EP2524993A1 - Textile fireproofing method - Google Patents

Textile fireproofing method Download PDF

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Publication number
EP2524993A1
EP2524993A1 EP20110166319 EP11166319A EP2524993A1 EP 2524993 A1 EP2524993 A1 EP 2524993A1 EP 20110166319 EP20110166319 EP 20110166319 EP 11166319 A EP11166319 A EP 11166319A EP 2524993 A1 EP2524993 A1 EP 2524993A1
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EP
European Patent Office
Prior art keywords
textile
bath
component
process according
drying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20110166319
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German (de)
French (fr)
Inventor
Johan Deschietere
Luc Carlier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CTF 2000 NV
Original Assignee
CTF 2000 NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CTF 2000 NV filed Critical CTF 2000 NV
Priority to EP20110166319 priority Critical patent/EP2524993A1/en
Priority to PCT/EP2012/057627 priority patent/WO2012156190A1/en
Priority to CN201280023618.9A priority patent/CN103534404B/en
Priority to ES12718640.1T priority patent/ES2526795T3/en
Priority to US14/117,614 priority patent/US9074316B2/en
Priority to EP20120718640 priority patent/EP2710184B1/en
Priority to BR112013029415-9A priority patent/BR112013029415B1/en
Publication of EP2524993A1 publication Critical patent/EP2524993A1/en
Priority to HK14106364A priority patent/HK1193129A1/en
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/272—Unsaturated compounds containing sulfur atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/392—Nitroso compounds; Nitro compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/41—Amides derived from unsaturated carboxylic acids, e.g. acrylamide
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/422—Hydrazides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • D06M13/53—Cooling; Steaming or heating, e.g. in fluidised beds; with molten metals
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
    • D06M15/673—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain containing phosphorus and nitrogen in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention relates to a flameproofing process of textiles, as well as flame retardant textiles thus obtained.
  • the flame retardancy of textiles is a technique that is well known today and used in many fields where it is desired to have textiles (clothing (work), fabrics, fabrics, and others) comprising natural and / or synthetic fibers. , flame resistant, that is to say, little flammable, even non-flammable.
  • US 4,765,796 for example, relates to a fireproofing treatment of a colored textile, in particular cotton, comprising a step of immersion in a bath containing a salt of tetrakis (hydroxymethyl) phosphonium (THPx) and urea, followed by steps of polymerization, neutralization and oxidation, washing and drying.
  • THPx hydroxymethyl phosphonium
  • the documents US 4,842,609 and US 4,750,911 relate to similar treatments applicable respectively to cotton / polyester and cotton / nylon textiles.
  • a first object of the invention is to provide a flame retardant treatment suitable for any type of textile, which allows to optimize their quality simultaneously in terms of aesthetics, feel and resistance to washing.
  • Another object of the invention is to provide a flame retardant treatment for any type of textile that is simple to implement, without, or with little, release of irritating and toxic odors (due to formaldehyde), both during treatment itself, only in the finished product.
  • This mixture crosslinks the phosphorus compound / urea polymer on the fabric. Furthermore, the oxidation in steps c) (due to the increase in pH following the decomposition of urea to ammonia) and d) in the phosphorus of the abovementioned polymer increases its insolubility.
  • the crosslinking mixture contributes to a better fixation of the polymer on the textile, and thus, with the aforementioned oxidation, excellent washing resistance. At the same time, it greatly reduces the content of free formaldehyde that can evaporate from fireproof textiles and thus irritate and intoxicate their users.
  • the excellent resistance to washing the flame retarded textiles according to the method of the invention makes it possible to reduce their transport rate, which is beneficial for the touch (hand) and therefore for the comfort of the user, and / or to prolong their flame retardancy and therefore their duration of use.
  • the main constituent of component A is chosen from phosphorus compounds known for their flame-retarding properties, and more particularly chosen from phosphates, phosphines, phosphinates and phosphonium salts.
  • phosphonium salts the tetrakis (hydroxymethyl) phosphonium salts, known under the generic name THPx, are particularly preferred, and in particular THPS (THP sulfate), THPC (THP chloride), THPP (THP phosphate), and others such as THPS-Urea, THPC-Urea, ... THPS is particularly preferred.
  • compatible means “non-reactive and stable under the conditions of use according to the invention.
  • Components A and B may optionally comprise one or more anti-odor agents capable, where appropriate of absorbing or masking the odor of the phosphorus compound described above. Indeed, some phosphorus compounds, especially THPx, very often have a very unpleasant odor, and it is not uncommon for them to cause headaches and severe irritation in people who have to work with these products without specific protections.
  • the anti-odorous agents may be chosen from covering scenting agents (odor absorbing or masking agents or the like) commonly used and compatible with components A and B.
  • the anti-odorant agent (s) are chosen from those which are stable. in component A, inert with respect to components A and B, and resistant to the temperature of use, that is to say during the textile treatment process which is described later in the present description.
  • phosphorus compounds and in particular THPx, more particularly THPS, prepared according to selective processes, making it possible to obtain phosphorus compounds of high purity, containing no or very little impurities, by-products, which are responsible for the bad odors usually associated with said phosphorus compounds.
  • THPx produced using a method operating without excess formaldehyde is used.
  • an anti-odorant is not necessary.
  • one or more anti-odorants may be added with the phosphorus compounds of high purity described above, in order to provide a pleasant odor to component A, if desired or required for the intended use.
  • the amount of anti-odorant agent (s) used can vary in large proportions depending on the desired effect, the nature of the anti-odor agent (s), the nature and the amount of the compound (s) present in the component. A. As a rule, this amount varies from a few ppm by weight to a few percent by weight, typically from 1 ppm by weight to 10% by weight, preferably from 5 ppm by weight to 5% by weight, preferably 10 ppm. at 3% by weight, more preferably from 100 ppm by weight to 2% by weight relative to the total weight of component A.
  • Component A can be prepared according to any method known per se, and generally by simply mixing together the various compounds of component A, in any order.
  • the pH buffer may be chosen from pH buffers known to those skilled in the art, it being understood that it is compatible with urea and inert with respect to it.
  • the pH buffers that may be used are advantageously chosen from ammonium phosphates, ammonium chlorides, ammonium sulphates, and ammonium carbonates, and mixtures thereof, phosphate ammonium is preferred.
  • These pH buffers can also be used in combination / mixing with one or more acids selected from phosphoric acid, sulfuric acid, citric acid, maleic acid and others in order to precisely adjust the pH to the required value. for the process according to the invention.
  • the pH buffer allows the pH to be fixed, but also and above all acts as a "catalyst" for the decomposition of urea into ammonia, this decomposition giving rise, as indicated above, to increasing the pH to a preliminary oxidation of the polymer during step c) of drying.
  • Component B comprises, optionally but advantageously, at least one oxidizing agent, preferably chosen from nitrogen compounds, of more preferably, among the nitro-aryls, and, by way of non-limiting example, the oxidizing agent is the sodium salt of 3-nitrobenzenesulphonic acid.
  • This oxidizing agent gives the polymer, in the oven, an oxidation additional to that which takes place in step c) following the decomposition of urea ammonia, and the maintenance of the latter oxidation when the textile is waiting in the dry state before undergoing the final oxidation in the second bath.
  • the action of this oxidizing agent contributes to maximizing the oxidation of the polymer, thus the washing resistance of the flame-retarded textile and its duration of use.
  • the amount of oxidizing agent can vary in large proportions and is generally set at an oxidative weight / urea weight ratio of between 1/2 and 1/4, advantageously about 1/3.
  • Component B may also include various other additives, fillers, anti-odorants, softeners, rheology agents, viscosifiers, foaming agents, anti-foaming agents, stabilizers, and the like, as well as one or more flame retardant or retardant agents. of flames.
  • the two-component composition A and B as defined above may be in the form of two separate components, which will be mixed just before use.
  • the two-component composition may be in the form of a ready-to-use solution comprising both components A and B.
  • the two-component composition comprising components A and B, as just defined, in separate or mixed form, finds a particularly suitable use in the flame retardant treatment of textiles.
  • the textiles which can receive the flame-retardant treatment with the two-component composition according to the present invention can be of any type, and in particular textiles based on natural fibers, whether they be vegetable or animal (cotton, linen, wool, and others), and / or based on synthetic fibers, such as for example polyester-based fibers, polyamide 6 and 6.6, and others.
  • Cotton / cotton / cotton based textiles based on cotton / polyamide are preferred, and among these are those whose weight per square meter is between about 100 g / m 2 and about 600 g / m 2 .
  • the textiles which can be subjected to the flame retardant treatment according to the present invention can be at any stage of their manufacture, that is to say that they can be subjected to flame retardant treatment when they are in the form of sewn textile or knitted, before or after dyeing, or in the form of textiles that have already undergone one or more finishing treatments.
  • the component B used for the flame retardant treatment according to the present invention will be adapted according to the nature of the fibers constituting the textile, for example depending on whether the textile is cotton or polyester / cotton blend fibers .
  • the first bath (step a) is prepared by simple mixing of component A and component B (or using the mixture of components A and B ready for use).
  • the weight ratio component A / component B can vary in large proportions, in particular depending on the nature of the phosphorus compound. This ratio is adjusted so as to form a polymer between the phosphorus compound of component A and the urea of component B.
  • the first bath may further comprise a fabric softener which may have a role of processing aid in English.
  • the fabric softener may be of any type known to those skilled in the art and advantageously chosen from fatty acids, silicone emulsions, silicone microemulsions, polysiloxanes, and for example, without limitation, the softening agent is the Addisoft ®, marketed by CTF 2000.
  • a polysiloxane reacts with both the textile with the polymer so give the coated fabric of the qualities of flexibility and thus comfort for the user.
  • it because of its hydrophilic character, it promotes the oxidation step d) the reaction with hydrogen peroxide and therefore improves the resistance to washing the flame retarded textile by means of this oxidizing compound.
  • the textile to be impregnated in the first bath prepared in step a), is advantageously, but not necessarily, previously washed with water to make it clean and in particular free of any alkali or other chemical residues from any previous treatment.
  • the pH of the water used for this prewash is advantageously between 6 and 7, which may be finely adjusted by adding an acid, for example an organic acid, such as citric acid.
  • the impregnated fabric obtained in step b), "undried”, generally in continuous rotary motion can be left on standby for a period that can vary between about 2 hours and 24 hours, before performing the next step.
  • This operation (“pad / batch process” in English) is advantageous, but not mandatory. It is also possible to dry and polymerize directly after impregnation as described below.
  • the impregnated textile is then subjected to a high oven temperature, typically greater than or equal to 130 ° C., advantageously at a temperature of between 150 and 160 ° C. vs.
  • the upper limit is set at about 200 ° C oven temperature and preferably 165 ° C.
  • the temperatures measured on the textile are preferably between 145 and 154 ° C.
  • step c) during which the above-mentioned polymerization reaction takes place, is carried out for as short a time as possible, for obvious reasons of efficiency of the complete flame retardant treatment process.
  • the drying is considered satisfactory when the relative humidity of the dried textile at the outlet of the oven is between 0% and 5% by weight, this level being preferably 0% by weight.
  • the polymer thus formed, already polymerized around and in the textile fibers is then subjected to oxidation in the second bath, preferably by increasing the pH, to a value of between 8 and 10 and by means of the at least one compound oxidant.
  • this oxidation reaction it is preferred to carry out this oxidation reaction by increasing the pH, by immersing the textile comprising the polymer in a basic bath comprising an aqueous solution of alkaline hydroxide, such as sodium hydroxide. Under these conditions, the oxidation reaction is relatively slow and is accelerated by means of an effective amount of the at least one oxidizing compound, which will preferably be hydrogen peroxide.
  • the amount of hydrogen peroxide can vary in large proportions depending on the amount of polymer to be oxidized and the pH value.
  • the crosslinking mixture of diacetone acrylamide and at least one organic acid dihydrazide preferably selected from the dihydrazides of adipic acid, sebacic acid, succinic acid and isophthalic acid is also used. as a "chemical scavenger" of aldehyde. It has a double effect, that is to say to improve by crosslinking the washing resistance of the flame retardant textile and to avoid the diffusion of harmful substances into the environment.
  • adipic acid dihydrazide and diacetone acrylamide are present in the second bath in a weight ratio of 1, and preferably each at a concentration of 0.5% by weight bath.
  • the textile thus treated is then subjected to several washes, in order to eliminate the residues of the fireproofing treatment.
  • the washing is advantageously carried out at a temperature of between 25 ° C. and 75 ° C., for example at around 60 ° C., with water brought to a pH greater than or equal to 7, in order to eliminate any product having not reacted.
  • the washings are advantageously added with a base, such as, for example, an alkaline hydroxide, preferably sodium hydroxide. You can also add a soap in the wash water.
  • the last washes are carried out with pure water in order to bring the pH of the final washing waters to a pH value close to or greater than 7. If this is necessary to adjust the pH value to a value close to or greater than 7, an acid may be added, for example a weak acid, such as citric acid, maleic acid.
  • the washing waters may also comprise, where appropriate, one or more textile softeners, such as, for example, those indicated above.
  • the flame retardant textile is recovered and dried according to the usual drying methods.
  • the textile can then be subjected to one or more usual post-treatments for textiles well known to those skilled in the art, selected from, but not limited to, antimicrobial treatment, water repellent treatment, oil repellent treatment, coating, and others.
  • the flame retarded textiles obtained by the process according to the invention can then be cut, sewn and more generally be used for the manufacture and manufacture of any textile-based element, such as protective clothing, draperies, technical textiles, mattress ticks, upholstery fabrics, tent cloths, and others.
  • the method of the present invention as described above has many advantages over fireproofing treatments known in the prior art, and among them, that of the excellent resistance to washing fireproof textiles to reduce their rate of carriage, which is beneficial for the touch (hand) and therefore for the comfort of the user, and / or extend their flame retardancy and therefore their lifetime.
  • the textiles obtained by the process according to the invention respect the human-ecological standards such as ⁇ ko-Tex 100 class 1.
  • composition 1.18 gives rise to fireproof coatings having both a content free formaldehyde significantly lower (165 against 253 ppm) and a higher surface weight (303 against 291 g / m 2 ) after oxidation and 1 washing.
  • the selection of a diacetone acrylamide / dihydrazide mixture instead of a conventional aldehyde trap therefore makes it possible to achieve an optimum in terms of human-ecological compatibility and washing resistance.
  • Table 2 below compares the washing resistance (50 washes) of 50/50 flame retarded cotton / polyester textiles according to the invention by means of a mixture of adipic acid dihydroxide / diacetone acrylamide (samples 2.1 and 2). 2.2 below) to that obtained without resorting to this mixture (2.3 and 2.4).
  • the results of limited flame spread tests according to EN ISO 15025 are also included.
  • Table 3 shows the results of tests performed on 8 samples of polyester / cotton. Optimum results in wash resistance and feel are obtained for oven temperatures between 150 and 160 ° C. ⁇ b> Table 3 ⁇ / b> No. Dry weight (g) Weight after padding (g) Emport (g) Weight after fixation (g) Oven temperature (° C) Add on (g) Attaching / touch Weight loss after washing (%) 3.1 71.13 144.07 102.5 110.30 120 35.5 No fixing 32.0 3.2 78.05 145.56 86.5 108.19 130 27.8 Light fixation 17.0 3.3 75,60 148.62 96.75 108.06 140 30.0 Fixation 5.6 3.4 71.38 144.32 102.2 104.31 150 31.5 Fixation 0.9 3.5 73,20 150.53 105,64 107.61 160 31.9 Fixing / hard touch 0.8 3.6 73.22 153,06 104.80 108.30 170 32.4 Fixing / hard touch 0.8 3.7
  • Example 4 Incidence of the temperature measured on the textile and its relative humidity (RH) at the outlet of the oven on the resistance to washing textiles and their flammability.
  • Table 4 shows the results of flammability tests (FR) carried out on 9 samples of polyester / cotton and made according to standard EN 531-532, after 50 washes according to ISO 1715797.
  • the temperature T of the samples is measured by the intermediate thermostrips.
  • Table 4 ⁇ / b> Sample no HR (%) Residence time in the oven (s) T (° C)

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Abstract

Treating fireproofing textiles, comprises (a) preparing a first bath comprising a composition having two components A and B, (b) impregnating the textile to be treated in the bath obtained in the step (a), (c) heat-drying the impregnated textile, during the polymerization reaction of the urea of component B and the phosphorous compound of component A, (d) stabilizing and neutralizing by an oxidation reaction of the polymer obtained in the step (c) in a second bath, (e) washing in water and drying the treated textile, and (f) recovering the fireproofed textile. Treating fireproofing textiles, comprises (a) preparing a first bath comprising a composition having two components A and B, where the component A comprises at least one phosphorous compound and the component B comprises urea and at least one pH buffer, (b) impregnating the textile to be treated in the bath obtained in the step (a) of which the pH is 4-6, (c) heat-drying the impregnated textile, during the polymerization reaction of the urea of component B and the phosphorous compound of component A, (d) stabilizing and neutralizing by an oxidation reaction of the polymer obtained in the step (c) in a second bath, (e) washing in water and drying the treated textile, and (f) recovering the fireproofed textile, where the second bath comprises, in addition to at least one oxidizing compound, a mixture of diacetone acrylamide and at least one organic acid dihydrazide.

Description

Domaine de l'inventionField of the invention

La présente invention concerne un procédé d'ignifugation de textiles, ainsi que les textiles ignifuges ainsi obtenus.The present invention relates to a flameproofing process of textiles, as well as flame retardant textiles thus obtained.

IntroductionIntroduction

L'ignifugation des textiles est une technique aujourd'hui bien connue et utilisée dans de très nombreux domaines où l'on souhaite disposer de textiles (vêtements (de travail), tissus, toiles, et autres) comprenant des fibres naturelles et/ou synthétiques, résistants aux flammes, c'est-à-dire peu inflammables, voire ininflammables.The flame retardancy of textiles is a technique that is well known today and used in many fields where it is desired to have textiles (clothing (work), fabrics, fabrics, and others) comprising natural and / or synthetic fibers. , flame resistant, that is to say, little flammable, even non-flammable.

Cependant, aucun des traitements proposés jusqu'à aujourd'hui n'est pleinement satisfaisant pour le consommateur final, les textiles traités présentant des propriétés inadaptées au marché. Les utilisateurs demandent des textiles ignifugés à la fois résistant au lavage, agréables à porter, présentant une ignifugation durable, et non toxiques pour le corps et l'environnement. A cet égard, ils doivent respecter des normes humano-écologiques telles que l'Öko-Tex 100 classe 1.However, none of the treatments proposed until today is fully satisfactory for the end consumer, treated textiles with properties unsuitable for the market. Users require flame retardant textiles that are both wash-resistant, comfortable to wear, durable in flame retardance, and non-toxic to the body and the environment. In this respect, they must respect humano-ecological standards such as the Öko-Tex 100 class 1.

Etat de la techniqueState of the art

On connaît dans la technique des traitements d'ignifugation de textiles recourrant à des compositions de bain d'immersion comprenant un composé phosphoré et de l'urée.Flame retardant textile treatments using immersion bath compositions comprising a phosphorus compound and urea are known in the art.

US 4 765 796 , par exemple, concerne un traitement d'ignifugation d'un textile coloré, notamment de coton, comprenant une étape d'immersion dans un bain contenant un sel de tétrakis(hydroxyméthyl)phosphonium (THPx) et de l'urée, suivie par des étapes de polymérisation, de neutralisation et d'oxydation, de lavage et de séchage.
Les documents US 4 842 609 et US 4 750 911 portent sur des traitements similaires applicables respectivement sur des textiles en coton/polyester et en coton/nylon. US 4,765,796 for example, relates to a fireproofing treatment of a colored textile, in particular cotton, comprising a step of immersion in a bath containing a salt of tetrakis (hydroxymethyl) phosphonium (THPx) and urea, followed by steps of polymerization, neutralization and oxidation, washing and drying.
The documents US 4,842,609 and US 4,750,911 relate to similar treatments applicable respectively to cotton / polyester and cotton / nylon textiles.

Ces traitements ne confèrent pas au textile une résistance au lavage suffisante, ce qui nécessite un taux d'emport important afin de satisfaire aux tests d'ignifugation réalisés après de multiples lavages.
Cet important taux d'emport se traduit malheureusement par un défaut d'esthétique et de confort des textiles traités, qui sont très rigides au toucher et ne permettent donc pas une grande liberté de mouvement, ce qui est particulièrement désavantageux pour des vêtements de travail en raison de la répercussion sur la productivité. Par ailleurs, le piégeage du formaldéhyde, irritant et toxique, qui est dégagé lors de l'étape d'oxydation du polymère THPx/urée, n'est décrit dans aucun des documents précités.These treatments do not give the textile a sufficient resistance to washing, which requires a significant carry rate to meet fireproofing tests carried out after multiple washings.
This high rate of carriage unfortunately results in a lack of aesthetics and comfort of treated textiles, which are very rigid to the touch and therefore do not allow great freedom of movement, which is particularly disadvantageous for work clothes in because of the impact on productivity. Furthermore, the entrapment of formaldehyde, irritating and toxic, which is released during the oxidation step of the THPx / urea polymer, is not described in any of the aforementioned documents.

Par conséquent, le besoin demeure quant à un procédé d'ignifugation de textiles permettant d'obtenir des produits finis présentant à la fois des qualités humano-écologiques, esthétiques, de confort, et d'ignifugation sur la durée.Therefore, the need remains for a textile flame retardant process for obtaining finished products having both humano-ecological qualities, aesthetics, comfort, and fireproof over time.

Résumé de l'inventionSummary of the invention

Un premier but de l'invention est de procurer un traitement ignifuge adapté à tout type de textiles, qui permet d'optimaliser leur qualité simultanément sur le plan de l'esthétique, du toucher et de la résistance au lavage.A first object of the invention is to provide a flame retardant treatment suitable for any type of textile, which allows to optimize their quality simultaneously in terms of aesthetics, feel and resistance to washing.

Un autre but de l'invention vise à procurer un traitement ignifuge pour tout type de textiles qui est simple de mise en oeuvre, sans, ou avec peu, de dégagement de mauvaises odeurs irritantes et toxiques (dues au formaldéhyde), tant pendant le traitement lui-même, que dans le produit fini.Another object of the invention is to provide a flame retardant treatment for any type of textile that is simple to implement, without, or with little, release of irritating and toxic odors (due to formaldehyde), both during treatment itself, only in the finished product.

D'autres objectifs encore apparaîtront dans la description de la présente invention qui suit.Still other objects will become apparent from the description of the present invention which follows.

Il a maintenant été découvert que ces objectifs sont atteints, en totalité ou au moins en partie, grâce au procédé d'ignifugation des textiles selon la présente invention.It has now been discovered that these objectives are achieved, in whole or at least in part, by the textile flame retardancy method of the present invention.

Ainsi, un objet de l'invention consiste en un procédé de traitement d'ignifugation de textiles comprenant au moins les étapes suivantes :

  1. a) préparation d'un premier bain comprenant une composition à deux composants A et B, le composant A comprenant au moins un composé phosphoré et le composé B comprenant de l'urée et au moins un tampon pH ;
  2. b) imprégnation du textile à traiter dans le bain obtenu à l'étape a) dont le pH est compris entre en substance 4 et en substance 6 ;
  3. c) séchage du textile imprégné par chauffage, séchage au cours duquel se produit la réaction de polymérisation de l'urée du composant B et du composé phosphoré du composant A ;
  4. d) stabilisation et neutralisation par réaction d'oxydation du polymère obtenu à l'étape c) dans un deuxième bain ;
  5. e) lavage à l'eau et séchage du textile traité ; et
  6. f) récupération du textile ignifugé,
Selon l'invention, le deuxième bain comprend, outre au moins un composé oxydant, un mélange de diacétone acrylamide et d'au moins un dihydrazide d'acide organique.Thus, an object of the invention is a textile flame retardant treatment process comprising at least the following steps:
  1. a) preparing a first bath comprising a two-component composition A and B, component A comprising at least one phosphorus compound and compound B comprising urea and at least one pH buffer;
  2. b) impregnation of the textile to be treated in the bath obtained in step a), the pH of which is between substance 4 and substance 6;
  3. c) drying the impregnated textile by heating, drying during which the polymerization reaction of the urea of component B and the phosphorus compound of component A;
  4. d) stabilization and neutralization by oxidation reaction of the polymer obtained in step c) in a second bath;
  5. e) washing with water and drying the treated textile; and
  6. f) recovery of the flame retarded textile,
According to the invention, the second bath comprises, in addition to at least one oxidizing compound, a mixture of diacetone acrylamide and at least one dihydrazide of organic acid.

Ce mélange réticule le polymère composé phosphoré/urée sur le textile. Par ailleurs, l'oxydation aux étapes c) (due à la hausse du pH suite à la décomposition de l'urée en ammoniac) et d) du phosphore du polymère précité augmente son insolubilité.This mixture crosslinks the phosphorus compound / urea polymer on the fabric. Furthermore, the oxidation in steps c) (due to the increase in pH following the decomposition of urea to ammonia) and d) in the phosphorus of the abovementioned polymer increases its insolubility.

Par conséquent, le mélange réticulant contribue à une meilleure fixation du polymère sur le textile, et donc, avec l'oxydation précitée, à une excellente résistance au lavage. Par la même occasion, il diminue fortement la teneur en formaldéhyde libre susceptible de s'évaporer des textiles ignifugés et donc d'irriter et d'intoxiquer leurs utilisateurs.Therefore, the crosslinking mixture contributes to a better fixation of the polymer on the textile, and thus, with the aforementioned oxidation, excellent washing resistance. At the same time, it greatly reduces the content of free formaldehyde that can evaporate from fireproof textiles and thus irritate and intoxicate their users.

D'autre part, l'excellente tenue au lavage des textiles ignifugés selon le procédé de l'invention permet de réduire leur taux d'emport, ce qui est bénéfique pour le toucher (main) et donc pour le confort de l'utilisateur, et/ou de prolonger leur caractère ignifuge et donc leur durée d'utilisation.On the other hand, the excellent resistance to washing the flame retarded textiles according to the method of the invention makes it possible to reduce their transport rate, which is beneficial for the touch (hand) and therefore for the comfort of the user, and / or to prolong their flame retardancy and therefore their duration of use.

Description de formes de réalisation particulièresDescription of particular embodiments

Le constituant principal du composant A est choisi parmi les composés phosphorés connus pour leurs propriétés ignifugeantes, et plus particulièrement choisis parmi les phosphates, phosphines, phosphinates et sels de phosphonium. Parmi les sels de phosphonium, on préfère les sels de tétrakis(hydroxyméthyl)-phosphonium, connus sous la dénomination générique de THPx, et en particulier les THPS (sulfate de THP), THPC (chlorure de THP), THPP (phosphate de THP), et autres comme le THPS-Urée, THPC-Urée,... On préfère en particulier le THPS.The main constituent of component A is chosen from phosphorus compounds known for their flame-retarding properties, and more particularly chosen from phosphates, phosphines, phosphinates and phosphonium salts. Of the phosphonium salts, the tetrakis (hydroxymethyl) phosphonium salts, known under the generic name THPx, are particularly preferred, and in particular THPS (THP sulfate), THPC (THP chloride), THPP (THP phosphate), and others such as THPS-Urea, THPC-Urea, ... THPS is particularly preferred.

Dans la description de la présente invention, le terme « compatible » signifie « non susceptible de réagir et stable, dans les conditions d'utilisation selon l'invention ».In the description of the present invention, the term "compatible" means "non-reactive and stable under the conditions of use according to the invention".

Les composants A et B peuvent éventuellement comprendre un ou plusieurs agents anti-odorants capables, le cas échéant d'absorber ou de masquer l'odeur du composé phosphoré décrit plus haut. En effet, certains composés phosphorés, en particulier les THPx, sont très souvent dotés d'une odeur très désagréable, et il n'est pas rare qu'ils provoquent des maux de tête et des irritations sévères chez les personnes qui sont amenées à travailler avec ces produits sans protections spécifiques.Components A and B may optionally comprise one or more anti-odor agents capable, where appropriate of absorbing or masking the odor of the phosphorus compound described above. Indeed, some phosphorus compounds, especially THPx, very often have a very unpleasant odor, and it is not uncommon for them to cause headaches and severe irritation in people who have to work with these products without specific protections.

Les agents anti-odorants peuvent être choisis parmi les agents odorants couvrants (absorbants ou masquants d'odeurs ou autres) communément utilisés et compatibles avec les composants A et B. En particulier le ou les agents anti-odorants sont choisis parmi ceux qui sont stables dans le composant A, inertes vis-à-vis des composants A et B, et résistants à la température d'utilisation, c'est-à-dire au cours du procédé de traitement textile qui est décrit plus loin dans la présente description.The anti-odorous agents may be chosen from covering scenting agents (odor absorbing or masking agents or the like) commonly used and compatible with components A and B. In particular, the anti-odorant agent (s) are chosen from those which are stable. in component A, inert with respect to components A and B, and resistant to the temperature of use, that is to say during the textile treatment process which is described later in the present description.

En variante, il peut être envisagé d'utiliser des composés phosphorés, et en particulier des THPx, plus particulièrement un THPS, préparés selon des procédés sélectifs, permettant d'obtenir des composés phosphorés de haute pureté, ne contenant pas ou très peu d'impuretés, de sous-produits, qui sont responsables des mauvaises odeurs habituellement associées auxdits composés phosphorés. De préférence, un THPx produit au moyen d'un procédé fonctionnant sans excès de formaldéhyde est utilisé.Alternatively, it may be envisaged to use phosphorus compounds, and in particular THPx, more particularly THPS, prepared according to selective processes, making it possible to obtain phosphorus compounds of high purity, containing no or very little impurities, by-products, which are responsible for the bad odors usually associated with said phosphorus compounds. Preferably, a THPx produced using a method operating without excess formaldehyde is used.

Lorsque de tels composés phosphorés de haute pureté sont utilisés, l'ajout d'un agent anti-odorant n'est pas nécessaire. On pourra toutefois ajouter un ou plusieurs agents anti-odorants avec les composés phosphorés de haute pureté décrits ci-dessus, afin d'apporter une odeur agréable au composant A, si cela est souhaité ou requis pour l'utilisation envisagée.When such high purity phosphorus compounds are used, the addition of an anti-odorant is not necessary. However, one or more anti-odorants may be added with the phosphorus compounds of high purity described above, in order to provide a pleasant odor to component A, if desired or required for the intended use.

La quantité d'agent(s) anti-odorant(s) utilisée peut varier dans de grandes proportions selon l'effet recherché, la nature du ou des agents anti-odorants, la nature et la quantité du ou des composés présents dans le composant A. En règle générale, cette quantité varie de quelques ppm en poids à quelques pourcents en poids, typiquement de 1 ppm en poids à 10% en poids, de préférence de 5 ppm en poids à 5% en poids, de préférence de 10 ppm à 3% en poids, de préférence encore de 100 ppm en poids à 2% en poids par rapport au poids total de composant A.The amount of anti-odorant agent (s) used can vary in large proportions depending on the desired effect, the nature of the anti-odor agent (s), the nature and the amount of the compound (s) present in the component. A. As a rule, this amount varies from a few ppm by weight to a few percent by weight, typically from 1 ppm by weight to 10% by weight, preferably from 5 ppm by weight to 5% by weight, preferably 10 ppm. at 3% by weight, more preferably from 100 ppm by weight to 2% by weight relative to the total weight of component A.

Le composant A peut être préparé selon toute méthode connue en soi, et généralement par simple mélange entre eux des divers composés du composant A, dans un ordre quelconque.Component A can be prepared according to any method known per se, and generally by simply mixing together the various compounds of component A, in any order.

Comme indiqué précédemment, le composant B comprend de l'urée (H2N(C=O)NH2) et au moins un tampon pH, c'est-à-dire un composé permettant de contrôler et de maintenir le pH du composant B à une valeur comprise entre 4 et 6, avantageusement à une valeur comprise entre 3,5 et 5,5.As indicated above, component B comprises urea (H 2 N (C = O) NH 2 ) and at least one pH buffer, that is to say a compound making it possible to control and maintain the pH of the component B at a value between 4 and 6, preferably at a value between 3.5 and 5.5.

Le tampon pH peut être choisi parmi les tampons pH connus de l'homme du métier, étant entendu qu'il est compatible avec l'urée et inerte vis-à-vis de celle-ci. À titre d'exemples non limitatifs, les tampons pH qui peuvent être utilisés sont avantageusement choisis parmi les phosphates d'ammonium, les chlorures d'ammonium, les sulfates d'ammonium, et les carbonates d'ammonium, et leurs mélanges, le phosphate d'ammonium étant préféré. Ces tampons pH peuvent également être utilisés en association/mélange avec un ou plusieurs acides choisis parmi l'acide phosphorique, l'acide sulfurique, l'acide citrique, l'acide maléique et autres afin d'ajuster précisément le pH à la valeur requise pour le procédé selon l'invention.The pH buffer may be chosen from pH buffers known to those skilled in the art, it being understood that it is compatible with urea and inert with respect to it. By way of nonlimiting examples, the pH buffers that may be used are advantageously chosen from ammonium phosphates, ammonium chlorides, ammonium sulphates, and ammonium carbonates, and mixtures thereof, phosphate ammonium is preferred. These pH buffers can also be used in combination / mixing with one or more acids selected from phosphoric acid, sulfuric acid, citric acid, maleic acid and others in order to precisely adjust the pH to the required value. for the process according to the invention.

Sans vouloir être lié par la théorie, le tampon pH permet la fixation du pH, mais aussi et surtout agit en tant que « catalyseur » de la décomposition de l'urée en ammoniac, cette décomposition donnant lieu, comme indiqué ci-dessus, par l'augmentation du pH à une oxydation préliminaire du polymère lors de l'étape c) de séchage.Without wishing to be bound by the theory, the pH buffer allows the pH to be fixed, but also and above all acts as a "catalyst" for the decomposition of urea into ammonia, this decomposition giving rise, as indicated above, to increasing the pH to a preliminary oxidation of the polymer during step c) of drying.

Le composant B comprend, éventuellement mais avantageusement, au moins un agent oxydant, de préférence choisi parmi les composés azotés, de préférence encore, parmi les nitro-aryles, et, à titre d'exemple non limitatif, l'agent oxydant est le sel de sodium de l'acide 3-nitrobenzènesulfonique. Cet agent oxydant procure au polymère, dans le four, une oxydation supplémentaire à celle qui a lieu à l'étape c) suite à la décomposition de l'urée en ammoniac, ainsi que le maintien de cette dernière oxydation lorsque le textile est en attente à l'état sec avant de subir l'oxydation finale dans le deuxième bain. L'action de cet agent oxydant contribue à maximaliser l'oxydation du polymère, donc la résistance au lavage du textile ignifugé et sa durée d'utilisation.Component B comprises, optionally but advantageously, at least one oxidizing agent, preferably chosen from nitrogen compounds, of more preferably, among the nitro-aryls, and, by way of non-limiting example, the oxidizing agent is the sodium salt of 3-nitrobenzenesulphonic acid. This oxidizing agent gives the polymer, in the oven, an oxidation additional to that which takes place in step c) following the decomposition of urea ammonia, and the maintenance of the latter oxidation when the textile is waiting in the dry state before undergoing the final oxidation in the second bath. The action of this oxidizing agent contributes to maximizing the oxidation of the polymer, thus the washing resistance of the flame-retarded textile and its duration of use.

La quantité d'agent oxydant peut varier dans de grandes proportions et est généralement fixée à un ratio pondéral oxydant/urée compris entre 1/2 et 1/4, avantageusement environ 1/3.The amount of oxidizing agent can vary in large proportions and is generally set at an oxidative weight / urea weight ratio of between 1/2 and 1/4, advantageously about 1/3.

Le composant B peut également comprendre divers autres additifs, charges, agents anti-odorants, adoucissants, agents de rhéologie, agents de viscosité, agents moussants, agents anti-moussants, stabilisants, et autres, ainsi qu'un ou plusieurs agents ignifugeant ou retardant de flammes.Component B may also include various other additives, fillers, anti-odorants, softeners, rheology agents, viscosifiers, foaming agents, anti-foaming agents, stabilizers, and the like, as well as one or more flame retardant or retardant agents. of flames.

La composition à deux composants A et B telle que définie ci-dessus peut se présenter sous forme de deux composants séparés, qui seront mélangés juste avant emploi. En variante, la composition bi-composant peut se présenter sous la forme d'une solution prête à l'emploi comprenant les deux composants A et B.The two-component composition A and B as defined above may be in the form of two separate components, which will be mixed just before use. Alternatively, the two-component composition may be in the form of a ready-to-use solution comprising both components A and B.

La composition bi-composante comprenant les composants A et B, tels qu'ils viennent d'être définis, sous forme séparée ou mélangée, trouve une utilisation tout particulièrement appropriée dans le traitement d'ignifugation de textiles.The two-component composition comprising components A and B, as just defined, in separate or mixed form, finds a particularly suitable use in the flame retardant treatment of textiles.

Les textiles qui peuvent recevoir le traitement ignifugeant avec la composition bi-composante selon la présente invention peuvent être de tout type, et en particulier les textiles à base de fibres naturelles, qu'elles soient végétales ou animales (coton, lin, laine, et autres), et/ou à base de fibres synthétiques, comme par exemple les fibres à base de polyester, polyamide 6 et 6.6, et autres. On préfère les textiles à base de coton, à base de coton/polyester, à base de coton/polyamide, et parmi ceux-ci ceux dont le poids par mètre carré est compris entre environ 100 g/m2 et environ 600 g/m2.The textiles which can receive the flame-retardant treatment with the two-component composition according to the present invention can be of any type, and in particular textiles based on natural fibers, whether they be vegetable or animal (cotton, linen, wool, and others), and / or based on synthetic fibers, such as for example polyester-based fibers, polyamide 6 and 6.6, and others. Cotton / cotton / cotton based textiles based on cotton / polyamide are preferred, and among these are those whose weight per square meter is between about 100 g / m 2 and about 600 g / m 2 .

Les textiles qui peuvent être soumis au traitement ignifuge selon la présente invention peuvent l'être à une étape quelconque de leur fabrication, c'est-à-dire qu'ils peuvent être soumis au traitement ignifuge lorsqu'ils sont sous forme de textile cousus ou tricotés, avant ou après teinture, ou sous forme de textiles qui ont déjà subi un ou plusieurs traitements de finition.The textiles which can be subjected to the flame retardant treatment according to the present invention can be at any stage of their manufacture, that is to say that they can be subjected to flame retardant treatment when they are in the form of sewn textile or knitted, before or after dyeing, or in the form of textiles that have already undergone one or more finishing treatments.

Selon un mode de réalisation de l'invention, le composant B utilisé pour le traitement ignifuge selon la présente invention, sera adapté selon la nature des fibres constitutives du textile, par exemple selon que ce textile est en coton ou en fibres mélangées polyester/coton.According to one embodiment of the invention, the component B used for the flame retardant treatment according to the present invention, will be adapted according to the nature of the fibers constituting the textile, for example depending on whether the textile is cotton or polyester / cotton blend fibers .

Le premier bain (étape a) est préparé par simple mélange du composant A et du composant B (ou encore en utilisant le mélange des composants A et B prêt à l'emploi). Le ratio pondéral composant A / composant B peut varier dans de grandes proportions, notamment en fonction de la nature du composé phosphoré. Ce ratio est ajusté de manière à pouvoir former un polymère entre le composé phosphoré du composant A et l'urée du composant B.The first bath (step a) is prepared by simple mixing of component A and component B (or using the mixture of components A and B ready for use). The weight ratio component A / component B can vary in large proportions, in particular depending on the nature of the phosphorus compound. This ratio is adjusted so as to form a polymer between the phosphorus compound of component A and the urea of component B.

Le premier bain peut comprendre en outre un adoucissant pour textile qui peut avoir un rôle d'auxiliaire de traitement (« processing aid » en langue anglaise). L'adoucissant textile peut être de tout type connu de l'homme du métier et avantageusement choisi parmi les acides gras, les émulsions siliconées, les microémulsions de silicone, les polysiloxanes, et par exemple, à titre non limitatif, l'agent adoucissant est l'Addisoft®, commercialisé par CTF 2000. Un polysiloxane réagit aussi bien avec le textile qu'avec le polymère de manière conférer au textile revêtu des qualités de souplesse et donc de confort pour l'utilisateur. En outre, vu son caractère hydrophile, il favorise à l'étape d'oxydation d) la réaction avec de l'eau oxygénée et par conséquent améliore la tenue au lavage du textile ignifugé au moyen de ce composé oxydant.The first bath may further comprise a fabric softener which may have a role of processing aid in English. The fabric softener may be of any type known to those skilled in the art and advantageously chosen from fatty acids, silicone emulsions, silicone microemulsions, polysiloxanes, and for example, without limitation, the softening agent is the Addisoft ®, marketed by CTF 2000. A polysiloxane reacts with both the textile with the polymer so give the coated fabric of the qualities of flexibility and thus comfort for the user. In addition, because of its hydrophilic character, it promotes the oxidation step d) the reaction with hydrogen peroxide and therefore improves the resistance to washing the flame retarded textile by means of this oxidizing compound.

Le textile qui doit être imprégné dans le premier bain préparé à l'étape a), est avantageusement, mais non nécessairement, préalablement lavé à l'eau afin de le rendre propre et en particulier exempt de tout alcalin ou autres résidus chimiques provenant d'un éventuel traitement antérieur. Le pH de l'eau utilisée pour ce prélavage est avantageusement compris entre 6 et 7, celui-ci pouvant être ajusté finement par ajout d'un acide, par exemple un acide organique, tel que l'acide citrique.The textile to be impregnated in the first bath prepared in step a), is advantageously, but not necessarily, previously washed with water to make it clean and in particular free of any alkali or other chemical residues from any previous treatment. The pH of the water used for this prewash is advantageously between 6 and 7, which may be finely adjusted by adding an acid, for example an organic acid, such as citric acid.

Le tissu imprégné obtenu à l'étape b),« non séché », généralement en mouvement rotatif continu peut être laissé en attente pendant une durée pouvant varier entre environ 2 heures et 24 heures, avant d'opérer l'étape suivante. Cette opération (« pad/batch process » en langue anglaise) est avantageuse, mais non obligatoire. Il est également possible de sécher et polymériser directement après imprégnation comme décrit ci-dessous.The impregnated fabric obtained in step b), "undried", generally in continuous rotary motion can be left on standby for a period that can vary between about 2 hours and 24 hours, before performing the next step. This operation ("pad / batch process" in English) is advantageous, but not mandatory. It is also possible to dry and polymerize directly after impregnation as described below.

Après emport du bain préparé à l'étape a) par le textile comme indiqué précédemment, le textile imprégné est alors soumis à une haute température de four, typiquement supérieure ou égale à 130°C, avantageusement à une température comprise entre 150 et 160°C. La limite supérieure est fixée à environ 200°C température four et de préférence 165°C. Les températures mesurées sur le textile sont de préférence comprises entre 145 et 154°C. Ces formes de réalisation favorisent la polymérisation, donc la fixation du revêtement ignifuge sur le textile et par conséquent sa résistance au lavage.After taking the bath prepared in step a) by the textile as indicated above, the impregnated textile is then subjected to a high oven temperature, typically greater than or equal to 130 ° C., advantageously at a temperature of between 150 and 160 ° C. vs. The upper limit is set at about 200 ° C oven temperature and preferably 165 ° C. The temperatures measured on the textile are preferably between 145 and 154 ° C. These embodiments promote the polymerization, thus the fixation of the flame retardant coating on the textile and therefore its resistance to washing.

Le séchage de l'étape c), au cours duquel se produit la réaction de polymérisation indiquée plus haut, est conduit sur une période de temps la plus courte possible, pour des raisons évidentes de rendement du procédé complet de traitement ignifuge. Toutefois le séchage est considéré comme satisfaisant lorsque le taux d'humidité relative du textile séché, à la sortie du four, est compris entre 0% et 5% en poids, ce taux étant de préférence de 0% en poids. Le polymère ainsi formé, déjà polymérisé autour et dans les fibres textiles est ensuite soumis à oxydation dans le deuxième bain, de préférence par augmentation du pH, jusqu'à une valeur comprise entre 8 et 10 et au moyen de l'au moins un composé oxydant.The drying of step c), during which the above-mentioned polymerization reaction takes place, is carried out for as short a time as possible, for obvious reasons of efficiency of the complete flame retardant treatment process. However, the drying is considered satisfactory when the relative humidity of the dried textile at the outlet of the oven is between 0% and 5% by weight, this level being preferably 0% by weight. The polymer thus formed, already polymerized around and in the textile fibers is then subjected to oxidation in the second bath, preferably by increasing the pH, to a value of between 8 and 10 and by means of the at least one compound oxidant.

On préfère réaliser cette réaction d'oxydation par augmentation du pH, par immersion du textile comportant le polymère dans un bain basique comprenant une solution aqueuse d'hydroxyde alcalin, tel que l'hydroxyde de sodium. Dans ces conditions, la réaction d'oxydation est relativement lente et est accélérée au moyen d'une quantité efficace de l'au moins un composé oxydant, qui sera, de manière préférée, de l'eau oxygénée. La quantité d'eau oxygénée peut varier dans de grandes proportions en fonction de la quantité de polymère à oxyder et de la valeur du pH.It is preferred to carry out this oxidation reaction by increasing the pH, by immersing the textile comprising the polymer in a basic bath comprising an aqueous solution of alkaline hydroxide, such as sodium hydroxide. Under these conditions, the oxidation reaction is relatively slow and is accelerated by means of an effective amount of the at least one oxidizing compound, which will preferably be hydrogen peroxide. The amount of hydrogen peroxide can vary in large proportions depending on the amount of polymer to be oxidized and the pH value.

Dans ce bain basique, il y a lieu de procéder à l'élimination, totale ou partielle, des sous-produits de la réaction d'oxydation du polymère. Par exemple, lorsque le polymère résulte de la réaction entre un THPx et l'urée, la réaction d'oxydation conduit à la formation d'aldéhyde, en particulier de formaldéhyde, qu'il est nécessaire d'éliminer vu sa toxicité, comme indiqué précédemment. Pour ce faire, le mélange réticulant de diacétone acrylamide et d'au moins un dihydrazide d'acide organique sélectionné de préférence parmi les dihydrazides d'acide adipique, d'acide sébacique, d'acide succinique et d'acide isophtalique, est utilisé également en tant que« piégeur chimique » d'aldéhyde. Il a donc un double effet, c'est-à-dire d'améliorer par réticulation la résistance au lavage du textile ignifugé et d'éviter la diffusion de substances nuisibles dans l'environnement.In this basic bath, it is necessary to proceed to the total or partial elimination of by-products of the oxidation reaction of the polymer. For example, when the polymer results from the reaction between a THPx and urea, the oxidation reaction leads to the formation of aldehyde, in particular formaldehyde, which must be eliminated due to its toxicity, as indicated previously. For this purpose, the crosslinking mixture of diacetone acrylamide and at least one organic acid dihydrazide preferably selected from the dihydrazides of adipic acid, sebacic acid, succinic acid and isophthalic acid is also used. as a "chemical scavenger" of aldehyde. It has a double effect, that is to say to improve by crosslinking the washing resistance of the flame retardant textile and to avoid the diffusion of harmful substances into the environment.

Selon une autre forme de réalisation, le dihydrazide d'acide adipique et le diacétone acrylamide sont présents dans le deuxième bain dans un rapport de concentrations pondéral de 1, et de préférence chacun à une concentration de 0,5% en poids de bain.According to another embodiment, adipic acid dihydrazide and diacetone acrylamide are present in the second bath in a weight ratio of 1, and preferably each at a concentration of 0.5% by weight bath.

Enfin, le textile ainsi traité est alors soumis à plusieurs lavages, afin d'éliminer les résidus du traitement d'ignifugation. Le lavage est avantageusement réalisé à une température comprise entre 25°C et 75°C, par exemple aux environs de 60°C, avec de l'eau portée à un pH supérieur ou égal à 7, afin d'éliminer tout produit n'ayant pas réagi. Ainsi les eaux de lavages sont avantageusement additionnées d'une base, telle que par exemple un hydroxyde alcalin, de préférence l'hydroxyde de sodium. On peut également ajouter un savon dans les eaux de lavage.Finally, the textile thus treated is then subjected to several washes, in order to eliminate the residues of the fireproofing treatment. The washing is advantageously carried out at a temperature of between 25 ° C. and 75 ° C., for example at around 60 ° C., with water brought to a pH greater than or equal to 7, in order to eliminate any product having not reacted. Thus, the washings are advantageously added with a base, such as, for example, an alkaline hydroxide, preferably sodium hydroxide. You can also add a soap in the wash water.

Les derniers lavages sont réalisés à l'eau pure afin de ramener le pH des eaux de lavage finales à une valeur de pH voisine de, ou supérieure à 7. Si cela est nécessaire pour ajuster la valeur du pH à une valeur voisine de, ou supérieure à 7, on peut ajouter un acide, par exemple un acide faible, tel que l'acide citrique, acide maléique. De même, les eaux de lavage peuvent également comprendre, le cas échéant, un ou plusieurs adoucissants textile, tels que par exemple, ceux indiqués précédemment.The last washes are carried out with pure water in order to bring the pH of the final washing waters to a pH value close to or greater than 7. If this is necessary to adjust the pH value to a value close to or greater than 7, an acid may be added, for example a weak acid, such as citric acid, maleic acid. Similarly, the washing waters may also comprise, where appropriate, one or more textile softeners, such as, for example, those indicated above.

À l'issue des lavages, le textile ignifugé est récupéré et séché selon les procédés habituels de séchage. Le textile peut alors être soumis à un ou plusieurs post-traitements habituels destinés aux textiles bien connus de l'homme du métier, choisis parmi, de manière non limitative, traitement antimicrobien, traitement hydrofuge, traitement oléofuge, enduction, et autres.After washing, the flame retardant textile is recovered and dried according to the usual drying methods. The textile can then be subjected to one or more usual post-treatments for textiles well known to those skilled in the art, selected from, but not limited to, antimicrobial treatment, water repellent treatment, oil repellent treatment, coating, and others.

Les textiles ignifugés obtenus par le procédé selon l'invention peuvent alors être découpés, cousus et plus généralement être utilisés pour la confection et la manufacture de tout élément à base textile, tels que vêtements de protection, tentures, textiles techniques, coutils de matelas, tissus d'ameublements, toiles de tentes, et autres.The flame retarded textiles obtained by the process according to the invention can then be cut, sewn and more generally be used for the manufacture and manufacture of any textile-based element, such as protective clothing, draperies, technical textiles, mattress ticks, upholstery fabrics, tent cloths, and others.

Le procédé de la présente invention, tel que décrit ci-dessus présente de nombreux avantages par rapport aux traitements d'ignifugation connus dans l'art antérieur, et parmi eux, celui de l'excellente tenue au lavage des textiles ignifugés permettant de réduire leur taux d'emport, ce qui est bénéfique pour le toucher (main) et donc pour le confort de l'utilisateur, et/ou de prolonger leur caractère ignifuge et donc leur durée de vie. Par ailleurs les textiles obtenus par le procédé selon l'invention respectent les normes humano-écologiques telles que l'Öko-Tex 100 classe 1.The method of the present invention as described above has many advantages over fireproofing treatments known in the prior art, and among them, that of the excellent resistance to washing fireproof textiles to reduce their rate of carriage, which is beneficial for the touch (hand) and therefore for the comfort of the user, and / or extend their flame retardancy and therefore their lifetime. Moreover, the textiles obtained by the process according to the invention respect the human-ecological standards such as Öko-Tex 100 class 1.

La présente invention est maintenant illustrée au moyen des exemples qui suivent et qui ne présentent aucun but limitatif au regard de la portée de la présente invention, portée par ailleurs définie par les revendications annexées. Ces exemples illustrent notamment l'action de certains paramètres du procédé selon l'invention sur la polymérisation (donc la fixation) du revêtement ignifuge sur les fibres, qui, à coté de l'oxydation du polymère, favorise la résistance au lavage et la durée de vie des textiles ignifugés.The present invention is now illustrated by means of the following examples, which are not intended to limit the scope of the present invention and are otherwise defined by the appended claims. These examples illustrate, in particular, the action of certain parameters of the process according to the invention on the polymerization (and therefore the fixation) of the flame-retardant coating on the fibers, which, in addition to the oxidation of the polymer, promotes washing resistance and the duration of fireproof textiles.

Exemple 1 :Example 1

Au tableau 1 ci-dessous on peut voir l'influence de différentes compositions du bain d'oxydation (1.0 à 1.18) sur la résistance au lavage ainsi que sur la teneur en formaldéhyde libre des textiles ignifugés.In Table 1 below can be seen the influence of different compositions of the oxidation bath (1.0 to 1.18) on the washing resistance and on the free formaldehyde content of fireproof textiles.

Si l'on compare 1.8 (utilisation de l'éthylène urée comme piégeur d'aldéhyde) avec 1.18 selon l'invention (mélange diacétone acrylamide/dihydrazide d'acide adipique en lieu et place de l'éthylène urée), l'on constate que bien que ces deux compositions soient pour le reste fort similaires, la composition 1.18 donne lieu à des revêtements ignifuges présentant à la fois une teneur en formaldéhyde libre nettement plus basse (165 contre 253 ppm) et un poids surfacique plus élevé (303 contre 291 g/m2) après oxydation et 1 lavage. La sélection d'un mélange diacétone acrylamide/dihydrazide au lieu d'un piègeur d'aldéhyde classique permet donc d'atteindre un optimum en termes de compatibilité humano-écologique et de résistance au lavage. Tableau 1 Composition 1.0 (sans additif) 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12/1.14 1.13 1.15 1.16 1.17 1.18 H2O2 g/l 60 60 60 60 60 60 50 50 50 50 50 50 60 60 60 60 60 60 Prestogène g/l 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 TEA g/l 70 70 70 70 70 70 50 50 50 50 50 50 50 50 50 50 50 50 Urée g/l 100 100 100 100 100 100 50 - 50 50 50 50 50 50 50 50 50 50 NaOH g/l 30 30 30 30 30 30 pH 10 pH 10 pH 10 pH 10 pH 10 pH 10 pH 10 pH 10 pH10 pH10 pH10 pH10 DAP g/l - 20 - 10 - 10 - 10 - - 10 - - - - - - MAP g/l - - - - - - - - - - - 10 - 10 - - - Ethylène urée g/l - - 10 10 - - - - 10 - 10 - 10 10 10 10 10 - Dihydrazide d'acide adipique g/l - - - - 10 10 - - - 10 - 10 10 10 10 10 10 10 Diacétone acrylamide g/l - - - - - - - - - - - - 10 - - - - 10 NH4Cl g/l - - - - - - - - - - - - - - 10 - - - Bicarbonate g/l - - - - - - - - - - - - - - - 10 - (NH4)2SO4 g/l - - - - - - - - - - - - - - - - 10 - SODA ASH g/l - - - - - - - - - - - - - - - - - 15 Poids après oxydation et 1 lavage g/m2 305 284 288 293 300 296 292 297 291 295 290 299 304 (12)
296 (14) 309 298 294 299 303 Odeur ok NH3 ok NH3 ok NH3 ok NH3 ok ok ok NH3 après 10' NH3 NH3 NH3 ok NH3 * ok Formaldéhyde libre ppm 640 320 238 302 320 338 248 296 253 242 239 262 212 165 * Forte odeur d'ammoniac If we compare 1.8 (use of ethylene urea as an aldehyde scavenger) with 1.18 according to the invention (diacetone mixture acrylamide / adipic acid dihydrazide instead of ethylene urea), it is found that although these two compositions are for the rest very similar, the composition 1.18 gives rise to fireproof coatings having both a content free formaldehyde significantly lower (165 against 253 ppm) and a higher surface weight (303 against 291 g / m 2 ) after oxidation and 1 washing. The selection of a diacetone acrylamide / dihydrazide mixture instead of a conventional aldehyde trap therefore makes it possible to achieve an optimum in terms of human-ecological compatibility and washing resistance. <b> Table 1 </ b> Composition 1.0 (without additive) 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12 / 1.14 1.13 1.15 1.16 1.17 1.18 H 2 O 2 g / l 60 60 60 60 60 60 50 50 50 50 50 50 60 60 60 60 60 60 Prestogene g / l 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 TEA g / l 70 70 70 70 70 70 50 50 50 50 50 50 50 50 50 50 50 50 Urea g / l 100 100 100 100 100 100 50 - 50 50 50 50 50 50 50 50 50 50 NaOH g / l 30 30 30 30 30 30 pH 10 pH 10 pH 10 pH 10 pH 10 pH 10 pH 10 pH 10 pH10 pH10 pH10 pH10 DAP g / l - 20 - 10 - 10 - 10 - - 10 - - - - - - MAP g / l - - - - - - - - - - - 10 - 10 - - - Ethylene urea g / l - - 10 10 - - - - 10 - 10 - 10 10 10 10 10 - Adipic acid dihydrazide g / l - - - - 10 10 - - - 10 - 10 10 10 10 10 10 10 Diacetone acrylamide g / l - - - - - - - - - - - - 10 - - - - 10 NH 4 Cl g / l - - - - - - - - - - - - - - 10 - - - Bicarbonate g / l - - - - - - - - - - - - - - - 10 - (NH4) 2 SO 4 g / l - - - - - - - - - - - - - - - - 10 - SODA ASH g / l - - - - - - - - - - - - - - - - - 15 Weight after oxidation and 1 wash g / m 2 305 284 288 293 300 296 292 297 291 295 290 299 304 (12)
296 (14) 309 298 294 299 303 Odour okay NH 3 okay NH 3 okay NH 3 okay NH 3 okay okay okay NH 3 after 10 'NH 3 NH 3 NH 3 okay NH 3 * okay Free Formaldehyde ppm 640 320 238 302 320 338 248 296 253 242 239 262 212 165 * Strong smell of ammonia

Le tableau 2 ci-dessous permet de comparer la résistance au lavage (50 lavages) de textiles en coton/polyester 50/50 ignifugés selon l'invention au moyen d'un mélange de dihydrazide d'acide adipique/diacétone acrylamide (échantillons 2.1 et 2.2 ci-après) à celle obtenue sans recourir à ce mélange (2.3 et 2.4). Les résultats d'essais de propagation de flammes limitée selon la norme EN ISO 15025 y sont également repris. Tableau 2 Réf. échantillon Poids en g Perte de poids après 50 lavages % Test d'inflammabilité Avant lavage Après lavages 2.1 843,5 839,1 0,5 réussi 2.2 876,3 868,5 0,9 réussi 2.3 309,0 288,5 6,6 échoué 2.4 305,6 288,7 5,5 échoué Table 2 below compares the washing resistance (50 washes) of 50/50 flame retarded cotton / polyester textiles according to the invention by means of a mixture of adipic acid dihydroxide / diacetone acrylamide (samples 2.1 and 2). 2.2 below) to that obtained without resorting to this mixture (2.3 and 2.4). The results of limited flame spread tests according to EN ISO 15025 are also included. <b> Table 2 </ b> Ref. sample Weight in g Weight loss after 50 washes% Flammability test Before washing After washes 2.1 843.5 839.1 0.5 successful 2.2 876.3 868.5 0.9 successful 2.3 309.0 288.5 6.6 failed 2.4 305.6 288.7 5.5 failed

L'effet favorable du mélange dihydrazide d'acide adipique/diacétone acrylamide sur la tenue au feu de textiles est démontré ici clairement.The favorable effect of the adipic acid / diacetone acrylamide dihydrazide mixture on the fire resistance of textiles is clearly demonstrated here.

Exemple 3 :Example 3

Incidence de la température du four sur la tenue au lavage de textiles (donc sur leur inflammabilité) et sur leur toucher.Effect of oven temperature on the washing ability of textiles (hence their flammability) and on their feel.

Au tableau 3 ci-dessous sont réunis des résultats de tests pratiqués sur 8 échantillons de polyester/cotton. Des résultats optimaux du point de vue de la résistance au lavage et du toucher sont obtenus pour des températures de four comprises entre 150 et 160°C. Tableau 3 N° Poids sec (g) Poids après foulardage (g) Emport (g) Poids après fixation (g) Température four (°C) Add on (g) Fixation/toucher Perte de poids après lavage (%) 3.1 71,13 144,07 102,5 110,30 120 35,5 Pas de fixation 32,0 3.2 78,05 145,56 86,5 108,19 130 27,8 Fixation légère 17,0 3.3 75,60 148,62 96,75 108,06 140 30,0 Fixation 5,6 3.4 71,38 144,32 102,2 104,31 150 31,5 Fixation 0,9 3.5 73,20 150,53 105,64 107,61 160 31,9 Fixation/dur au toucher 0,8 3.6 73,22 153,06 104,80 108,30 170 32,4 Fixation/dur au toucher 0,8 3.7 75,10 152,55 103,12 107,87 180 30,2 Fixation/dur au toucher 0,8 3.8 77,38 151,23 95,43 111,30 190 30,5 Fixation/dur au toucher 0,9 Table 3 below shows the results of tests performed on 8 samples of polyester / cotton. Optimum results in wash resistance and feel are obtained for oven temperatures between 150 and 160 ° C. <b> Table 3 </ b> No. Dry weight (g) Weight after padding (g) Emport (g) Weight after fixation (g) Oven temperature (° C) Add on (g) Attaching / touch Weight loss after washing (%) 3.1 71.13 144.07 102.5 110.30 120 35.5 No fixing 32.0 3.2 78.05 145.56 86.5 108.19 130 27.8 Light fixation 17.0 3.3 75,60 148.62 96.75 108.06 140 30.0 Fixation 5.6 3.4 71.38 144.32 102.2 104.31 150 31.5 Fixation 0.9 3.5 73,20 150.53 105,64 107.61 160 31.9 Fixing / hard touch 0.8 3.6 73.22 153,06 104.80 108.30 170 32.4 Fixing / hard touch 0.8 3.7 75.10 152.55 103,12 107.87 180 30.2 Fixing / hard touch 0.8 3.8 77.38 151.23 95.43 111.30 190 30.5 Fixing / hard touch 0.9

Exemple 4 : Incidence de la température mesurée sur le textile et de son humidité relative (HR) à la sortie du four sur la tenue au lavage de textiles et sur leur inflammabilité. Example 4 : Incidence of the temperature measured on the textile and its relative humidity (RH) at the outlet of the oven on the resistance to washing textiles and their flammability.

Au tableau 4 sont réunis des résultats de tests d'inflammabilité (FR) pratiqués sur 9 échantillons de polyester/cotton et réalisés selon la norme EN 531-532, après 50 lavages suivant ISO 1715797. La température T des échantillons est mesurée par l'intermédiaire de thermostrips. Tableau 4 N° échantillon HR (%) Temps de séjour dans le four (s) T (°C) Test FR 4.1 35 30 <116 échoué 4.2 30 35 <116 échoué 4.3 20 40 <116 échoué 4.4 20 45 127 échoué 4.5 10 50 143 échoué 4.6 0-5 55 149 réussi 4.7 0 60 149 réussi 4.8 0 65 154 réussi 4.9 0 70 154 réussi Table 4 shows the results of flammability tests (FR) carried out on 9 samples of polyester / cotton and made according to standard EN 531-532, after 50 washes according to ISO 1715797. The temperature T of the samples is measured by the intermediate thermostrips. <b> Table 4 </ b> Sample no HR (%) Residence time in the oven (s) T (° C) FR test 4.1 35 30 <116 failed 4.2 30 35 <116 failed 4.3 20 40 <116 failed 4.4 20 45 127 failed 4.5 10 50 143 failed 4.6 0-5 55 149 successful 4.7 0 60 149 successful 4.8 0 65 154 successful 4.9 0 70 154 successful

Le revêtement ignifuge des échantillons 4.1 à 4.3. disparaît complètement au lavage. Les échantillons 4.4 et 4.5 présentent une polymérisation partielle. A partir de 4.6 la polymérisation est totale, ce qui donne des tests d'inflammabilité satisfaisants. Des valeurs optimales de température et d'humidité relative du textile sont respectivement de 149 à 154 °C et de 0 %.The flame retardant coating of samples 4.1 to 4.3. disappears completely in the wash. Samples 4.4 and 4.5 show partial polymerization. From 4.6 the polymerization is complete, which gives satisfactory flammability tests. Optimum values of temperature and relative humidity of the textile are respectively 149 to 154 ° C and 0%.

Claims (13)

Procédé de traitement d'ignifugation de textiles comprenant au moins les étapes suivantes : a) préparation d'un premier bain comprenant une composition à deux composants A et B, le composant A comprenant au moins un composé phosphoré et le composé B comprenant de l'urée et au moins un tampon pH ; b) imprégnation du textile à traiter dans le bain obtenu à l'étape a) dont le pH est compris entre en substance 4 et en substance 6 ; c) séchage du textile imprégné par chauffage, séchage au cours duquel se produit la réaction de polymérisation de l'urée du composant B et du composé phosphoré du composant A ; d) stabilisation et neutralisation par réaction d'oxydation du polymère obtenu à l'étape c) dans un deuxième bain ; e) lavage à l'eau et séchage du textile traité ; et f) récupération du textile ignifugé, caractérisé en ce que le deuxième bain comprend, outre au moins un composé oxydant, un mélange de diacétone acrylamide et d'au moins un dihydrazide d'acide organique.A textile flame retardant treatment method comprising at least the following steps: a) preparing a first bath comprising a two-component composition A and B, component A comprising at least one phosphorus compound and compound B comprising urea and at least one pH buffer; b) impregnation of the textile to be treated in the bath obtained in step a), the pH of which is between substance 4 and substance 6; c) drying the impregnated textile by heating, drying during which the polymerization reaction of the urea of component B and the phosphorus compound of component A; d) stabilization and neutralization by oxidation reaction of the polymer obtained in step c) in a second bath; e) washing with water and drying the treated textile; and f) recovery of the flame retarded textile, characterized in that the second bath comprises, in addition to at least one oxidizing compound, a mixture of diacetone acrylamide and at least one dihydrazide of organic acid. Procédé selon la revendication 1, caractérisé en ce que l'au moins un composant phosphoré du composant A est un sel de tétrakis(hydroxyméthyl)phosphonium .A method according to claim 1, characterized in that the at least one component of a phosphorus component A is tetrakis (hydroxymethyl) phosphonium. Procédé selon la revendication 2, caractérisé en ce que le sel de tétrakis(hydroxyméthyl)phosphonium est produit sans excès de formaldéhyde.Process according to Claim 2, characterized in that the tetrakis (hydroxymethyl) phosphonium salt is produced without excess formaldehyde. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'au moins un dihydrazide d'acide organique est sélectionné parmi les dihydrazides d'acide adipique, d'acide sébacique, d'acide succinique et d'acide isophtalique.Process according to any one of the preceding claims, characterized in that the at least one organic acid dihydrazide is selected from dihydrazides of adipic acid, sebacic acid, succinic acid and isophthalic acid. Procédé selon la revendication 4, caractérisé en ce que le dihydrazide d'acide adipique et le diacétone acrylamide sont présents dans le deuxième bain dans un rapport de concentrations pondéral de 1.Process according to Claim 4, characterized in that the adipic acid dihydrazide and the diacetone acrylamide are present in the second bath in a weight concentration ratio of 1. Procédé selon la revendication 5, caractérisé en ce que le dihydrazide d'acide adipique et le diacétone acrylamide sont chacun présents dans le deuxième bain à une concentration de 0,5% en poids de bain.Process according to Claim 5, characterized in that the adipic acid dihydrazide and the diacetone acrylamide are each present in the second bath at a concentration of 0.5% by weight bath. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le composant B comprend en outre au moins un agent oxydant.Process according to any one of the preceding claims, characterized in that component B further comprises at least one oxidizing agent. Procédé selon la revendication 7, caractérisé en ce que l'au moins un agent oxydant est le sulfonate de 3-nitrobenzène.Process according to Claim 7, characterized in that the at least one oxidizing agent is 3-nitrobenzene sulphonate. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le premier bain est préparé en y ajoutant un agent adoucissant.Process according to any one of the preceding claims, characterized in that the first bath is prepared by adding a softening agent. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que dans lequel l'étape c) de séchage est effectuée à une température de four comprise entre 130°C et 165°C.A process as claimed in any one of the preceding claims, characterized in that the drying step c) is carried out at a furnace temperature of between 130 ° C and 165 ° C. Procédé selon la revendication 10, caractérisé en ce que l'étape c) de séchage est effectuée à une température de four comprise entre 150°C et 160°C.Process according to claim 10, characterized in that the drying step c) is carried out at a furnace temperature of between 150 ° C and 160 ° C. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'étape d) d'oxydation est effectuée par augmentation du pH jusqu'à une valeur comprise entre 8 et 10, et au moyen de l'au moins un composé oxydant.A process according to any one of the preceding claims, wherein the oxidation step d) is carried out by increasing the pH to a value between 8 and 10, and by means of the at least one oxidizing compound. Procédé selon la revendication 12, dans lequel de l'eau oxygénée est utilisée à l'étape d) en tant que l'au moins un composé oxydant.The process of claim 12, wherein hydrogen peroxide is used in step d) as the at least one oxidizing compound.
EP20110166319 2011-05-17 2011-05-17 Textile fireproofing method Withdrawn EP2524993A1 (en)

Priority Applications (8)

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EP20110166319 EP2524993A1 (en) 2011-05-17 2011-05-17 Textile fireproofing method
PCT/EP2012/057627 WO2012156190A1 (en) 2011-05-17 2012-04-26 Method for fireproofing textiles
CN201280023618.9A CN103534404B (en) 2011-05-17 2012-04-26 The resistance to ignition method of fabric
ES12718640.1T ES2526795T3 (en) 2011-05-17 2012-04-26 Methods for manufacturing fireproof textiles
US14/117,614 US9074316B2 (en) 2011-05-17 2012-04-26 Method for fireproofing textiles
EP20120718640 EP2710184B1 (en) 2011-05-17 2012-04-26 Method for fireproofing textiles
BR112013029415-9A BR112013029415B1 (en) 2011-05-17 2012-04-26 method for making fabrics fireproof
HK14106364A HK1193129A1 (en) 2011-05-17 2014-06-24 Method for fireproofing textiles

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CN105200768B (en) * 2015-09-01 2017-11-28 广东德美精细化工股份有限公司 The durable fire resistant finish method of cotton/nylon blends and colouring method
EP3178987A1 (en) * 2015-12-11 2017-06-14 Rhodia Operations Flame retardant compositions with low formaldehyde content
CN109235029A (en) * 2018-09-03 2019-01-18 常熟华尚新材料科技有限公司 Cotton fabric category fire retardant

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453296A (en) * 1973-11-16 1976-10-20 Ciba Geigy Ag Process for flameproofing organic fibre material and a preparatio for use therein
US4750911A (en) 1986-09-26 1988-06-14 Burlington Industries, Inc. Flame-resistant nylon/cotton fabrics
US4765796A (en) 1987-07-20 1988-08-23 The United States Of America As Represented By The Secretary Of Agriculture Process for flameproofing cellulosic fibers prior to dyeing
US4842609A (en) 1986-06-05 1989-06-27 Burlington Industries, Inc. Flame retardant treatments for polyester/cotton fabrics
US6869996B1 (en) * 1999-06-08 2005-03-22 The Sherwin-Williams Company Waterborne coating having improved chemical resistance
US20110092119A1 (en) * 2009-10-21 2011-04-21 Cliver James D Flame resistant textile

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076650A (en) * 1976-03-01 1978-02-28 Stauffer Chemical Company Catalyst system for flame retardant finishing
CN101094952A (en) * 2005-01-07 2007-12-26 名古屋油化株式会社 Flame-retardant fiber sheet and formed article thereof
WO2008006395A1 (en) * 2006-07-14 2008-01-17 Ctf 2000 N.V. Process of manufacturing a laminated flame-retardant fabric
WO2011143077A1 (en) * 2010-05-11 2011-11-17 Milliken & Company Flame resistant textile materials providing protection from near infrared radiation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453296A (en) * 1973-11-16 1976-10-20 Ciba Geigy Ag Process for flameproofing organic fibre material and a preparatio for use therein
US4842609A (en) 1986-06-05 1989-06-27 Burlington Industries, Inc. Flame retardant treatments for polyester/cotton fabrics
US4750911A (en) 1986-09-26 1988-06-14 Burlington Industries, Inc. Flame-resistant nylon/cotton fabrics
US4765796A (en) 1987-07-20 1988-08-23 The United States Of America As Represented By The Secretary Of Agriculture Process for flameproofing cellulosic fibers prior to dyeing
US6869996B1 (en) * 1999-06-08 2005-03-22 The Sherwin-Williams Company Waterborne coating having improved chemical resistance
US20110092119A1 (en) * 2009-10-21 2011-04-21 Cliver James D Flame resistant textile

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BR112013029415B1 (en) 2020-12-01
EP2710184A1 (en) 2014-03-26
ES2526795T3 (en) 2015-01-15
US9074316B2 (en) 2015-07-07
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EP2710184B1 (en) 2014-11-12
HK1193129A1 (en) 2014-09-12

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