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WO1990013699A2 - Preparation ignifuge et son utilisation - Google Patents

Preparation ignifuge et son utilisation Download PDF

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Publication number
WO1990013699A2
WO1990013699A2 PCT/NL1990/000061 NL9000061W WO9013699A2 WO 1990013699 A2 WO1990013699 A2 WO 1990013699A2 NL 9000061 W NL9000061 W NL 9000061W WO 9013699 A2 WO9013699 A2 WO 9013699A2
Authority
WO
WIPO (PCT)
Prior art keywords
flame
weight
preparation
retardant
ammonium
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.)
Ceased
Application number
PCT/NL1990/000061
Other languages
English (en)
Other versions
WO1990013699A3 (fr
Inventor
Christiaan Bruynes
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.)
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Original Assignee
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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 Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO filed Critical Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority to FI915161A priority Critical patent/FI915161A0/fi
Publication of WO1990013699A2 publication Critical patent/WO1990013699A2/fr
Publication of WO1990013699A3 publication Critical patent/WO1990013699A3/fr
Priority to NO91914307A priority patent/NO914307L/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids

Definitions

  • the invention relates to a flame-retardant preparation which contains ammonium phosphate and one or more nitrogen compounds liberating ammonia on decomposition.
  • a preparation of this type is disclosed in US Patent 3,398,019. More particularly, this US Patent relates to the treatment of wood fibre products with an aqueous solution of a flame- retardant preparation which contains ammonitm phosphate and in which a decomposition inhibitor for the ammonium phosphate is also incorporated.
  • a decomposition inhibitor of this type is defined as a nitrogen compound which must decompose below the decomposition temperature of the ammonium phosphate (i.e. monoammonium phosphate or diammonium phosphate) with the liberation of ammonia.
  • inorganic nitrogen compounds such as water-soluble ammonium salts, for example the ammonium halides, ammonium carbonate and ammonium sulphide
  • organic nitrogen compounds such as amides and amidines, for example urea, formamide, acetamide and guanine
  • the aim of the invention described in this US Patent 3,398,019 lies in the prevention or substantial minimilization of the undesired discoloration of wood fibre products impregnated with the aqueous ammonium phosphate solution during the drying process for said products, which process is carried out above the decomposition temperature of ammonium phosphate.
  • the aim of the invention is to develop a flame-retardant preparation which is both particularly effective and can be applied in a simple manner to, or in some cases in, the materials to be protected.
  • a flame-retardant preparation of this type since the fire hazard which is associated with the use of many combustible materials, such as textile materials, is appreciable and must in no way be underestimated.
  • nitrogen compounds examples include urea, dimethylurea, melamine, glycine, guanidine, guanylurea, acetamidine and formamide, of which melamine and, for reasons of cost and availability, especially urea are to be preferred.
  • the more intensive flame- retardant action of the preparations according to the invention can, moreover, be ascribed in particular to the formation of phosphoric acid and phosphoric acid amides at elevated temperature, for example about 300oC, this being termed the phosphorus-nitrogen synergism within the framework of the invention.
  • elevated temperature for example about 300oC
  • the phosphorus-nitrogen synergism within the framework of the invention.
  • an accelerated dehydration of cellulose is obtained.
  • the hydrogen is withdrawn from the cellulose molecule so that no compounds present- ing a fire hazard are able to form.
  • the dehydration mechanism presumably proceeds via an acid protonation of a hydroxyl group of the cellulose molecule.
  • ammonium halide such as ammonium chloride, ammonium bromide and ammonium fluoride
  • ammonium halides generally decompose into ammonia and the hydrogen halide gas at elevated temperature. These gases are diluted with the pyrolysis products of the material which has been treated with the preparation according to the invention and may itself be regarded as flame-retardant.
  • compounds of this type display a synergistic effect with respect to the flame retardancy.
  • the eminent fire-retardant action of the preparations according to the invention is based on a combination of synergistic effects.
  • urea as such has no flame-retardant action but produces the synergistic effect described above only in the presence of phosphates, that is to say the action of the mixture of phosphates and urea is greater than that of the separate components themselves.
  • the invention relates in particular to flame-retardant preparations which contain
  • ammonium chloride and/or ammonium bromide preferably ammoninm chloride, as the ammonium halide.
  • the above- mentioned three types of components are advantageously dissolved in an effective amount in water; the pH of such a solution is in the range 6-8. More particularly, the three types of components are dissolved in the amounts indicated above in x. 100 parts by weight of water, x having a value in the range 0.25-5.
  • the abovementioned three types of components can also be formed in situ when making up a water-containing preparation according to the invention, it is possible in the case of a preparation built up from urea, diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride to use, in addition to urea, suitable amounts of ammonia, hydrogen chloride and phosphoric acid.
  • the three lastmentioned reagents are used in the form of an aqueous solution, such as ammonia (25 % solution), hydrochloric acid (30 % solution) and phosphoric acid (85 % solution).
  • the preparation in question is made up of substances which are non-toxic or are of very low toxicity, so that there can hardly be objection to the use thereof from the environmental standpoint.
  • the preparation in question as a solution in water, has a neutral pH, that is to say a pH in a range of 6-8, and can therefore be regarded as non-irritant for the skin.
  • Tests carried out in accordance with OECD guidelines with a preparation made up of urea, diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride have shown that a preparation of this type is not irritant for the skin and eyes and is even considered non-toxic when taken orally (in small amounts).
  • an effective amount of glycerol can be added to the preparations in question.
  • the amount of glycerol to which there likewise can hardly be objection from the environmental standpoint, to be used in the preparation according to the invention is, for example, 0.5-1-5 parts by weight, preferably 0.7-1-0 part by weight, relative to the ranges indicated above with regard to the amounts of the com-ponents to be used.
  • the preparation when used on textile fibres and/or wood fibres, the preparation can be provided with a water-repellent agent so that the treated fibres acquire a certain degree of water repellency and/or fastness to washing.
  • a water-repellent agent such as water repellency
  • the product "HYDROB FC” Caldic Belgium N.V., Hemiksen, Belgium
  • the manufacturer indicates that on heating the materials treated herewith to, for example, 120oC or even 180°C the effect achieved, such as water repellency, is fast to washing.
  • the preparation of the flame-retardant preparations according to the invention can take place by simple mixing of the components in a mixing vessel provided with a stirrer device.
  • the mixing vessel and the auxiliary apparatus belonging thereto are made of corrosion-resistant material, such as stainless steel.
  • the said components can be used as such, but usually are advantageously used as a solution in water. Specifically, hydrogen chloride, phosphoric acid and ammonia are used as solutions, which may be concentrated, in water.
  • concentrated hydrochloric acid for example 30 % w/w
  • concentrated phosphoric acid for example 85 % w/w
  • ammonia for example 25 % w/w
  • the water-containing flame-resistant preparations according to the invention usually contain 10-20 % by weight, advantageously 13-15 % by weight, of active substances.
  • the preparations according to the invention can also exist in concentrated form, for example in connection with transport and for certain applications. Examples of such applications are the production processes for paper and cardboard, the end products of which must have a low final moisture content. In the latex industry also it is considered desirable to work with concentrated solutions as far as possible.
  • the flame-retardant preparations according to the invention can, as has already been stated in part, be used for many materials, such as textiles, paper, cardboard, wood and products derived therefrom, and waterbased paint and also as extinguishing material.
  • textile materials such as cotton, cotton/polyester material preferably containing at least 50 % cotton (is used as curtain material), wool, wool/cotton woven fabrics, wool/viscose woven fabrics, such as, for example, 70/30 wool/viscose woven fabric, which is used as upholstery material, and also other textile materials may be mentioned.
  • cotton, cotton/polyester material preferably containing at least 50 % cotton (is used as curtain material)
  • wool wool/cotton woven fabrics
  • wool/viscose woven fabrics such as, for example, 70/30 wool/viscose woven fabric, which is used as upholstery material
  • other textile materials may be mentioned.
  • the textile materials flame-retardant it already suffices to moisten these once completely with the water-containing preparation according to the invention by, for example, immersion or spraying with an atomizer device.
  • any finishes which may be present on the textile material are removed from the textile material beforehand.
  • this textile material After moistening the textile material with the aqueous preparation according to the invention, this textile material may be force-dried if appropriate.
  • the flame retardancy of the textile materials treated in this way which are used, inter alia, as curtain or upholstery materials, is considered to be appreciable. Even on dry cleaning (that is to say cleaning without H 2 O), the flame retardancy of the treated materials is virtually completely retained.
  • Wood such as deal
  • products derived from wood such as Triplex and chipboard
  • a preparation according to the invention Apart from by spraying or immersion, the preparation can be applied to porous wood materials, such as chipboard and the like, using a brush, while the generally known vacuum treatment is preferred for types of wood such as deal.
  • the preparations according to the invention can be added to water-based paints, such as latex paints, which are then applied to, for example, sheet materials. After applying a latex paint having a composition of this type, and drying, a surface is obtained which is both fire-resistant and aesthetically pleasing.
  • water-based paints such as latex paints
  • the preparations according to the invention can be used as such in the form of an extinguishing agent for fighting fires which are usually fought with water, such as in dwellings, wood fires and the like.
  • the relative amounts of the components are advantageously
  • the content of active substances in the extinguishing water is advantageously very appreciable, for example in the range 20-60 % by weight, preferably 30-50 % by weight.
  • the multi-purpose nature of the extinguishing water indicated above can, moreover, be broadened if a foam-forming agent, such as a suitable detergent, is also used in the extinguishing water, in a concentration of, for example, 1-10 % by weight calculated relative to the total composition of the extinguishing water.
  • This lastmentioned additive renders the said extinguishing water suitable for so-called A-type fires (wood and paper fires) and B-type fires (liquid fires).
  • a suitable foam-forming agent is the commercially available product "HCA Polar Newtonian” (a fluorocarbon compound) (Uniser, Amplepuis, France).
  • the flameretardant preparations according to the invention can be used in diverse fields and for this reason constitute a particularly attractive product from the industrial standpoint.
  • the amount of active constituents was 504 kg per 3000 litres or 16.8 % by weight of active substances per unit volume of preparation.
  • the pH of the flame-retardant preparation obtained was about 7.0-7.3.
  • the amount of active substances in this case also was 504 kg per 3000 litres or 16.8 % by weight per unit volume of preparation.
  • the pH of the flame-retardant agent was likewise between 7-0 and 7-3- Example III
  • Example IV The procedure described in Example 1 was followed, except that 30 kg of glycerol were also added. A flame-retardant preparation with improved adhesion characteristics was obtained.
  • Example IV The procedure described in Example 1 was followed, except that 30 kg of glycerol were also added. A flame-retardant preparation with improved adhesion characteristics was obtained.
  • Example II The procedure described in Example II was followed, except that 30 kg of glycerol were also added. In accordance with this example also, a water-containing preparation was obtained which had improved adhesion characteristics with respect to the materials to be treated.
  • Example II results are given of a study which was carried out to determine the effectiveness of a treatment with the preparation of Example I on the burning characteristics of textile materials of diverse composition on heating briefly with a small heat source. In this study tests were also carried out to determine whether the fire-retardant action of the product was influenced when the treated materials had undergone dry cleaning without the use of water. Twelve textile materials, which are listed in Table A below, were included in the study. Before treating the materials with the preparation of Example 1, these materials were washed in a washing machine with a conventional detergent in order to remove any finishes which may be present and were then dried in a drying oven or stored over silica gel in a desiccator. The pretreated materials were immersed in the water-containing preparation of Example I and then centrifuged and dried.
  • the untreated textile material was tested by applying a flame for a contact time of 5 sec.
  • the preparation according to the invention which has been used has a favourable influence on the burning characteristics of textile materials which are made up for the greater part from natural fibres.
  • Tests in respect of the flame propagation and flame flash-over were carried out in accordance with NEN 3883 using the samples treated in the above manner and using untreated samples. The samples were assigned to the relevant class category on the basis of the results obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Fireproofing Substances (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne une préparation ignifuge contenant au moins un composé d'azote organique contenant comme groupes fonctionnels un ou plusieurs groupes OC=NH(y), des groupes CH(x)-NH(y) et/ou des groupes =C-NH(y), les symboles y indépendamment l'un de l'autre ayant une valeur de 0, 1, 2 ou 3 et x ayant une valeur de 1, 2 ou 3, par exemple l'urée ou la mélamine, le phosphate d'hydrogène diammoniacal et/ou le phosphate de dihydrogène ammoniacal; et un haloïde d'ammonium. Des préparations de ce genre sont utilisées avantageusement pour rendre ignifuges des matières combustibles telles que les textiles et les produits en bois. En outre, ces préparations, notamment en forme concentrée, peuvent agir comme de l'eau d'extinction.
PCT/NL1990/000061 1989-05-02 1990-05-02 Preparation ignifuge et son utilisation Ceased WO1990013699A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FI915161A FI915161A0 (fi) 1989-05-02 1990-05-02 Brandhindrande komposition och anvaendning av denna.
NO91914307A NO914307L (no) 1989-05-02 1991-11-01 Flammehemmende materiale og anvendelse av dette

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8901118A NL8901118A (nl) 1989-05-02 1989-05-02 Vlamwerend preparaat, werkwijze voor het vlamwerend maken van produkten met een dergelijk preparaat alsmede de vlamwerend gemaakte produkten.
NL8901118 1989-05-02

Publications (2)

Publication Number Publication Date
WO1990013699A2 true WO1990013699A2 (fr) 1990-11-15
WO1990013699A3 WO1990013699A3 (fr) 1990-12-13

Family

ID=19854594

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1990/000061 Ceased WO1990013699A2 (fr) 1989-05-02 1990-05-02 Preparation ignifuge et son utilisation

Country Status (6)

Country Link
EP (1) EP0471786A1 (fr)
AU (1) AU5677390A (fr)
CA (1) CA2054759A1 (fr)
FI (1) FI915161A0 (fr)
NL (1) NL8901118A (fr)
WO (1) WO1990013699A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2301122A (en) * 1995-05-24 1996-11-27 Cyril Glass Flame retardant compositions
WO2008064737A1 (fr) * 2006-11-29 2008-06-05 Union Marketing Gmbh Composition utilisée comme agent ignifuge temporaire préventif, application de celle-ci sur des produits, production et utilisation de celle-ci
WO2013159510A1 (fr) * 2012-04-24 2013-10-31 Winnitex Limited Compositions ignifugeantes exemptes de formaldéhyde et leur utilisation pour la fabrication de matières cellulosiques ignifuges exemptes de formaldéhyde durables
BE1025604B1 (fr) * 2017-10-02 2019-04-29 Uniteq Sa Cylindre pour extincteur d'incendie
CN116535633A (zh) * 2023-04-29 2023-08-04 中国科学院长春应用化学研究所 一种磷化聚丙撑碳酸酯共聚物的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225464A (en) * 1992-04-02 1993-07-06 Material Technologies & Sciences, Inc. Intumescent coating and method of manufacture

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2225831A (en) * 1935-03-13 1940-12-24 Herz Walter Fireproofing composition
GB819190A (en) * 1957-06-20 1959-09-02 Dow Chemical Co Fire retardant coating composition
US3398019A (en) * 1963-02-21 1968-08-20 Monsanto Co Method for fireproofing cellulosic material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2301122A (en) * 1995-05-24 1996-11-27 Cyril Glass Flame retardant compositions
WO2008064737A1 (fr) * 2006-11-29 2008-06-05 Union Marketing Gmbh Composition utilisée comme agent ignifuge temporaire préventif, application de celle-ci sur des produits, production et utilisation de celle-ci
WO2013159510A1 (fr) * 2012-04-24 2013-10-31 Winnitex Limited Compositions ignifugeantes exemptes de formaldéhyde et leur utilisation pour la fabrication de matières cellulosiques ignifuges exemptes de formaldéhyde durables
AU2012323990B2 (en) * 2012-04-24 2015-08-13 Winnitex Limited Formaldehyde-free flame retardant compositions and their use for manufacturing durable formaldehyde-free flame retardant cellulosic materials
CN104995246A (zh) * 2012-04-24 2015-10-21 浙江庆茂纺织印染有限公司 无甲醛阻燃组合物及其用于制造耐洗的无甲醛阻燃纤维素材料的用途
EP2841495A4 (fr) * 2012-04-24 2016-01-13 Winnitex Ltd Compositions ignifugeantes exemptes de formaldéhyde et leur utilisation pour la fabrication de matières cellulosiques ignifuges exemptes de formaldéhyde durables
US9675998B2 (en) 2012-04-24 2017-06-13 Winnitex Limited Formaldehyde-free flame retardant compositions and their use for manufacturing durable formaldehyde-free flame retardant cellulosic materials
BE1025604B1 (fr) * 2017-10-02 2019-04-29 Uniteq Sa Cylindre pour extincteur d'incendie
CN116535633A (zh) * 2023-04-29 2023-08-04 中国科学院长春应用化学研究所 一种磷化聚丙撑碳酸酯共聚物的制备方法

Also Published As

Publication number Publication date
EP0471786A1 (fr) 1992-02-26
CA2054759A1 (fr) 1990-11-03
NL8901118A (nl) 1990-12-03
WO1990013699A3 (fr) 1990-12-13
AU5677390A (en) 1990-11-29
FI915161A7 (fi) 1991-11-01
FI915161A0 (fi) 1991-11-01

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