EP0471786A1 - Flammverzögernde zusammensetzung und ihre verwendung - Google Patents
Flammverzögernde zusammensetzung und ihre verwendungInfo
- Publication number
- EP0471786A1 EP0471786A1 EP19900908691 EP90908691A EP0471786A1 EP 0471786 A1 EP0471786 A1 EP 0471786A1 EP 19900908691 EP19900908691 EP 19900908691 EP 90908691 A EP90908691 A EP 90908691A EP 0471786 A1 EP0471786 A1 EP 0471786A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flame
- weight
- preparation
- ammonium
- retardant
- 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- Withdrawn
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)
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 (1)
Publication Number | Publication Date |
---|---|
EP0471786A1 true EP0471786A1 (de) | 1992-02-26 |
Family
ID=19854594
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19900908691 Withdrawn EP0471786A1 (de) | 1989-05-02 | 1990-05-02 | Flammverzögernde zusammensetzung und ihre verwendung |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0471786A1 (de) |
AU (1) | AU5677390A (de) |
CA (1) | CA2054759A1 (de) |
FI (1) | FI915161A0 (de) |
NL (1) | NL8901118A (de) |
WO (1) | WO1990013699A2 (de) |
Families Citing this family (6)
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 |
GB2301122A (en) * | 1995-05-24 | 1996-11-27 | Cyril Glass | Flame retardant compositions |
DE102006056661A1 (de) * | 2006-11-29 | 2008-06-05 | Union Marketing Gmbh | Flammhemmende Ausrüstung, ihre Herstellung, Aufbringung auf brennbare Produkte und Verwendung |
EP3098259A1 (de) | 2012-04-24 | 2016-11-30 | Winnitex Limited | Formaldehydfreie flammhemmende zusammensetzungen und deren verwendung zur herstellung haltbarer formaldehydfreier flammhemmender cellulosematerialien |
BE1025604B1 (fr) * | 2017-10-02 | 2019-04-29 | Uniteq Sa | Cylindre pour extincteur d'incendie |
CN116535633B (zh) * | 2023-04-29 | 2024-08-23 | 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 |
Family Cites Families (3)
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 |
-
1989
- 1989-05-02 NL NL8901118A patent/NL8901118A/nl not_active Application Discontinuation
-
1990
- 1990-05-02 WO PCT/NL1990/000061 patent/WO1990013699A2/en not_active Application Discontinuation
- 1990-05-02 EP EP19900908691 patent/EP0471786A1/de not_active Withdrawn
- 1990-05-02 CA CA 2054759 patent/CA2054759A1/en not_active Abandoned
- 1990-05-02 AU AU56773/90A patent/AU5677390A/en not_active Abandoned
-
1991
- 1991-11-01 FI FI915161A patent/FI915161A0/fi not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9013699A2 * |
Also Published As
Publication number | Publication date |
---|---|
WO1990013699A2 (en) | 1990-11-15 |
AU5677390A (en) | 1990-11-29 |
FI915161A0 (fi) | 1991-11-01 |
WO1990013699A3 (en) | 1990-12-13 |
NL8901118A (nl) | 1990-12-03 |
CA2054759A1 (en) | 1990-11-03 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19911031 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19920810 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19921221 |