CA2137112A1 - Expandable, flame-retardant coating compositions - Google Patents

Expandable, flame-retardant coating compositions

Info

Publication number
CA2137112A1
CA2137112A1 CA002137112A CA2137112A CA2137112A1 CA 2137112 A1 CA2137112 A1 CA 2137112A1 CA 002137112 A CA002137112 A CA 002137112A CA 2137112 A CA2137112 A CA 2137112A CA 2137112 A1 CA2137112 A1 CA 2137112A1
Authority
CA
Canada
Prior art keywords
weight
coating composition
salts
substituted ammonium
coating compositions
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.)
Abandoned
Application number
CA002137112A
Other languages
French (fr)
Inventor
Guido Scholz
Wolf-Dieter Pirig
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.)
Clariant Produkte Deutschland GmbH
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of CA2137112A1 publication Critical patent/CA2137112A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00Fireproofing materials
    • C09K21/06Organic materials
    • C09K21/12Organic materials containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D125/00Coating 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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02Homopolymers or copolymers of hydrocarbons
    • C09D125/04Homopolymers or copolymers of styrene
    • C09D125/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D125/00Coating 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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02Homopolymers or copolymers of hydrocarbons
    • C09D125/04Homopolymers or copolymers of styrene
    • C09D125/08Copolymers of styrene
    • C09D125/14Copolymers of styrene with unsaturated esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D131/00Coating 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04Homopolymers or copolymers of vinyl acetate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • C09D5/185Intumescent paints

Abstract

The expandable, flame-retardant coating compositions comprise at least from 4 to 25% by weight of a film-forming binder, from 10 to 40% by weight of an ammonium polyphos-phate, from 8 to 40% by weight of at least one substance which is carbonized under the effect of heat, from 6 to 25% by weight of an expansion agent, from 0 to 5% by weight of dispersants and from 0 to 25% by weight of fillers.
As substance which is carbonized under the effect of heat and/or as expansion agent, and as additional acid donor, these coating compositions contain ammonium salts of alkyl phosphates.

Description

The present invention relates to eYpAn~Ahle~ flame-retardant coating compositions which comprise at least from 4 to 25% by weight of a film-forming binder, from 10 to 40% by weight of an ammonium polyphos-phate, from 8 to 40% by weight of at least one substance which is carbonized under the effect of heat, from 6 to 25% by weight of an expansion agent, from 0 to 5% by weight of dispersants and from 0 to 25% by weight of fillers.

US-A-4,166,743 discloses ~YpAn~Ahle coating compositions comprising a film former, an ammonium polyphosphate, at least one substance which is carbonized under the effect of heat, a dispersant, a salt contA;n;ng water of crys-tallization, an expansion agent and, if desired, fillers.The film formers in these compositions may be aqueous dispersions of polyvinyl acetate or of a copolymer of vinyl acetate and dibutyl maleate, whereas the substance which is carbonized is suitably dicyandiamide, penta-erythritol or melamine. Suitable dispersants, other thanwater, are ethyl acetate, butyl acetate, xylene or toluene, whereas chlorinated paraffins are used as expansion agent.

According to a new reference (cf. J. Troitsch:

"International Plastics Flammability Handbook", 2nd.
Edition, Oxford University Press, New York, 1990, pages 52 and 53) typical examples of substances which are carbonized are pentaerythritol and starch, whereas guanidines, for example cyanoguanidine (dicyandiamide), melamine and chlorinated paraffins are classed as expan-sion agents.

A disadvantage of the known ~p~n~Ahle coating composi-tions is that they contain, in the expansion agent and/or in the substance which is carbonized under the effect of heat, organically bonded halogen, whereby corrosive and toxic gases are released as the coating compositions break down.

The object of the present invention is therefore to provide expandable coating compositions which possess flame-retardant properties but which break down without releasing halogen-cont~;n;ng compounds. This is achieved in accordance with the invention in that the coating compositions contain ammonium salts of alkyl phosphates as substance which is carbonized under the effect of heat and/or as expansion agent and as additional acid donor.

Furthermore, the coating compositions according to the invention may also, optionally, have compositions in which a) monoalkyl phosphates are present;

b) dialkyl phosphates are present;

c) the salts are hydroxyalkyl-substituted ammonium salts;

d) monoethanolamine is used as hydroxyalkyl-substituted ammOnium;

e) diethanolamine is used as hydroxyalkyl-substituted ammonium;

f) triethanolamine is used as hydroxyalkyl-substituted ammonium;

g) the salts are alkyl-substituted ammonium salts;

h) the alkyl radical has 1 to 6 carbon atoms;

i) the salts are aryl-substituted ammonium salts.

The ammonium salts of alkyl phosphates which are present in the coating compositions according to the invention can be prepared, for example, by the process known from US-A-4,118,443.

In the coating compositions according to the invention it is also possible for mixtures of monoalkyl phosphates and dialkyl phosphates to be present.

The ammonium salts of alkyl phosphates which are present in the coating compositions according to the in~ention do 213711~

not only have a flame-retardant action but also give the compositions plasticizing properties. They therefore have a positive effect on the film tear resistance of the coating compositions which form the insulating layer, and can therefore be used as complete substitutes for chlorinated paraffins and other halogen-cont~; n; ng additives, for example tris(2-chloroethyl) phosphate (TCEP) or tris(2-chloroisopropyl) phosphate (TCPP).

In the examples below, flame-retardant coating composi-tions are prepared and their effectiveness is determined, the incorporated ~-m~onium polyphosphate being Hostaflam AP 462 (from Hoechst AG, Frankfurt). The insulation efficiency of the intumescent paints prepared using these coating compositions was carried out in accordance with DIN 4102, part 2 (1977) in a small-scale test set-up according to DIN 4102, part 8 (1986), while the testing of the surface quality was carried out visually.

Example 1 (Comparative example) The following components were introduced in succession into a stirred vessel fitted with a dissolver disc:
20.8 % by weight of water 3 % by weight of ~Tylose 0.2 % by weight of ~Lopon 890 4 % by weight of titanium dioxide 12 % by weight of pentaerythritol 24 % by weight of ~mm~n; um polyphosphate 14 % by weight of melamine % by weight of ~Mowilith DM 230 2 % by weight of chlorinated paraffin 50, li~uid.

The resulting coating composition was roller-coated onto one side of a steel panel (St 37) of dimensions 280 x 280 x 6 mm3. After drying for one day at room temperature coating composition was again applied. The weight of the applied composition was now 2 kg/m2.
Finally, the coated panel was dried in air at 20C for 2 weeks.

The surface of the coating was smooth and free from cracks .

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 60.

Example 2 (Comparative example) The- same coating composition as in Example 1 was prepared, but without the chlorinated paraffin component.

The Rurface of the panel provided with this coating composition was rough and traversed by fine cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

21371~2 Example 3 (Comparative example) The same coating composition as in Example 1 was prepared, but without the chlorinated paraffin component.
In addition, the film-forming binder Mowilith DM 230 (vinyl acetate-vinyl ester copolymer from Hoechst AG, Frankfurt) was replaced by ~Impranil DLP (anionic, aliphatic polyester-polyurethane dispersion from Bayer AG, Leverkusen).

The surface of the panel provided with this coating composition was rough and traversed by fine cracks.

The fire testing of the coated panel according to DIN 4102 did not meet the requirements of fire resistance class F 30.

Example 4 (Comparative example) The same coating composition as in Example 1 was prepared, but the film-forming binder Mowilith DM 230 was replaced by ~Impranil DLP.

The surface of the panel provided with this coating composition was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 5 (Comparative example) The same coating composition as in Example 1 was prepared, but the film-forming binder Mowilith DM 230 was replaced by ~Mowilith DM 60 (styrene-acrylate copolymer from Hoechst AG, Frankfurt).

The surface of the panel provided with this coating composition was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 6 (Comparative example) A coating composition analogous to that in Example 1 was prepared, with the film-forming binder Mowilith DM 230 being replaced by ~Mowilith DC (homopolymer based on vinyl acetate, from Hoechst AG, Frankfurt) and the chlorinated paraffin being replaced by tris(2-chloro-ethyl) phosphate.

The surface of the panel provided with this coating composition was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 7 (according to the invention) The same coating composition as in Example 1 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a monoethanolammonium salt of the ~Knapsack cleaner component MPS, adjusted to a pH of 7, were used.

The surface of the panel coated with this coating com-position was free from cracks and smoother than in the ca~e of Example 1.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 60.

Example 8 (according to the invention) The same coating composition as in Example 1 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a monoethanol~mo~;um salt of the ~napsack phosphate MDE, adjusted to a pH of 7, were used.

The surface of the panel coated with this coating com-position was free from cracks and smoother than in the case of Example 1.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 60.

213711~ `

Example 9 (according to the invention) The same coating composition as in Example 4 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a monoethanolammonium salt of the ~Knapsack phosphate MDE, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-position was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 10 (according to the invention) The same coating composition as in Example 5 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a monoethanolammonium salt of the ~Knapsack phosphate MDE, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-position was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 11 (according to the invention) The same coating composition as in Example 6 was prepared, but instead of 2% by weight of tris(2-chloro-ethyl) phosphate 1.5% by weight of a monoethanol~mmonium salt of the ~Rnapsack phosphate MDE, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-position was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 12 (according to the invention) The same coating composition as in Example 5 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a triethylA~mo~ium salt of the ~Knapsack phosphate MDE, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-position was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 13 (according to the invention) The same coating composition as in Example 5 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a triphenylammonium salt of the ~Rnapsack phosphate MDE, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-position was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 14 (according to the invention) The same coating composition as in Example 5 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a tribenzylammonium salt of the ~Rnapsack phosphate MDE, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-po~ition was smooth and free from cracks.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 30.

Example 15 (according to the invention) The same coating composition as in Example 1 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a diethanolammonium salt of the ~Rnapsack cleaner component MPS, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-position was free from cracks and smoother than in the case of Example 1.

The fire testing of the coated panel according to DIN 4102 gave the fire resistance class F 60.

Example 16 (according to the invention) The same coating composition as in Example 1 was prepared, but instead of 2% by weight of chlorinated paraffin 1.5% by weight of a triethanolamm~;um salt of the ~Knapsack cleaner component MPS, adjusted to a pH of 7, were used.

The surface of the panel provided with this coating com-position was free from cracks and smoother than in the case of Example 1.

The fire testing of the coated panel according to DIN 4102 ga~e the fire resistance class F 60.

Claims (10)

1. An expandable, flame-retardant coating composi-tion comprising at least from 4 to 25% by weight of a film-forming binder, from 10 to 40% by weight of a ammonium polyphos-phate, from 8 to 40% by weight of at least one substance which is carbonized under the effect of heat, from 6 to 25% by weight of an expansion agent, from 0 to 5% by weight of dispersants and from 0 to 25% by weight of fillers, wherein ammonium salts of alkyl phosphates are present as substance which is carbonized under the effect of heat and as expansion agent.
2. A coating composition as claimed in claim 1, wherein monoalkyl phosphates are present as alkyl phos-phates.
3. A coating composition as claimed in claim 1, wherein dialkyl phosphates are present as alkyl phos-phates.
4. A coating composition as claimed in claim 1, wherein the salts are hydroxyalkyl-substituted ammonium salts.
5. A coating composition as claimed in claim 4, wherein monoethanolamine is used as hydroxyalkyl-substituted ammonium.
6. A coating composition as claimed in claim 4, wherein diethanolamine is used as hydroxyalkyl-substituted ammonium.
7. A coating composition as claimed in claim 4, wherein triethanolamine is used as hydroxyalkyl-substituted ammonium.
8. A coating composition as claimed in claim 1, wherein the salts are alkyl-substituted ammonium salts.
9. A coating composition as claimed in claim 8, wherein the alkyl radical has 1 to 6 carbon atoms.
10. A coating composition as claimed in claim 1, wherein the salts are aryl-substituted ammonium salts.
CA002137112A 1993-12-21 1994-12-01 Expandable, flame-retardant coating compositions Abandoned CA2137112A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4343668A DE4343668A1 (en) 1993-12-21 1993-12-21 Inflatable, flame-retardant coating compounds
DEP4343668.4 1993-12-21

Publications (1)

Publication Number Publication Date
CA2137112A1 true CA2137112A1 (en) 1995-06-22

Family

ID=6505659

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002137112A Abandoned CA2137112A1 (en) 1993-12-21 1994-12-01 Expandable, flame-retardant coating compositions

Country Status (7)

Country Link
US (1) US5749948A (en)
EP (1) EP0659850B1 (en)
JP (1) JPH07252438A (en)
AT (1) ATE165859T1 (en)
CA (1) CA2137112A1 (en)
DE (2) DE4343668A1 (en)
ES (1) ES2117750T3 (en)

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US10640657B2 (en) 2013-10-11 2020-05-05 Huntsman International Llc Polyisocyanate-based intumescent coating

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Also Published As

Publication number Publication date
JPH07252438A (en) 1995-10-03
EP0659850B1 (en) 1998-05-06
DE59405901D1 (en) 1998-06-10
EP0659850A2 (en) 1995-06-28
ES2117750T3 (en) 1998-08-16
US5749948A (en) 1998-05-12
DE4343668A1 (en) 1995-06-22
EP0659850A3 (en) 1996-09-18
ATE165859T1 (en) 1998-05-15

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Legal Events

Date Code Title Description
FZDE Discontinued