CA2310438A1 - Intumescent, flame-retardant coating compositions - Google Patents
Intumescent, flame-retardant coating compositions Download PDFInfo
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- CA2310438A1 CA2310438A1 CA002310438A CA2310438A CA2310438A1 CA 2310438 A1 CA2310438 A1 CA 2310438A1 CA 002310438 A CA002310438 A CA 002310438A CA 2310438 A CA2310438 A CA 2310438A CA 2310438 A1 CA2310438 A1 CA 2310438A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
The invention relates to intumescent flame-retardant coatings, containing 10 to 150 parts by weight of an aqueous artificial resin dispersion and 10 to 80 parts by weight of a mixture of at least two different phosphoric acid partial esters.
Description
Intumescent, flame-retardant coating compositions The invention relates to intumescent, flame-retardant coating compositions and to their use.
Flame-retardant coating compositions based on solvent-containing binders and comprising chlorinated paraffins as their flame-retardant component are known (Bhatnagar and Vergnaud in Fire Safety Journal 4(3), 163-7 and Paintindia 32(1) 3-6, 14; 1982).
A disadvantage of these systems is that solvent vapors are given off in the course of drying, and corrosive and toxic, halogen-containing combustion gases are released in the event of .fire. , US-A 4,166,743 discloses expandable coating compositions consisting of a film former, an ammonium polyphosphate, at least one substance which carbonizes on exposure to heat, a dispersant, a salt containing water of crystallization, an expansion agent, and, if desired, fillers. Film formers which can be employed in these compositions are aqueous dispersions of polyvinyl acetate or of a copolymer of vinyl acetate and dibutyl maleate, while a suitable carbonizing substance is dicyandiamide, pentaerythritol or melamine. Apart from water, suitable dispersants are ethyl acetate, butyl acetate, xylene or toluene, whereas chlorinated paraffins are used as expansion agents.
Flame-retardant coating compositions based on solvent-containing binders and comprising chlorinated paraffins as their flame-retardant component are known (Bhatnagar and Vergnaud in Fire Safety Journal 4(3), 163-7 and Paintindia 32(1) 3-6, 14; 1982).
A disadvantage of these systems is that solvent vapors are given off in the course of drying, and corrosive and toxic, halogen-containing combustion gases are released in the event of .fire. , US-A 4,166,743 discloses expandable coating compositions consisting of a film former, an ammonium polyphosphate, at least one substance which carbonizes on exposure to heat, a dispersant, a salt containing water of crystallization, an expansion agent, and, if desired, fillers. Film formers which can be employed in these compositions are aqueous dispersions of polyvinyl acetate or of a copolymer of vinyl acetate and dibutyl maleate, while a suitable carbonizing substance is dicyandiamide, pentaerythritol or melamine. Apart from water, suitable dispersants are ethyl acetate, butyl acetate, xylene or toluene, whereas chlorinated paraffins are used as expansion agents.
According to . Troitzsch (International Plastics Flammability Handbook, 2nd edition, Oxford University Press, New York, 1990, pages 52 and 53) typical representatives of carbonizing substances are pentaerythritol and starch, while guanidines, melamine and chlorinated paraffins are classified as expansion agents.
A disadvantage of the abovementioned expandable coating compositions is that they contain organically bonded halogen in the expansion agent and/or in the substance which carbonizes on exposure to heat, thereby releasing corrosive and toxic gases when the coating compositions decompose.
In addition, DE 43 43 668 A1 describes expandable, flame-retardant coating compositions consisting of a film-forming binder, ammonium polyphosphate, at least one substance which carbonizes on exposure to heat, an expansion agent and, if desired, dispersants and fillers.
DE 43 43 669 A1 describes expandable, flame-retardant coating compositions of similar composition but without ammonium polyphosphate.
However, the existing systems only achieve short, inadequate service lives.
A disadvantage of the abovementioned expandable coating compositions is that they contain organically bonded halogen in the expansion agent and/or in the substance which carbonizes on exposure to heat, thereby releasing corrosive and toxic gases when the coating compositions decompose.
In addition, DE 43 43 668 A1 describes expandable, flame-retardant coating compositions consisting of a film-forming binder, ammonium polyphosphate, at least one substance which carbonizes on exposure to heat, an expansion agent and, if desired, dispersants and fillers.
DE 43 43 669 A1 describes expandable, flame-retardant coating compositions of similar composition but without ammonium polyphosphate.
However, the existing systems only achieve short, inadequate service lives.
A pr-oposal has also been made of water-based, flame-retardant coating compositions in which polyol-based phosphoric acid partial esters act as acid donors and carbonizing substances (EP 0 556 350 B1).
The disadvantage in this case is that polyol-based phosphoric acid partial esters are very complex to prepare on an industrial scale and are therefore not available in great amounts. Furthermore, the service lives achievable with the existing systems are only of the order of minutes.
Finally, EP 0 417 490 B1 describes phosphoric esters and their salts, molding compounds and coating materials comprising them, the use of these phosphoric esters and their salts as dispersants, and the solids coated with them.
Overall, the prior art provides, on the one hand, formulations which contain halogen and therefore release toxic and corrosive gases in the event of fire.
With the halogen-free systems, on the other hand, the service lives are very short and in some cases the products do not achieve adequate cure. With some systems there are also problems associated with their technical production; with others, the scope for application is small.
The disadvantage in this case is that polyol-based phosphoric acid partial esters are very complex to prepare on an industrial scale and are therefore not available in great amounts. Furthermore, the service lives achievable with the existing systems are only of the order of minutes.
Finally, EP 0 417 490 B1 describes phosphoric esters and their salts, molding compounds and coating materials comprising them, the use of these phosphoric esters and their salts as dispersants, and the solids coated with them.
Overall, the prior art provides, on the one hand, formulations which contain halogen and therefore release toxic and corrosive gases in the event of fire.
With the halogen-free systems, on the other hand, the service lives are very short and in some cases the products do not achieve adequate cure. With some systems there are also problems associated with their technical production; with others, the scope for application is small.
It is therefore an object of the present invention to provide intumescent coating compositions which are halogen-free, have sufficient service lives and form fully cured products without the addition of further (curing) substances.
This object is achieved by intumescent, flame-retardant coating compositions of the type described at the outset, comprising from 10 to 150 parts by weight of an aqueous synthetic-resin dispersion, and from 10 to 80 parts by weight of a mixture of at least two different phosphoric acid partial esters.
Preferably, the intumescent, flame-retardant coating compositions comprise from 50 to 90 parts by weight of an aqueous synthetic-resin dispersion, and from 20 to 60 parts by weight of a mixture of at least two different phosphoric acid partial esters, and from 1 to 80 parts by weight of further constituents.
Preferably, a mixture of 3 different phosphoric acid partial esters is present.
This object is achieved by intumescent, flame-retardant coating compositions of the type described at the outset, comprising from 10 to 150 parts by weight of an aqueous synthetic-resin dispersion, and from 10 to 80 parts by weight of a mixture of at least two different phosphoric acid partial esters.
Preferably, the intumescent, flame-retardant coating compositions comprise from 50 to 90 parts by weight of an aqueous synthetic-resin dispersion, and from 20 to 60 parts by weight of a mixture of at least two different phosphoric acid partial esters, and from 1 to 80 parts by weight of further constituents.
Preferably, a mixture of 3 different phosphoric acid partial esters is present.
With particular preference, a mixture of 4 different phosphoric acid partial esters is present.
In particular, the intumescent, flame-retardant coating composition consists of a) a mixture of a monoalkyl phosphate and a dialkyl phosphate with the same alkyl group, and b) a mixture of a monoalkyl phosphate and a dialkyl phosphate with the same alkyl group which, however, is different from that of a).
The phosphoric acid partial esters are preferably monomethyl, monoethyl, monopropyl, monoisopropyl, monobutyl, monoisobutyl, monopentyl, monoisopentyl, monohexyl, monooctyl, mono(2-ethylhexyl), monoethylene glycol, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, diisobutyl, dipentyl, dihexyl, dioctyl, di(2-ethylhexyl) and/or diethylene glycol phosphate, and mixtures thereof.
The aqueous synthetic-resin dispersion is preferably a nitrogen-containing synthetic-resin dispersion.
The aqueous synthetic-resin dispersion is preferably a melamine-formaldehyde and/or urea-formaldehyde resin.
The aqueous synthetic-resin dispersion is with particular preference an etherified melamine-formaldehyde and/or urea-formaldehyde resin.
In particular, the intumescent, flame-retardant coating composition consists of a) a mixture of a monoalkyl phosphate and a dialkyl phosphate with the same alkyl group, and b) a mixture of a monoalkyl phosphate and a dialkyl phosphate with the same alkyl group which, however, is different from that of a).
The phosphoric acid partial esters are preferably monomethyl, monoethyl, monopropyl, monoisopropyl, monobutyl, monoisobutyl, monopentyl, monoisopentyl, monohexyl, monooctyl, mono(2-ethylhexyl), monoethylene glycol, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, diisobutyl, dipentyl, dihexyl, dioctyl, di(2-ethylhexyl) and/or diethylene glycol phosphate, and mixtures thereof.
The aqueous synthetic-resin dispersion is preferably a nitrogen-containing synthetic-resin dispersion.
The aqueous synthetic-resin dispersion is preferably a melamine-formaldehyde and/or urea-formaldehyde resin.
The aqueous synthetic-resin dispersion is with particular preference an etherified melamine-formaldehyde and/or urea-formaldehyde resin.
The-abovementioned melamine resins used in accordance with the invention are usually reaction products of melamine with formaldehyde in a molar ratio of from 1:1 to 1:6 (melamine: formaldehyde).
The melamine-formaldehyde resins can also be in a form etherified with alcohols of chain length 1-20 carbon atoms, preferably 1-4 carbon atoms.
The further constitutents are preferably dispersants, fillers, curing agents, thixotropic agents, plasticizers, acid donors, further flame retardants, surface auxiliaries and/or binders.
By colorants for the purposes of the invention are meant those as specified, for example, as coloring agents in Rompp's Chemie Lexikon, 9th Edition, 1992, page 1237. This term includes organic and inorganic, natural and synthetic colorants, in other words pigments and dyes.
Without the use of colorants, the intumescent flame-retardant coating compositions of the invention are normally clear (transparent). By adding fillers, especially talc et cetera, the coating compositions can also be given a cloudy appearance. Through the choice of an appropriate colorant, especially the inorganic pigments, it is also possible to prepare intumescent, _ ~j flame-retardant coating compositions which are colored, preferably white-, in the dry state.
With particular preference, the further constituents are thixotropic agents and/or fillers.
The phosphoric acid partial esters are preferably those of the formula O=P-OH
in which R1 and Rz are identical or different and are H, CH3, CzHs, C3H,, C4H9, CSHll, C6H13, CaHls and/or CHZ-CHZ-OH
but are not both hydrogen.
The novel mixture of at least two different phosphoric acid partial esters consists usually of from 2 to 98%.
by weight of one phosphoric acid partial ester and from 98 to 2% by weight of a different phosphoric acid partial ester.
It is preferred to employ from 10 to 90% by weight of the one and from 90 to 10% by weight of the other phosphoric acid partial ester.
In the case of the mixtures of 3 different phosphoric acid partial esters, the proportions are usually (from 2 to 98) . (from 4 to 96) . (from 4 to 96) % by weight.
_ g _ In the case of .the mixtures of 4 different phosphoric acid partial --esters the proportion of mixture a) to mixture b) is (from 98 to 2) . (from 2 to 98) % by weight and preferably (from 10 to 90) . (from 90 to 10)% by weight. For the mixture within a) and, b), respectively, the proportion of monoalkyl phosphate to dialkyl phosphate is (from 2 to 98) . (from 98 to 2)%
by weight, preferably (from 10 to 90) . (from 90 to 10)% by weight.
Examples of dispersants which can be employed for solids are phosphoric acid mono(polyethylene glycol)-alkyl esters, phosphoric acid mono(polyethylene glycol)aryl esters, phosphoric acid di(polyethylene glycol)alkyl esters and/or phosphoric acid di(poly-ethylene glycol)aryl esters and mixtures thereof.
The phosphorus content of the intumescent, flame retardant coating compositions after curing is from 1 to 15% by weight.
The phosphorus content of the intumescent, flame-retardant coating compositions after curing is preferably from 4 to 10% by weight.
The invention also provides for the use of the coating compositions of the invention to produce coatings on articles made of wood, plastics, building materials, - g _ cellulose materials, rubber and metal and to impregnate textiles and leathers.
The invention is illustrated by the examples below, in which the following substance have been used.
~Maprenal MF 920 ~Maprenal MF 920 (Vianova Resins) is an unplasticized, methyl-etherified melamine-formaldehyde resin.
~Maprenal VMF 3921 w ~Maprenal VMF 3921 w (Vianova Resins) is an unplasticized, methyl-etherified melamine-formaldehyde resin.
Plastopal BTW
This is an elastic, urethane-functional, methanol-etherified urea-formaldehyde resin (manufacturer:
BASF) .
~Knapsack Phosphorsaureester MDE
This is a mixture of a monoethyl phosphate and a diethyl phosphate.
°Knapsack Phosphorsaureester MDIP
This is a mixture of a monoisopropyl phosphate and a diisopropyl phosphate.
°Knapsack Phosphorsaureester 122 This dispersant_ is a mixture of a phosphoric acid mono(polyethylene glycol)alkyl ester and a phosphoric acid di(polyethylene glycol)alkyl ester.
°Knapsack Reinigerkomponente MIS
This cleaner ingredient is a mixture of monoisopropyl phosphate, monomethyl phosphate and phosphoric acid.
°Knapsack Phosphorsaureester MOE
This is a mixture of monoethyl phosphate and phosphoric acid.
°Knapsack Reinigerkomponente MS
This cleaner ingredient is monomethyl phosphate.
°Knapsack Phosphorsaureester MDB
This is a mixture of monobutyl and dibutyl phosphates.
The abovementioned commercial products °Knapsack Phosphorsaureester and °Knapsack Reinigerkomponente are produced by Clariant GmbH, Werk Knapsack.
°Mistrofil 500 This is a commercial talc.
°Aerosil R 816 This is pyrogenic silica from Degussa AG.
The various components were mixed with one another in the- sequence stated in the examples, applied to pinewood or chipboard and dried, and their intumescence behavior was determined. The sequence in which the components are applied is arbitrary, and depends on their desired coat thickness and on other conditions (viscosity, substrate, service life, etc.).
Other substances, if appropriate, are explained in the respective examples.
The coating compositions obtained in accordance with the examples below are clear, smooth and free from cracks. The service life is on average more than 24 hours. After less than 24 hours (on average) the applied coating composition is tack-free and hard. In fire tests of these formulations on pinewood and chipboard, classifications B1 and B2 were achieved.
Example 1 68 parts by weight of °Maprenal MF 920 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Reinigerkomponente MS
Example 2 68 parts by weight of °Maprenal MF 920 24.8 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Reinigerkomponente MS
Example 3 68 parts by weight of °Maprenal MF 920 24.9 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MOE and 30% by weight °Knapsack Reinigerkomponente MS
Repetition of Examples 1 to 3 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of ~Maprenal MF 920 gave similar results.
Example 4 68 parts by weight of °Maprenal MF 920 24.9 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Reinigerkomponente MIS
Example 5 68 parts by weight of °Maprenal MF 920 24.8 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MOE and 30% by weight °Knapsack Reinigerkomponente MIS
Example 6 68 parts by weight of °Maprenal MF 920 24.9 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Reinigerkomponente MIS
Repetition of Examples 4 to 6 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of ~Maprenal MF 920 gave similar results.
Example 7 68 parts by weight of °Maprenal MF 920 26.1 parts by weight of a mixture of 90% by weight Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Phosphorsaureester MDIP
Example 8 68 parts by weight of ~Maprenal MF 920 26.4 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Phosphorsaureester MDIP
Example 9 68 parts by weight of °Maprenal MF 920 28.7 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MOE and 30% by weight °Knapsack Phosphorsaureester MDIP
Example 10 68 parts by weight of °Maprenal MF 920 26.4 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Phosphorsaureester MDB
Example 11 68 parts by weight of °Maprenal MF 920 27.9 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Phosphorsaureester MDB
Example 12 68 parts by weight of °Maprenal MF 920 29.6 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Phosphorsaureester MDB
Repetition of Examples 7 to 12 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of °Maprenal MF 920 gave similar results.
Example 13 68 parts by weight of °Maprenal MF 920 24.3 parts by weight of a mixture of 90% by weight °Knapsack Reinigerkomponente MS and 10% by weight °Knapsack Reinigerkomponente MIS
Example 14 68 parts by weight of °Maprenal MF 920 24.4 parts by weight of a mixture of 80% by weight _ °Knapsack Reinigerkomponente MS and 20% by weight °Knapsack Reinigerkomponente MIS
Example 15 68 parts by weight of °Maprenal MF 920 24.3 parts by weight of a mixture of 70% by weight °Knapsack Reinigerkomponente MS and 30% by weight °Knapsack Reinigerkomponente MIS
Example 16 68 parts by weight of °Maprenal MF 920 25.5 parts by weight of a mixture of 90% by weight °Knapsack Reinigerkomponente MS and 10% by weight ~Knapsack Phosphorsaureester MDIP
Example 17 68 parts by weight of ~Maprenal MF 920 26.7 parts by weight of a mixture of 80% by weight °Knapsack Reinigerkomponente MS and 20% by weight °Knapsack Phosphorsaureester MDIP
Example 18 68 parts by weight of ~Maprenal MF 920 28.0 parts by weight of a mixture of 70% by weight °Knapsack Reinigerkomponente MS and 30% by weight °Knapsack Phosphorsaureester MDIP
Example 19 68 garts by weight of °Maprenal MF 920 25.7 parts by weight of a mixture of 90% by weight °Knapsack Reinigerkomponente MS and 10% by weight °Knapsack Phosphorsaureester MDB
Example 20 68 parts by weight of °Maprenal MF 920 27.2 parts by weight of a mixture of 80% by weight °Knapsack Reinigerkomponente MS and 20% by weight °Knapsack Phosphorsaureester MDB
Example 21 68 parts by weight of °Maprenal MF 920 29.0 parts by weight of a mixture of 70% by weight °Knapsack Reinigerkomponente MS and 30% by weight Knapsack Phosphorsaureester MDB
Example 22 68 parts by weight of ~Maprenal MF 920 30.1 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MDE and 10% by weight ~Knapsack Reinigerkomponente MS
Example 23 68 parts by weight of °Maprenal MF 920 30.1 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MDE and 20% by weight °Knapsack Reinigerkomponente MS
Example 24 68 parts by weight of °Maprenal MF 920 29.3 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MDE and 30% by weight °Knapsack Reinigerkomponente MS
Repetition of Examples 13 to 24 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of ~Maprenal MF 920 gave similar results.
Example 25 60 parts by weight of °Maprenal MF 3921 w 27 parts by weight of ~Knapsack Phosphorsaureester MDE
The melamine-formaldehyde resins can also be in a form etherified with alcohols of chain length 1-20 carbon atoms, preferably 1-4 carbon atoms.
The further constitutents are preferably dispersants, fillers, curing agents, thixotropic agents, plasticizers, acid donors, further flame retardants, surface auxiliaries and/or binders.
By colorants for the purposes of the invention are meant those as specified, for example, as coloring agents in Rompp's Chemie Lexikon, 9th Edition, 1992, page 1237. This term includes organic and inorganic, natural and synthetic colorants, in other words pigments and dyes.
Without the use of colorants, the intumescent flame-retardant coating compositions of the invention are normally clear (transparent). By adding fillers, especially talc et cetera, the coating compositions can also be given a cloudy appearance. Through the choice of an appropriate colorant, especially the inorganic pigments, it is also possible to prepare intumescent, _ ~j flame-retardant coating compositions which are colored, preferably white-, in the dry state.
With particular preference, the further constituents are thixotropic agents and/or fillers.
The phosphoric acid partial esters are preferably those of the formula O=P-OH
in which R1 and Rz are identical or different and are H, CH3, CzHs, C3H,, C4H9, CSHll, C6H13, CaHls and/or CHZ-CHZ-OH
but are not both hydrogen.
The novel mixture of at least two different phosphoric acid partial esters consists usually of from 2 to 98%.
by weight of one phosphoric acid partial ester and from 98 to 2% by weight of a different phosphoric acid partial ester.
It is preferred to employ from 10 to 90% by weight of the one and from 90 to 10% by weight of the other phosphoric acid partial ester.
In the case of the mixtures of 3 different phosphoric acid partial esters, the proportions are usually (from 2 to 98) . (from 4 to 96) . (from 4 to 96) % by weight.
_ g _ In the case of .the mixtures of 4 different phosphoric acid partial --esters the proportion of mixture a) to mixture b) is (from 98 to 2) . (from 2 to 98) % by weight and preferably (from 10 to 90) . (from 90 to 10)% by weight. For the mixture within a) and, b), respectively, the proportion of monoalkyl phosphate to dialkyl phosphate is (from 2 to 98) . (from 98 to 2)%
by weight, preferably (from 10 to 90) . (from 90 to 10)% by weight.
Examples of dispersants which can be employed for solids are phosphoric acid mono(polyethylene glycol)-alkyl esters, phosphoric acid mono(polyethylene glycol)aryl esters, phosphoric acid di(polyethylene glycol)alkyl esters and/or phosphoric acid di(poly-ethylene glycol)aryl esters and mixtures thereof.
The phosphorus content of the intumescent, flame retardant coating compositions after curing is from 1 to 15% by weight.
The phosphorus content of the intumescent, flame-retardant coating compositions after curing is preferably from 4 to 10% by weight.
The invention also provides for the use of the coating compositions of the invention to produce coatings on articles made of wood, plastics, building materials, - g _ cellulose materials, rubber and metal and to impregnate textiles and leathers.
The invention is illustrated by the examples below, in which the following substance have been used.
~Maprenal MF 920 ~Maprenal MF 920 (Vianova Resins) is an unplasticized, methyl-etherified melamine-formaldehyde resin.
~Maprenal VMF 3921 w ~Maprenal VMF 3921 w (Vianova Resins) is an unplasticized, methyl-etherified melamine-formaldehyde resin.
Plastopal BTW
This is an elastic, urethane-functional, methanol-etherified urea-formaldehyde resin (manufacturer:
BASF) .
~Knapsack Phosphorsaureester MDE
This is a mixture of a monoethyl phosphate and a diethyl phosphate.
°Knapsack Phosphorsaureester MDIP
This is a mixture of a monoisopropyl phosphate and a diisopropyl phosphate.
°Knapsack Phosphorsaureester 122 This dispersant_ is a mixture of a phosphoric acid mono(polyethylene glycol)alkyl ester and a phosphoric acid di(polyethylene glycol)alkyl ester.
°Knapsack Reinigerkomponente MIS
This cleaner ingredient is a mixture of monoisopropyl phosphate, monomethyl phosphate and phosphoric acid.
°Knapsack Phosphorsaureester MOE
This is a mixture of monoethyl phosphate and phosphoric acid.
°Knapsack Reinigerkomponente MS
This cleaner ingredient is monomethyl phosphate.
°Knapsack Phosphorsaureester MDB
This is a mixture of monobutyl and dibutyl phosphates.
The abovementioned commercial products °Knapsack Phosphorsaureester and °Knapsack Reinigerkomponente are produced by Clariant GmbH, Werk Knapsack.
°Mistrofil 500 This is a commercial talc.
°Aerosil R 816 This is pyrogenic silica from Degussa AG.
The various components were mixed with one another in the- sequence stated in the examples, applied to pinewood or chipboard and dried, and their intumescence behavior was determined. The sequence in which the components are applied is arbitrary, and depends on their desired coat thickness and on other conditions (viscosity, substrate, service life, etc.).
Other substances, if appropriate, are explained in the respective examples.
The coating compositions obtained in accordance with the examples below are clear, smooth and free from cracks. The service life is on average more than 24 hours. After less than 24 hours (on average) the applied coating composition is tack-free and hard. In fire tests of these formulations on pinewood and chipboard, classifications B1 and B2 were achieved.
Example 1 68 parts by weight of °Maprenal MF 920 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Reinigerkomponente MS
Example 2 68 parts by weight of °Maprenal MF 920 24.8 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Reinigerkomponente MS
Example 3 68 parts by weight of °Maprenal MF 920 24.9 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MOE and 30% by weight °Knapsack Reinigerkomponente MS
Repetition of Examples 1 to 3 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of ~Maprenal MF 920 gave similar results.
Example 4 68 parts by weight of °Maprenal MF 920 24.9 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Reinigerkomponente MIS
Example 5 68 parts by weight of °Maprenal MF 920 24.8 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MOE and 30% by weight °Knapsack Reinigerkomponente MIS
Example 6 68 parts by weight of °Maprenal MF 920 24.9 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Reinigerkomponente MIS
Repetition of Examples 4 to 6 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of ~Maprenal MF 920 gave similar results.
Example 7 68 parts by weight of °Maprenal MF 920 26.1 parts by weight of a mixture of 90% by weight Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Phosphorsaureester MDIP
Example 8 68 parts by weight of ~Maprenal MF 920 26.4 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Phosphorsaureester MDIP
Example 9 68 parts by weight of °Maprenal MF 920 28.7 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MOE and 30% by weight °Knapsack Phosphorsaureester MDIP
Example 10 68 parts by weight of °Maprenal MF 920 26.4 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MOE and 10% by weight °Knapsack Phosphorsaureester MDB
Example 11 68 parts by weight of °Maprenal MF 920 27.9 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Phosphorsaureester MDB
Example 12 68 parts by weight of °Maprenal MF 920 29.6 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MOE and 20% by weight °Knapsack Phosphorsaureester MDB
Repetition of Examples 7 to 12 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of °Maprenal MF 920 gave similar results.
Example 13 68 parts by weight of °Maprenal MF 920 24.3 parts by weight of a mixture of 90% by weight °Knapsack Reinigerkomponente MS and 10% by weight °Knapsack Reinigerkomponente MIS
Example 14 68 parts by weight of °Maprenal MF 920 24.4 parts by weight of a mixture of 80% by weight _ °Knapsack Reinigerkomponente MS and 20% by weight °Knapsack Reinigerkomponente MIS
Example 15 68 parts by weight of °Maprenal MF 920 24.3 parts by weight of a mixture of 70% by weight °Knapsack Reinigerkomponente MS and 30% by weight °Knapsack Reinigerkomponente MIS
Example 16 68 parts by weight of °Maprenal MF 920 25.5 parts by weight of a mixture of 90% by weight °Knapsack Reinigerkomponente MS and 10% by weight ~Knapsack Phosphorsaureester MDIP
Example 17 68 parts by weight of ~Maprenal MF 920 26.7 parts by weight of a mixture of 80% by weight °Knapsack Reinigerkomponente MS and 20% by weight °Knapsack Phosphorsaureester MDIP
Example 18 68 parts by weight of ~Maprenal MF 920 28.0 parts by weight of a mixture of 70% by weight °Knapsack Reinigerkomponente MS and 30% by weight °Knapsack Phosphorsaureester MDIP
Example 19 68 garts by weight of °Maprenal MF 920 25.7 parts by weight of a mixture of 90% by weight °Knapsack Reinigerkomponente MS and 10% by weight °Knapsack Phosphorsaureester MDB
Example 20 68 parts by weight of °Maprenal MF 920 27.2 parts by weight of a mixture of 80% by weight °Knapsack Reinigerkomponente MS and 20% by weight °Knapsack Phosphorsaureester MDB
Example 21 68 parts by weight of °Maprenal MF 920 29.0 parts by weight of a mixture of 70% by weight °Knapsack Reinigerkomponente MS and 30% by weight Knapsack Phosphorsaureester MDB
Example 22 68 parts by weight of ~Maprenal MF 920 30.1 parts by weight of a mixture of 90% by weight °Knapsack Phosphorsaureester MDE and 10% by weight ~Knapsack Reinigerkomponente MS
Example 23 68 parts by weight of °Maprenal MF 920 30.1 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MDE and 20% by weight °Knapsack Reinigerkomponente MS
Example 24 68 parts by weight of °Maprenal MF 920 29.3 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MDE and 30% by weight °Knapsack Reinigerkomponente MS
Repetition of Examples 13 to 24 with 60 parts by weight of °Maprenal VMF 3921 w instead of 68 parts by weight of ~Maprenal MF 920 gave similar results.
Example 25 60 parts by weight of °Maprenal MF 3921 w 27 parts by weight of ~Knapsack Phosphorsaureester MDE
7 parts by weight of °Knapsack Phosphorsaureester MDIP
Example 26 60.0 parts by weight of ~Maprenal MF 920 24.0 parts by weight of °Knapsack Phosphorsaureester MDE
6.0 parts by weight of °Knapsack Phosphorsaureester MDIP
3.0 parts by weight of °Aerosil R 816 7.0 parts by weight of °Mistrofil 500 Example 27 60 parts by weight of °Maprenal MF 920 27.1 parts by weight of °Knapsack Phosphorsaureester MDE
6.8 parts by weight of °Knapsack Phosphorsaureester - MDIP
0.6 parts by weight of °Knapsack Phosphorsaureester 3.0 parts by weight of °Aerosil R 816 7.2 parts by weight of °Mistrofil 500 Example 28 60 parts by weight of ~Maprenal VMF 3921 w 34.5 parts by weight of a mixture of 75% by weight °Knapsack Phosphorsaureester MDE
and 25% by weight °Knapsack Phosphorsaure-ester MDIP
Example 29 80 parts by weight of ~Maprenal VMF 3921 w 44.6 parts by weight of a mixture of 85% by weight °Knapsack Phosphorsaureester MDE
and 15% by weight °Knapsack Phosphorsaure-ester MDIP
Example 30 80 parts by weight of ~Maprenal VMF 3921 w 46.5 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MDE
and 30% by weight °Knapsack Phosphorsaure-ester MDIP
9.6 parts by weight of °Mistrofil 500 4 parts by weight of highly disperse silica Further examples of the intumescent flame-retardant coating composition of the invention are given in Tables 1 to 11. Every formulation attained B1 or B2 in the fire test.
Table 1:
Constituents Parts by weight Example 31 Example 32 Example 33 Maprenal VMF 3921 w 80 80 80 MDE . MDIP *) 44.6 44.7 44.1 85 . 15 ~Mistrofil 500 8 9.2 10.4 *) MDE . MDIP Mixture of 85% by weight °Knapsack 85 . 15 Phosphorsaureester MDE and 15% by weight °Knapsack Phosphorsaureester MDIP. This notation applies analogously for the following tables.
Table 2:
Constituents Parts by weight Example 34 Example 35 Example 36 ~Maprenal MF 920 75 80 80 MDE . MDIP 37.5 40 40 ~Mistrofil 500 13.5 17 20.8 Table 3:
Constituents . _ Parts by weight Example 37 Example 38 Example 39 Maprenal VMF 3921 w 60 60 60 MDE . MDIP 34.5 34.5 34.5 Mistrofil 500 7.8 6 6.9 Table 4:
Constituents Parts by weight Ex. Ex. Ex. Ex. Ex. Ex.
~Maprenal VMF 3921 w 50 80 80 75 75 60 MDE . MDIP 28.3 46 46 42.4 42.3 33.5 Mistrofil 500 6.5 8 9.2 12.7 15.2 17.5 Table 5:
Constituents _, Parts by weight Ex. 46 Ex. 47 Ex. 48 Ex. 49 ~Maprenal VMF 3921 w 80 80 80 80 MDE . MDIP 45.4 45.3 45.2 45.2 80 . 20 highly disperse 4 6 8 10 silica SCAB-O-SIL ~Aerosil In this series of experiments, the highly disperse sili-ca used was_°CAB-O-SIL TS 530 (from CABOT, Hanau, Germany). °Aerosil OX-50 (pyrogenic silica from Degussa AG) was also used successfully.
Example 50 90 parts by weight of °Maprenal VMF 3921 w 41.15 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MDE
and 20% by weight Knapsack Reinigerkomponente MIS
11.7 parts by weight of °Mistrofil 500 0.9 parts by weight of °Knapsack Phosphorsaureester Table 6:
Constituents Parts by weight Example 51 Example Plastopal BTW 60 60 MDE . MDIP 31 30.4 Mistrofil 500 7.9 6.8 Knapsack Phosphorsaureester 122 0.6 0.2 Table 7:
Constituents Parts by weight Example 53 Example 54 Maprenal VMF 3921 w 90 90 MDE . MIS 45 45 80 . 20 Knapsack Phosphorsaureester 122 0.9 0.9 highly disperse silica 9 10.8 ~Aerosil OX 50 Table 8:
Constituents Parts by weight Example 55 Example 56 ~Maprenal VMF 3921 w 80 80 MDE . MDIP 45.2 45.5 80 . 20 ~Mistrofil 500 9.6 8 highly disperse silica 4.0 4.8 ~Aerosil R 972 Table 9:
Constituents Parts by weight Ex. Ex. Ex. Ex.
~Maprenal VMF 3921 w 75 75 75 75 MDE . MDIP 42.6 42.5 42.4 42.5 80 . 20 ~Knapsack 0.5 0.5 0.5 0.5 Phosphorsaureester 122 highly disperse silica 7.5 9 5.6 7.5 ~Aerosil SCAB-O-SIL
Table 10:
Constituents Parts by weight Ex. Ex. Ex. Ex.
~Maprenal VMF 3921 75 80 80 80 w MDE . MDIP 42.4 40 45.2 42.4 ~Knapsack Phosphor- 0.5 0.6 1.8 0.5 saureester 122 highly disperse 3 4 4 3 silica- CAB-O- Aerosil ~Aerosil CAB-O-Repetition of Examples 61 to 64 with ~Maprenal MF 920 instead of °Maprenal VMF 3921 w gave similar results.
Table 11:
Constituents Parts by weight Example 65 Example 66 ~Maprenal VMF 3921 90 90 w MDE . MDIP 45 45 80 . 20 Mistrofil 500 8 9 Knapsack Phosphor- 1 1 saureester 122 highly disperse 3.6 5.2 silica Aerosil ~Aerosil Example 67 80 parts by weight of °Maprenal VMF 3921 w 45.2 parts by weight of a mixture of 80 % by weight Knapsack Phosphorsaureester MDE
and 20% by weight °Knapsack Phosphorsaureester MDIP
4 parts by weight of titanium dioxide (°Kronos 2300) Example 68 80 parts by weight of ~Maprenal VMF 3921 w 45.2 parts by weight of a mixture of 80 % by weight °Knapsack Phosphorsaureester MDE
and 20% by weight °Knapsack Phosphorsaureester MDIP
0.9 part by weight of °Knapsack Phosphorsaureester 122 4 parts by weight of titanium dioxide (°Kronos 2300) The coating compositions obtained in accordance with Example 67 and 68 are smooth, white and free from cracks.
Example 26 60.0 parts by weight of ~Maprenal MF 920 24.0 parts by weight of °Knapsack Phosphorsaureester MDE
6.0 parts by weight of °Knapsack Phosphorsaureester MDIP
3.0 parts by weight of °Aerosil R 816 7.0 parts by weight of °Mistrofil 500 Example 27 60 parts by weight of °Maprenal MF 920 27.1 parts by weight of °Knapsack Phosphorsaureester MDE
6.8 parts by weight of °Knapsack Phosphorsaureester - MDIP
0.6 parts by weight of °Knapsack Phosphorsaureester 3.0 parts by weight of °Aerosil R 816 7.2 parts by weight of °Mistrofil 500 Example 28 60 parts by weight of ~Maprenal VMF 3921 w 34.5 parts by weight of a mixture of 75% by weight °Knapsack Phosphorsaureester MDE
and 25% by weight °Knapsack Phosphorsaure-ester MDIP
Example 29 80 parts by weight of ~Maprenal VMF 3921 w 44.6 parts by weight of a mixture of 85% by weight °Knapsack Phosphorsaureester MDE
and 15% by weight °Knapsack Phosphorsaure-ester MDIP
Example 30 80 parts by weight of ~Maprenal VMF 3921 w 46.5 parts by weight of a mixture of 70% by weight °Knapsack Phosphorsaureester MDE
and 30% by weight °Knapsack Phosphorsaure-ester MDIP
9.6 parts by weight of °Mistrofil 500 4 parts by weight of highly disperse silica Further examples of the intumescent flame-retardant coating composition of the invention are given in Tables 1 to 11. Every formulation attained B1 or B2 in the fire test.
Table 1:
Constituents Parts by weight Example 31 Example 32 Example 33 Maprenal VMF 3921 w 80 80 80 MDE . MDIP *) 44.6 44.7 44.1 85 . 15 ~Mistrofil 500 8 9.2 10.4 *) MDE . MDIP Mixture of 85% by weight °Knapsack 85 . 15 Phosphorsaureester MDE and 15% by weight °Knapsack Phosphorsaureester MDIP. This notation applies analogously for the following tables.
Table 2:
Constituents Parts by weight Example 34 Example 35 Example 36 ~Maprenal MF 920 75 80 80 MDE . MDIP 37.5 40 40 ~Mistrofil 500 13.5 17 20.8 Table 3:
Constituents . _ Parts by weight Example 37 Example 38 Example 39 Maprenal VMF 3921 w 60 60 60 MDE . MDIP 34.5 34.5 34.5 Mistrofil 500 7.8 6 6.9 Table 4:
Constituents Parts by weight Ex. Ex. Ex. Ex. Ex. Ex.
~Maprenal VMF 3921 w 50 80 80 75 75 60 MDE . MDIP 28.3 46 46 42.4 42.3 33.5 Mistrofil 500 6.5 8 9.2 12.7 15.2 17.5 Table 5:
Constituents _, Parts by weight Ex. 46 Ex. 47 Ex. 48 Ex. 49 ~Maprenal VMF 3921 w 80 80 80 80 MDE . MDIP 45.4 45.3 45.2 45.2 80 . 20 highly disperse 4 6 8 10 silica SCAB-O-SIL ~Aerosil In this series of experiments, the highly disperse sili-ca used was_°CAB-O-SIL TS 530 (from CABOT, Hanau, Germany). °Aerosil OX-50 (pyrogenic silica from Degussa AG) was also used successfully.
Example 50 90 parts by weight of °Maprenal VMF 3921 w 41.15 parts by weight of a mixture of 80% by weight °Knapsack Phosphorsaureester MDE
and 20% by weight Knapsack Reinigerkomponente MIS
11.7 parts by weight of °Mistrofil 500 0.9 parts by weight of °Knapsack Phosphorsaureester Table 6:
Constituents Parts by weight Example 51 Example Plastopal BTW 60 60 MDE . MDIP 31 30.4 Mistrofil 500 7.9 6.8 Knapsack Phosphorsaureester 122 0.6 0.2 Table 7:
Constituents Parts by weight Example 53 Example 54 Maprenal VMF 3921 w 90 90 MDE . MIS 45 45 80 . 20 Knapsack Phosphorsaureester 122 0.9 0.9 highly disperse silica 9 10.8 ~Aerosil OX 50 Table 8:
Constituents Parts by weight Example 55 Example 56 ~Maprenal VMF 3921 w 80 80 MDE . MDIP 45.2 45.5 80 . 20 ~Mistrofil 500 9.6 8 highly disperse silica 4.0 4.8 ~Aerosil R 972 Table 9:
Constituents Parts by weight Ex. Ex. Ex. Ex.
~Maprenal VMF 3921 w 75 75 75 75 MDE . MDIP 42.6 42.5 42.4 42.5 80 . 20 ~Knapsack 0.5 0.5 0.5 0.5 Phosphorsaureester 122 highly disperse silica 7.5 9 5.6 7.5 ~Aerosil SCAB-O-SIL
Table 10:
Constituents Parts by weight Ex. Ex. Ex. Ex.
~Maprenal VMF 3921 75 80 80 80 w MDE . MDIP 42.4 40 45.2 42.4 ~Knapsack Phosphor- 0.5 0.6 1.8 0.5 saureester 122 highly disperse 3 4 4 3 silica- CAB-O- Aerosil ~Aerosil CAB-O-Repetition of Examples 61 to 64 with ~Maprenal MF 920 instead of °Maprenal VMF 3921 w gave similar results.
Table 11:
Constituents Parts by weight Example 65 Example 66 ~Maprenal VMF 3921 90 90 w MDE . MDIP 45 45 80 . 20 Mistrofil 500 8 9 Knapsack Phosphor- 1 1 saureester 122 highly disperse 3.6 5.2 silica Aerosil ~Aerosil Example 67 80 parts by weight of °Maprenal VMF 3921 w 45.2 parts by weight of a mixture of 80 % by weight Knapsack Phosphorsaureester MDE
and 20% by weight °Knapsack Phosphorsaureester MDIP
4 parts by weight of titanium dioxide (°Kronos 2300) Example 68 80 parts by weight of ~Maprenal VMF 3921 w 45.2 parts by weight of a mixture of 80 % by weight °Knapsack Phosphorsaureester MDE
and 20% by weight °Knapsack Phosphorsaureester MDIP
0.9 part by weight of °Knapsack Phosphorsaureester 122 4 parts by weight of titanium dioxide (°Kronos 2300) The coating compositions obtained in accordance with Example 67 and 68 are smooth, white and free from cracks.
Claims (15)
1. An intumescent, flame-retardant coating composition comprising from 10 to 150 parts by weight of an aqueous synthetic-resin dispersion and from 10 to 80 parts by weight of a mixture of at least two different phosphoric acid partial esters.
2. The intumescent, flame-retardant coating composition as claimed in claim 1, which comprises from 50 to 90 parts by weight of an aqueous synthetic-resin dispersion, and from 20 to 60 parts by weight of a mixture of at least two different phosphoric acid partial esters, and from 1 to 80 parts by weight of further constituents.
3. The intumescent, flame-retardant coating composition as claimed in claim 1 or 2, which comprises a mixture of 3 different phosphoric acid partial esters.
4. The intumescent, flame-retardant coating composition as claimed in claim 1 or 2, which comprises a mixture of 4 different phosphoric acid partial esters.
5. The intumescent, flame-retardant coating composition as claimed in claim 4, wherein the mixture of 4 different phosphoric partial esters consists of a) a mixture of a monoalkyl phosphate and a dialkyl phosphate with the same alkyl group, and b) a mixture of a monoalkyl phosphate and a dialkyl phosphate with the same alkyl group which, however, is different from that of a).
6. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 5, wherein the aqueous synthetic-resin dispersion is a nitrogen-containing synthetic-resin dispersion.
7. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 6, wherein the aqueous synthetic-resin dispersion is a melamine-formaldehyde and/or urea-formaldehyde resin.
8. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 7, wherein the aqueous synthetic-resin dispersion is an etherified melamine-formaldehyde and/or urea-formaldehyde resin.
9. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 8, wherein the other constituents are dispersants, fillers, curing agents, thixotropic agents, plasticizers, acid donors, further flame retardants, surface auxiliaries and/or binders.
10. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 9, wherein the further constituents are thixotropic agents and/or fillers.
11. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 10, wherein the phosphoric acid partial esters are of the formula in which R1 and R2 are identical or different and are H, CH3, C2H5, C3H7, C4H9, C5H11, C6H13. C8H16 and/or CH2-CH2-OH but are not both hydrogen.
12. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 11, whose phosphorus content after curing is from 1 to 15% by weight.
13. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 11, whose phosphorus content after curing is from 5 to 10% by weight.
14. The intumescent, flame-retardant coating composition as claimed in at least one of claims 1 to 13, which is transparent after application and drying.
15. The use of a coating composition as claimed in at least one of claims 1 to 14 to produce coatings on articles made of wood, plastics, building materials, cellulose materials, rubber or metal or to impregnate textiles or leathers.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19751434A DE19751434A1 (en) | 1997-11-20 | 1997-11-20 | Intumescent, flame-retardant coating compounds |
| DE19751434.0 | 1997-11-20 | ||
| PCT/EP1998/007239 WO1999027021A1 (en) | 1997-11-20 | 1998-11-12 | Intumescent flame-retardant coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2310438A1 true CA2310438A1 (en) | 1999-06-03 |
Family
ID=7849302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002310438A Abandoned CA2310438A1 (en) | 1997-11-20 | 1998-11-12 | Intumescent, flame-retardant coating compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1034225A1 (en) |
| JP (1) | JP2001524571A (en) |
| KR (1) | KR20010032236A (en) |
| AR (1) | AR016690A1 (en) |
| AU (1) | AU1669699A (en) |
| BR (1) | BR9814673A (en) |
| CA (1) | CA2310438A1 (en) |
| DE (1) | DE19751434A1 (en) |
| TW (1) | TW419513B (en) |
| WO (1) | WO1999027021A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102193A (en) * | 2013-02-15 | 2015-11-25 | 汉莎航空技术股份公司 | Flame-retardant wooden substrate |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10221222A1 (en) * | 2002-05-13 | 2003-11-27 | Basf Ag | Flame retardant finishing of objects containing organic latent heat storage materials |
| DE10261213B4 (en) * | 2002-12-20 | 2006-08-17 | Raymaster Holding Ag | Intumescent textile |
| DE10305548A1 (en) * | 2003-02-10 | 2004-08-26 | Basf Ag | Flame retardant molded plastic parts |
| DE102010054341B3 (en) | 2010-09-27 | 2012-01-26 | Lufthansa Technik Ag | Method of applying a fire-resistant coating to a substrate and substrate with a fire-resistant coating |
| TW202122516A (en) * | 2019-08-30 | 2021-06-16 | 瑞士商克萊瑞特國際股份有限公司 | Intumescent flame-retardant clearcoat formulations |
| DE102021111074A1 (en) * | 2021-04-29 | 2022-11-03 | Lufthansa Technik Aktiengesellschaft | Flame retardant wooden substrate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993005118A1 (en) * | 1991-09-09 | 1993-03-18 | Chemische Fabrik Budenheim Rudolf A. Oetker | Composition with integral intumescence properties |
| AT400570B (en) * | 1991-09-09 | 1996-01-25 | Budenheim Rud A Oetker Chemie | Polymeric composition with integrated intumescent properties, coating material and process for the preparation of phosphoric acid partial esters |
| DE4307406A1 (en) * | 1993-03-09 | 1994-09-15 | Akro Fireguard Prod Inc | Intumescent composition of the two-component type |
| DE4343669A1 (en) * | 1993-12-21 | 1995-06-22 | Hoechst Ag | Clear, inflatable, flame-retardant coating compounds |
-
1997
- 1997-11-20 DE DE19751434A patent/DE19751434A1/en not_active Withdrawn
-
1998
- 1998-11-12 WO PCT/EP1998/007239 patent/WO1999027021A1/en not_active Application Discontinuation
- 1998-11-12 EP EP98961186A patent/EP1034225A1/en not_active Withdrawn
- 1998-11-12 CA CA002310438A patent/CA2310438A1/en not_active Abandoned
- 1998-11-12 BR BR9814673-4A patent/BR9814673A/en not_active Application Discontinuation
- 1998-11-12 AU AU16696/99A patent/AU1669699A/en not_active Abandoned
- 1998-11-12 KR KR1020007005437A patent/KR20010032236A/en not_active Application Discontinuation
- 1998-11-12 JP JP2000522169A patent/JP2001524571A/en not_active Withdrawn
- 1998-11-17 TW TW087119039A patent/TW419513B/en active
- 1998-11-18 AR ARP980105845A patent/AR016690A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102193A (en) * | 2013-02-15 | 2015-11-25 | 汉莎航空技术股份公司 | Flame-retardant wooden substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1669699A (en) | 1999-06-15 |
| EP1034225A1 (en) | 2000-09-13 |
| KR20010032236A (en) | 2001-04-16 |
| WO1999027021A1 (en) | 1999-06-03 |
| AR016690A1 (en) | 2001-07-25 |
| TW419513B (en) | 2001-01-21 |
| BR9814673A (en) | 2000-10-03 |
| JP2001524571A (en) | 2001-12-04 |
| DE19751434A1 (en) | 1999-07-29 |
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