.2 4.9 680 0 5 6.6 6.2 660 0 6 5.2 4.8 660 0 7 4.4 3.8 691 0 8 5,4 4.9 680 0 9 6.5 6.2 720 0

Table 7 Indicators of physical and mechanical properties of combined multilayer materials №№ Indicators Thickness mm Breaking load, kgf prod. e.g. e.g. Elongation,% prod. e.g. e.g. Tear resistance, kgf prod. e.g. e.g. Abrasion resistance, cycles Membrane thickness 0.08 mm one 0.63 86.3 / 68.2 26.7 / 37.3 21.0 / 13.2 over 45000 2 0.718 127.0 / 87.2 33.0 / 35.7 17.8 / 16.5 also 3 0.848 143.5 / 50.0 58.6 / 24.0 20.8 / 7.5 - “- Membrane thickness 0.10 mm four 0.63 91.1 / 71.7 25.0 / 37.7 14.3 / 10.4 - “- 5 0.784 146.6 / 41.0 51.1 / 19.5 6.0 / 5.9 45000 6 0.836 110.0 / 72.1 22.0 / 29.4 25.3 / 12.6 over 45000 Membrane thickness 0.12 mm 7 0.63 89.0 / 32.0 24.2 / 36.6 15.5 / 8.0 also 8 0.708 87.0 / 83.3 33.0 / 31.0 21.3 / 15.5 - “- 9 0.888 147.3 / 40.0 60.0 / 19.5 13.0 / 9.2 - “-

Analysis of the materials presented (Tables 2-7) allows us to state the fact that the proposed design of combined multilayer materials provides an increase in the physicomechanical properties of products based on them with improved hygienic indicators of clothing products and, in addition, this design is acceptable for all groups of fabrics with thicknesses and surface densities other than those given by examples in the ranges of 0.31-0.378 mm, 0.378-0.518 mm, 0.518-0.548 mm, and provides an extension of the range of finished clothing products (kurt ki, sportswear, special clothing, etc.) with a reduced energy intensity of the process of obtaining a combined multilayer material, which leads to a reduction in the cost of finished products.

Claims (1)

A combined multilayer material including an upper woven layer, a laminate of a polymer membrane and a hydrophilic polymer coating and a lower knitted layer, characterized in that the polymer membrane with a thickness of 0.08-0.12 mm is formed with a knife blade with a gap of 0.15-0.20 mm at a process speed of 2.0-7.0 m / min on the upper woven layer from a solution of a composition based on polyether urethane in an amount of 80.0-150.0 g / m ² obtained by the catalytic reaction of polyethylene butylene glycol adipate, ethylene glycol and 4,4'-diphenyl methanediisocyanate in dimethylformamide with dry matter content of 25.0-60.0 wt.%, dynamic viscosity at 25 and 80 ° C, respectively, 30.0-60.0 and 8.0-15.0 Pa · s, including nonionic surfactant in an amount 0.3-1.0 wt.%, Microcrystalline cellulose with a particle size of 20.0-40.0 microns in an amount of 2.0-20.0 wt.% And dimethylformamide in an amount of 19.0-45.4 wt.% , followed by immersion of the material in a coagulation bath containing a mixture of 20.0-40.0 wt.% dimethylformamide and 80.0-60.0 wt.% water with a temperature of 40-50 ° C, washing in a washing bath with water at a temperature 50 ° C until dimeti is contained in it formamide not more than 3.0 wt.%, with the simultaneous formation of a diffusion layer based on a coagulated polyester urethane composition in the structure of the woven layer at a depth of 16.7-30.0% of the thickness of the woven layer, drying the material at 110-160 ° C, applying to finished material from the membrane side of the adhesive layer in the form of a dot coating based on powdered thermoplastics with a melting point of 70-125 ° C in an amount of 10.0-20.0 g / m ² , duplication at a pressure of 0.7-1.5 kg / cm ² knitted with the foundation at a ratio of combined layers of a multilayer mat rial, respectively: 0,49-0,65: 0,10-0,19: 0,25-0,32.

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