RU2737373C1 - Method of imparting fire-resistance to textile materials - Google Patents

Abstract

FIELD: textile.

SUBSTANCE: invention relates to production of fire-resistant textile materials. Disclosed is a method of imparting fire-resistance to textile materials by treating the latter with flame-retardant antipyrene preparations. Antipyrenes from the group: antimony trioxide with additives of halogen-, phosphorus- and/or nitrogen-containing components are applied on surface of textile fabric in composition of polymer mass on the basis of plasticised PVC, pressed through perforated pattern-dispensers of plate-type or rotary types, having wall thickness of 0.12–0.40 mm, perforation holes diameter of 0.6–2.5 mm and their number per unit surface area of template (0.13–8.4) × 10⁵ m^-2. Further, the material is heat treated at temperature of 140–180 °C for 2–15 minutes.

EFFECT: technical result is increase in fire-retardant effect, resistance to washing, impact of abrasive loads (abrasion and adhesion), reduced contamination of material.

1 cl, 11 ex, 1 tbl, 2 dwg

Description

The invention relates to the field of production of fire-resistant textile materials used in the manufacture of personal protective equipment for various production and emergency repair teams, protective clothing for emergency rescue groups, for the production of tent, shelter and other materials, where fire-resistant and at the same time resistant to operation and to various processing textile materials.

Currently, for imparting fire resistance to textile materials, the most famous and widespread technological solution in our country and abroad is fire retardant impregnation of various textile bases. However, in recent years, developers of flame retardant fabrics have increasingly faced serious problems with this technology. For example, flame retardant impregnations are often not sufficiently resistant to washing, their use usually leads to a significant decrease in the level of resistance of materials to abrasion and to their increased contamination. In addition, many flame retardant impregnations are toxic, and due to this, they impair the sanitary and hygienic characteristics of the protected materials, as well as any impregnations, including fire retardants, are not universal, and they, as a rule, adhere very poorly to synthetic ones, for example, polyester or polyamide fabrics.

The use of the new technical solution proposed in this invention makes it possible to avoid the indicated disadvantages of the traditional technology and to achieve a significant improvement in the set of operational properties of fire-resistant materials - to increase the resistance of these materials to washing, abrasion and snagging, and, as you know, the ability to maintain the fire resistance of textile materials during washing and increasing their resistance to abrasion and to gearing are the most important factors that determine the operational stability of products made from fire-resistant materials processed in this way, and, consequently, improving these indicators has a high economic and technical feasibility. An important advantage of the new method in relation to the problem of fire-resistant clothing is also the fact that when it is used, the contamination of materials is significantly reduced, which contributes to an improved preservation of the appearance of materials during operation and maintaining protective-camouflage or signaling functions in them.

In addition, the use of fire retardants is not in pure form, as in impregnations, but in the form of encapsulated, i.e. as part of a multicomponent polymer capsule, significantly increases their stability on the material, and, consequently, their sanitary and hygienic safety, which is especially important for the use of these materials in various types of fire-resistant clothing or in personal protective equipment. The flame retardant polymer paste applied to the surface of the fabric has high adhesion to any textile substrates, and therefore, unlike the method of fire retardant impregnations, this method of fire protection is universal, because fire retardants in this case are equally well fixed on various textile fabrics and work effectively on any fabrics - cotton, synthetic and mixed.

The materials processed according to the claimed method retain a sufficient level of vapor permeability, and therefore, fire-resistant clothing based on them has good physiological and hygienic tolerance.

A known method of fire-resistant processing of fabrics from cellulose (cotton) fibers, as well as from mixed with polyamide, acrylic and other fibers, which consists in impregnating the fabric with an aqueous solution (polyhydroxyorgano) phosphonium salt (Pat. 2107761 Russian Federation, IPC D03D 15/12, D06M 11 / 68. A method of processing fabric to impart fire-resistant and water-resistant properties / XiaoPing Lei, David William Speak and others; applicant and patentee Albright & Wilson UK Limited - No. 93048156/12; filed. 10.21.1993; published 03.27.1998. No. 29). After impregnation, the fabric is dried and treated with gaseous ammonia to cure the polymer precondensate inside the fibers, followed by oxidation with hydrogen peroxide, ensuring effective fixation of the phosphonium compound inside the fabric fibers and its uniform distribution. With this method, it is possible to achieve good fire resistance of fabrics, but its disadvantage is the complexity of execution (multi-stage, including processing the fabric with an aqueous solution, spinning, long-term drying at low temperature, long exposure at room temperature, treatment with gaseous ammonia, oxidation with hydrogen peroxide, washing and final drying ), and in addition, the resulting material is not protected from the outside by a mechanoprotective layer, and therefore it does not have sufficient resistance to abrasion and snagging, and, in addition, for the same reason, it is easily contaminated upon contact with various, including hazardous media ...

Another known method of imparting flame retardancy to a material containing cellulose fibers (Patent 1830090 Russian Federation, IPC D06M 13/44, D06M 101/06, D06M 101/32. A method of imparting flame retardancy to a material containing cellulose fibers / Jeffrey William Smith; applicant and patentee Albright and Wilson Limited - No. 884355888; declared 06/05/1987; publ. 07/23/1993. Bull. No. 23), includes impregnation of the starting material with an aqueous solution of organophosphorus compounds, drying, treatment with ammonia, and in order to increase the efficiency of processing as organophosphorus compounds are used precondensate of tetrakisoxymethylphosphonium chloride and urea. The disadvantages of this method are also its multistage and complexity, as well as insufficient resistance of the resulting material to abrasion, to snagging and increased contamination upon contact with various, including hazardous media.

In the patent (Pat. 2614957 Russian Federation, IPC D06M 15/643, D06M 23/10, D06M 15/432, C09K 21/14, C09D 183/12, C09D 183/04, C08G 77/395, C08G 77/388, C08G 77/26, C08G 77/10, B05D 5/00. A method of obtaining coatings that impart fire resistance to materials / Izmailov B.A., Komarova L.G. and others; applicant and patentee Federal State Budgetary Institution of Science Institute of Organoelement Compounds named after A.N. Nesmeyanova of the Russian Academy of Sciences (INEOS RAS) - No. 2015136682; application 28.08.2015; published 31.03.2017. Bulletin No. 7) a method of fire protection of textile materials is proposed by obtaining grafted siloxane coatings on their surface, including sequential application of an alcoholic solution of oligo (aminopropyl) ethoxysiloxane and an aqueous solution of nitrilotrimethylenephosphonic acid to the surface of the material, and after each solution is applied, the material is dried in air and subjected to heat treatment to form a phosphorus-containing siloxane coating. The method, according to the authors, is very effective, but its disadvantages in this case are the need to use organic solvents, and besides, it is known that silicone-based coatings are characterized by low values of mechanical strength, and therefore in such materials there is a significant drop in the protective properties of the material over time. and their instability to aqueous treatments, in particular to washing. The material obtained by this method also has insufficient mechanical resistance in operation - low resistance to abrasion, to snagging and increased contamination upon contact with various, including hazardous, media.

There is also known a method of fire retardant impregnation (modification) of polyester fabrics, including applying to the surface of a composition containing an aqueous dispersion of an anionic polymer, a fire retardant and an aqueous emulsion of a fluoropolymer, drying and heat treatment of the resulting coating, and as a fire retardant, a phosphate-containing flame retardant is used in the composition, and a fluoropolymer is used as a fluoropolymer hyperbranched fluoropolymer based on perfluorinated carboxylic acids of the C ₆ -C ₇ series (Pat. 2666098 Russian Federation, IPC D06M 15/21, D06M 13/282. Method for modifying polyester fabrics / Lavrentieva E.P., Kovalchuk L.S., et al. ; applicant and patentee - Limited Liability Company "Chaikovskaya Textile Company" (OOO "Chaikovskaya Textile Company") - No. 2017141117; filed. 11/27/2017; published 09/05/2018. Bull. No. 25). The disadvantages of this method are the need to use poisonous organofluorine low molecular weight compounds, and also, as in the previous examples, due to the absence of special mechano-protective layers on the front side of such fabrics, the fire-resistant fabrics thus obtained have low resistance to abrasion, to entanglement, they easily contaminated by contact with various, including hazardous media, because during operation, the surface of the fabric, in this case, is in direct contact with pollutants.

The closest to the protected method of imparting fire resistance to textile materials is the method of flame retardant impregnation of fabrics with preparations based on phosphoric acid and nitrogen-containing compounds (for example, OP preparation), described in (Safronova, N.A. Overalls and special footwear for workers in the chemical, oil refining and petrochemical industries ( reference manual) - 2nd ed., revised and supplemented - Moscow: Chemistry, 1984 - S. 18-20.). According to this method, the fabric is treated with an aqueous solution of carbamide (or other nitrogen-containing compounds) and phosphoric acid and subjected to heat treatment at a temperature of 150 ° C and higher for several minutes. In the course of heat treatment, complex chemical transformations occur, leading to the formation of an insoluble product of the interaction of phosphoric acid and a nitrogen-containing base on the surface of the fabric. In the specific case of using impregnation with OP, the fabric is treated with an aqueous solution of dicyandiamide, phosphoric acid and diammonium phosphate, then the impregnated fabric is heat treated at a temperature of 170 ° C. Also, ammonia is added to the impregnating solution, which prevents the processes of tissue destruction as a result of the action of phosphoric acid at high temperatures. OP impregnation and its modified versions are widely used in industry. With this method, a sufficiently high level of fire resistance of fabrics is achieved, however, its significant disadvantages are the low resistance of fire retardant impregnation to water treatments, in particular to washing, low wear resistance of the protected fabrics themselves (their low resistance to abrasion and snagging), increased contamination upon contact with external environments. All these disadvantages are due to the fact that the fire retardants applied in this way to the fabric during processing and during the operation of the resulting fire-resistant fabrics are not protected from direct effects of the external environment - water, abrasive, polluting, etc.

The task is to search for a new technology for applying fire retardants to textile materials, in which, along with the required fire resistance, a new set of important consumer properties appears in the material: increased resistance of fire retardants, and therefore their fire retardant effect to water treatments, in particular to washing, at the same time increased resistance of the material itself to abrasive influences, i.e. to abrasion and to meshing and reduced contamination of the material in contact with various media.

The specified technical result is achieved by the fact that in the method of imparting fire resistance to textile materials, including the treatment of the latter with fire retardants - fire retardants, characterized in that fire retardants from the group: antimony trioxide with additives of halogen-, phosphorus- and / or nitrogen-containing components are applied to the surface of the textile fabric in the composition of a polymer mass based on plasticized PVC, pressed through perforated dispensing templates of plate or rotary types, having a wall thickness of 0.12-0.40 mm, a diameter of perforation holes of 0.6-2.5 mm and their number per unit area of the template surface (0.13-8.4) × 10 ⁵ m ^-2 , followed by heat treatment of the material at a temperature of 140-180 ° C for 2-15 minutes. As a result, polymeric, discretely located hemispherical elements - fire-retardant and mechanoprotective - are formed on the surface of the material, which are then hardened and hardened during the heat treatment of the resulting material. The mechanism of the fire-retardant action of such elements is that when the material is exposed to intense heat fluxes or an open flame, the polymer matrix collapses and from it into the ignition zone flammable substances are released, such as, for example, antimony oxyhalides, which neutralize OH * radicals - which, as you know are the most active sources of ignition of polymeric materials, or various nitrogen-containing phlegmatizers, i.e. diluents of combustible mixtures, and a number of other flame-extinguishing products (Bulgakov, V.K. Modeling the combustion of polymeric materials / V.K. Bulgakov, V.I. Kodolov, AM Lipanov - Moscow: Chemistry, 1990.). As a result, the activity of the processes of gas-phase ignition of the material is inhibited, and the material itself is extinguished. At the same time, in the usual state, fire-retardant elements, possessing high adhesion and cohesive strength, are well fixed on the surface of the fabric and form a discrete-polymer mechanoprotective layer on it, and due to this they effectively protect the material from its front side from various mechanical influences, in particular from abrasive loads and from gearing. The flame retardants encapsulated in the polymer have high water resistance, and they are not washed out of the polymer matrix during any water treatments, in particular during washing - hence the increased resistance to these treatments of the fire retardant effect with this technology, and, in addition, it also gives the obtained by this method special sanitary and hygienic safety materials. In addition, the presence on the outside of the material of bulk elements that limit its contact with the external environment also leads to a significant decrease in the contamination of the material, including such hazardous products as fuels and lubricants (POL), radioactive products, aggressive or toxic chemical and biological substances. This, in turn, contributes to improved preservation of the appearance of materials during operation and the maintenance of protective-masking or signaling functions in them.

Examples of manufacturing the claimed material

Example 1. In a paddle-type mixer with a capacity of 3 liters, the following components were loaded in the ratio: emulsion polyvinyl chloride grade PVC-EP-6602-S - 100 wt. h; plasticizer di (2-ethylhexyl) phthalate - 35 wt. h; plasticizer (fire retardant) trichloroethyl phosphate - 10 wt. h; heat stabilizer calcium stearate - 2 wt. hours, fire retardants: antimony trioxide - 16 wt. including and decabromodiphenyl oxide - 5 wt. h. The resulting mixture was stirred for 15 minutes and left to swell for 6 hours at room temperature. After holding, the mixture was thoroughly ground on a roller paint grinder to form a polymer paste with a grinding degree of 40-60 microns (assessment by the Klin device, GOST 6589-74). The thus prepared polymer paste was applied to polyester fabric art. 280/19 TU 8218-032-10725218-2006 by punching through a printed template - a perforated plate with the following parameters: plate thickness 0.40 mm, hole diameter 1.0 mm and number of holes 130,000 m ^-2 . Then the coated fabric was placed in a heat chamber with a temperature of 170 ° C for 4 min. The resulting material has the form (Fig. 1).

Example 2. Unlike example 1, polymer paste was applied to nylon fabric art. 56005 (GOST 16428-89) using a printed template - a perforated plate with the parameters: plate thickness 0.12 mm, hole diameter 0.6 mm and the number of holes 840,000 m ^-2 .

Example 3. Unlike example 1, polymer paste was applied to viscose fabric art. 36001 Cr (GOST 16428-89). The holding time and temperature in the heat chamber were 15 min and 140 ° C, respectively.

Example 4. Unlike example 1, the polymer composition contained 8 wt. including diammonium phosphate, and the polymer paste was applied to cotton fabric with a surface density of 220 g / m ² (GOST 21790-2005). The holding time and temperature in the heat chamber were 2 min and 180 ° C, respectively.

Example 5. In contrast to example 1, polymer paste was applied to cotton-polyester fabric TKO-O (TU 17-02-15-285-92) using a printed template - a perforated plate with parameters: plate thickness 0.30 mm, hole diameter 2, 5 mm and the number of holes 60,000 m ^-2 .

Example 6. In a mixer equipped with a slow-speed stirrer in the form of two Z-shaped rotors, with a capacity of 20 liters, the following components were loaded in the ratio: emulsion polyvinyl chloride of the PVC-EP-6602-S brand - 100 wt. h; plasticizer di (2-ethylhexyl) phthalate - 35 wt. h; plasticizer (fire retardant) trichloroethyl phosphate - 10 wt. h; heat stabilizer calcium stearate - 2 wt. hours, fire retardants: antimony trioxide - 16 wt. including and decabromodiphenyl oxide - 5 wt. h. The resulting mixture was stirred for 45 minutes and left to swell for 6 hours at room temperature. After holding, the mixture was thoroughly ground on a roller paint grinder to form a polymer paste with a grinding degree of 40-60 microns (assessment by the Klin device, GOST 6589-74). The thus prepared polymer paste was applied to a polyester fabric art. 280/19 TU 8218-032-10725218-2006 by punching through a rotary printing template with the parameters: thickness 0.35 mm, length of the working area 1620 mm, report 640 mm, hole diameter 1.0 mm and number of holes 61300 m ^-2 , after which the resulting material was passed through a heat chamber with a temperature of 180 ° C for 2 min. The material has the form (Fig. 2).

Example 7. In contrast to example 6, the following components were loaded into the mixer in the ratio: emulsion polyvinyl chloride grade PVC-EP-6602-S - 100 wt. h; plasticizer di (2-ethylhexyl) phthalate - 35 wt. h; plasticizer (fire retardant) trichloroethyl phosphate - 10 wt. h; heat stabilizer calcium stearate 2 wt. hours, fire retardant - antimony trioxide 20 wt. h.

Example 8. In contrast to example 6, the following components were loaded into the mixer in the ratio: emulsion polyvinyl chloride grade PVC-EP-6602-S - 100 wt. h; plasticizer di (2-ethylhexyl) phthalate - 35 wt. h; plasticizer (fire retardant) trichloroethyl phosphate - 10 wt. h; heat stabilizer calcium stearate - 2 wt. hours, fire retardants: antimony trioxide -15 wt. hours, diammonium phosphate - 5 wt. h and magnesium hydroxide - 5 wt. h.

Example 9. In contrast to example 6, the following components were loaded into the mixer in the ratio: emulsion polyvinyl chloride grade PVC-EP-6602-C - 100 wt. h; plasticizer di (2-ethylhexyl) phthalate - 45 wt. h; heat stabilizer calcium stearate - 2 wt. hours, fire retardants: antimony trioxide - 16 wt. including and decabromodiphenyl oxide - 5 wt. h., and the rotary printing template had the following parameters: hole diameter 2.1 mm and the number of holes 13100 m ^-2 .

Example 10. In contrast to example 6, the rotary printing template had the parameters: hole diameter 1.7 mm and the number of holes 24500 m ^-2 .

Example 11 is a prototype. In accordance with the description of the prototype (see p. 5-6), cotton fabric with a surface density of 220 g / m ² (GOST 21790-2005) was impregnated with an aqueous composition based on impregnation of OP with a concentration of 17%. The impregnated fabric was passed through squeeze rolls and placed in a heat chamber. Drying time and temperature in the heating chamber were 4 min and 170 ° C, respectively.

The results of evaluating the properties of the obtained materials are presented in the table.

As can be seen from the above experimental data, the use of the new technical solution proposed in this invention makes it possible, by providing sufficient fire resistance of various fabrics, to significantly increase the resistance of textile materials to abrasion and to snagging, while this effect is very significant - sometimes by 5-6 or more times. This means that products, in particular fire-resistant clothing made of fabrics made using the new method, have a significantly higher stability in operation, which increases the efficiency of the specialists using it, and in addition, this also gives an obvious economic effect. The data presented in the table also confirm the fact of improved preservation of the very effect of fire resistance of these fabrics during repeated washings, while the obtained data also implies the universality of the new fire retardant effect, i.e. its effectiveness for various types of fabrics, including cotton, polyester, mixed, etc., and this new method compares favorably with the traditional method of fire retardant impregnations, in particular the impregnation of OP, the effectiveness of which, as we have experimentally established on the example of polyester fabric art. 280 drops sharply after the first wash (these data are not shown in the table due to the low level of the characteristics obtained).

In the course of the experimental studies, the fact of a significant (1.5-2 times) decrease in the contamination of materials obtained by the new method was also confirmed. Corresponding experiments were carried out using I-12A oil, and these results are easily extrapolated to other products, including such as fuels and lubricants, radioactive products, aggressive or toxic chemical and biological substances. Achievement of this effect contributes to improved preservation of the appearance of products, including clothing made of appropriate materials during their operation and maintenance of protective-camouflage or signaling functions in them.

In addition, the analysis of the distinctive features of materials obtained by the new method of fire protection and the features of their appearance (see Fig. 1 and 2), allows us to make assumptions about their other advantages. So, in particular, the use of fire retardants not directly (with small amounts of fixers) on the canvases, as in impregnations, but as part of a multicomponent polymer capsule resistant to treatments and various contacts, obviously leads to a significant improvement in the sanitary and hygienic characteristics of fabrics with fire retardants, which is especially important for the use of these materials in the composition of various types of fire-resistant clothing.

Thus, the inventive method of applying fire retardants to textile materials provides, along with the required fire resistance, a new set of important consumer properties of textile materials, including: increased resistance of fire retardants, and therefore their fire retardant effect to water treatments, in particular to washing, at the same time, increased resistance of the material itself to abrasion (to abrasion and to meshing) and reduced contamination of the material in contact with various media.

Claims (1)

A method of imparting fire resistance to textile materials by processing the latter with fire retardants, fire retardants, characterized in that fire retardants from the group: antimony trioxide with additives of halogen-, phosphorus- and / or nitrogen-containing components are applied to the surface of the textile fabric as part of a polymer mass based on plasticized PVC, pushed through through perforated dispensing templates of plate or rotary types, having a wall thickness of 0.12-0.40 mm, diameter of perforations 0.6-2.5 mm and their number per unit area of the template surface (0.13-8.4) × 10 ⁵ m ^-2 , followed by heat treatment of the material at a temperature of 140-180 ° C for 2-15 minutes.

Images