JP2001524571A - Foamable flame retardant paint - Google Patents

Abstract

  (57) [Summary] The present invention relates to an intumescent flame-retardant paint containing from 10 to 150 parts by weight of a synthetic resin aqueous dispersion and from 10 to 80 parts by weight of a mixture of at least two different phosphoric acid partial esters.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Industrial applications]

 The present invention relates to an intumescent flameproof paint and its use.

[0002]

[Prior art]

Flame-retardant paints based on solvent-containing binders containing chloroparaffins as flame-retardant components are known (see “Fire Safety Journa by Bhatnagar and Vergnaud”).
l "4 (3), 163-1 and" Paintindia "32 (1) 3-6, 14; 1982).

[0003] A disadvantage of this system is that solvent vapors are evolved during drying and corrosive toxic combustion gases are released on burning.

[0004] From US Pat. No. 4,166,743, a film-forming agent, ammonium polyphosphate, at least one substance carbonized under the influence of heat, a dispersant, a salt with water of crystallization, a blowing agent In addition, foamable paints comprising fillers are known. In this case, an aqueous dispersion consisting of polyvinyl acetate or a copolymer of vinyl acetate and dibutyl maleate can be used as a film-forming agent, and dicyandiamide, pentaerythrit or Melamine is suitable. In addition to water, ethyl acetate, butyl acetate, xylene or toluene is suitable as a dispersant, and chloroparaffin is used as a foaming agent.

[0005] Troitzsch ("International Plastics Flammability Handbook", 2nd edition, Oxfo
According to rd University Press, New York, 1990, pp. 52-53), typical examples of carbonizing materials include pentaerythritol and starch, while blowing agents include guanidine, melamine and chloroparaffin.

[0006] In the case of the foamable coatings described above, organically bound halogens are contained in the blowing agent and / or in the substance which is carbonized under the influence of heat, so that when the coating is decomposed, There is the disadvantage that corrosive toxic gases are released.

[0007] Furthermore, German Offenlegungsschrift (A1) 4,343,668 discloses a film-forming binder, ammonium polyphosphate, at least one substance which carbonizes under the influence of heat, a blowing agent and possibly Discloses a foamable flameproof paint comprising a dispersant and a filler.

[0008] DE-A 4,343,669 also discloses a similar effervescent flame-retardant paint, which does not contain ammonium polyphosphate.

However, this system cannot achieve a sufficient pot life.

[0010] Aqueous flame-retardant coatings have also been proposed in which a polyol-based phosphoric acid partial ester and a carbonizing substance act as acid donors (EP 0,556,350). ).

The disadvantage here is that the production of polyol-based phosphoric acid partial esters on an industrial scale is very costly and therefore cannot be used in large quantities. Furthermore, this system can only achieve pot life on the order of minutes.

[0012] Furthermore, EP-A-0,417,490 describes phosphoric esters and their salts, coatings and molding materials containing them, the use of these phosphoric esters and their salts as dispersants and A solid material coated with this is disclosed.

Taken together, the prior art clearly shows compositions which contain halogens and therefore release toxic corrosive gases on combustion. In the case of halogen-free systems, the pot life is very short and some do not achieve sufficient product hardness. In some systems, there are problems in industrial production, in others the field of application is too narrow.

[0014]

[Problems to be solved by the invention]

It is therefore an object of the present invention to provide an intumescent flame-retardant paint which is halogen-free, exhibits a sufficient pot life and produces a fully cured product without the addition of other substances (curing agents). It is.

[0015]

[Means for Solving the Problems]

 This problem is solved by an intumescent flame-retardant paint of the type described at the outset comprising 10 to 150 parts by weight of an aqueous synthetic resin dispersion and 10 to 80 parts by weight of a mixture of at least two different phosphoric acid partial esters. You.

The foamable flame retardant paint comprises 50 to 90 parts by weight of an aqueous synthetic resin dispersion, 20 to 60 parts by weight of a mixture of at least two different phosphoric acid partial esters and 1 to 80 parts by weight of another Advantageously, it contains contained substances.

Advantageously, it contains a mixture of three different phosphoric acid partial esters.

It is particularly advantageous to include a mixture of four different phosphoric acid partial esters.

The foamable flame-retardant paint comprises: a) a mixture of a monoalkyl phosphate and a dialkyl phosphate having the same alkyl group and b) a monoalkyl phosphate having the same but different alkyl group from the alkyl group of a). It advantageously comprises a mixture of an ester and a dialkyl phosphate.

The phosphoric acid partial esters include monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monoisobutyl phosphate, monopentyl phosphate, monoisopentyl phosphate, and monoisopentyl phosphate. Hexyl ester, monooctyl phosphate, mono (2-ethylhexyl) phosphate, monoethylene glycol phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, diisobutyl phosphate, diphenyl phosphate Esters, dihexyl phosphate, dioctyl phosphate, di (2-ethylhexyl) phosphate and / or diethylene glycol ester And mixtures thereof.

The aqueous synthetic resin dispersion is advantageously a nitrogen-containing synthetic resin dispersion.

Advantageously, the aqueous synthetic resin dispersion is a melamine- and / or urea-formaldehyde resin.

Particularly preferably, the aqueous synthetic resin dispersion is an etherified melamine- and / or urea-formaldehyde resin.

The melamine resin used according to the invention described above is generally the reaction product of melamine and formaldehyde in a molar ratio of 1: 1 to 1: 6 (melamine: formaldehyde).

The melamine-formaldehyde-resin may be etherified with an alcohol having a chain length of 1 to 20, preferably 1 to 4, carbon atoms.

Advantageously, the further ingredients are dispersants, fillers, hardeners, thixotropic agents, plasticizers, acid donors, other flame retardants, surface aids and / or binders.

Colorants in the sense of the present invention are, for example, Roempp's Chemie Lexikon, 9th edition, 1992
, Page 1237. These include organic and inorganic natural and synthetic colorants, in other words pigments and dyes.

When no colorant is used, the foamable flame retardant coatings of the present invention are generally transparent.
Addition of fillers, especially talc, can make the paint turbid. It is likewise possible to produce a particularly white foaming flame-retardant paint which is colored in the dry state by the selection of suitable colorants, in particular inorganic pigments.

[0029] It is particularly advantageous if the further contained substances are thixotropic agents and / or fillers.

The phosphoric acid partial ester has the formula

[0031]

Embedded image

[Wherein R ¹ and R ² are the same or different from each other, and are H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₅ H ₁₁ , C ₆ H ₁₃ , C ₈ H ₁₆ and / or CH ₂ —CH ₂ —OH, and R ¹ and R ² do not simultaneously represent a hydrogen atom. The compounds represented by the following formulas are advantageous.

The mixtures according to the invention of at least two different phosphoric acid partial esters are generally from 2 to 9
It consists of 8% by weight of a phosphoric acid partial ester and 98-2% by weight of a different phosphoric acid partial ester.

It is particularly advantageous to use from 10 to 90% by weight of a phosphoric acid partial ester and from 90 to 10% by weight of other phosphoric acid partial esters.

In the case of a mixture of three different phosphoric acid partial esters, generally (2-98):
The ratio is (4 to 96) :( 4 to 96)% by weight.

In the case of a mixture of four phosphoric acid partial esters, the ratio of mixture a) to mixture b) is (98-2) :( 2-98), preferably (10-90) :( 90- 10)
% By weight. In the mixture of a) or b), the ratio of monoalkyl phosphate to dialkyl phosphate is (2-98) :( 98-2), preferably (10-90) :( 90-10) wt%. Is the ratio of

As dispersants for solid substances, use is made of, for example, monopolyethylene glycol alkyl phosphates, monopolyethylene glycol aryl phosphates, dipolyethylene glycol alkyl phosphates and / or dipolyethylene glycol aryl phosphates and mixtures thereof. Can be.

[0038] The phosphorus content of the foamable flameproof coating is from 1 to 15% by weight after curing.

Advantageously, the phosphorus content of the foamable flame retardant paint after curing is 4 to 10% by weight.

The present invention further provides a paint of the present invention for forming a coating on an object consisting of wood, synthetic resin, building material, cellulosic material, rubber and metal, and for impregnating textile material and leather. Also related to use.

The invention is illustrated in detail by the following examples using the following substances:

^(R) Maprenal MF920 ^(R) Maprenal MF920 (manufactured by Vianova Resins) is an unplasticized methyl etherified melamine-formaldehyde resin.

^(R) Mapprenal VMF3921w ^(R) Mapprenal VMF3921w (manufactured by Vianova Resins) is an unplasticized methyl etherified melamine-formaldehyde resin.

^(R) Plastopal BTW This is an elastic urethane group-containing methanol-etherified urea-formaldehyde resin (manufacturer: BASF).

^(R) Knappsack phosphate (Phosphorsaeureeste ⁾
r) MDE This is a mixture of monoethyl phosphate and diethyl phosphate.

^(R) Knappsack Phosphate MDIP This is a mixture of monoisopropyl phosphate and diisopropyl phosphate.

^(R) Knappsack Phosphate 122 This is a mixture of monopolyethylene glycol alkyl phosphate and dipolyethylene glycol alkyl phosphate (dispersant).

^(R) Knappsack Purified Component MIS This is a mixture of monoisopropyl phosphate, monomethyl phosphate and phosphoric acid.

^(R) Knappsack Phosphate MOE This is a mixture of monoethyl phosphate and phosphoric acid.

^(R) Knappsack Purified Component MS This is monomethyl phosphate.

^(R) Knappsack Phosphate MDB This is a mixture of monobutyl phosphate and dibutyl phosphate.

The above-mentioned commercially available product ^(R) Knappsack phosphate or ^(R) Knappsac
The k-purified components are manufactured at Clariant GmbH, Knapsack plant.

^(R) Mistrofil 500 This is a commercially available talc.

^(R) Aerosil R816 This is a high heat treated silica from Degussa AG.

The various components are mixed with one another in the order described in the examples, applied to pine or wood fiberboard, dried and the foaming behavior is measured. The order of application of the components can be arbitrarily determined and depends on the desired layer thickness and other conditions (viscosity, undercoat, pot life, etc.).

Other substances are optionally described in the respective examples.

The coatings obtained according to the following examples are transparent, glossy and free of cracks. Pot life is more than 24 hours on average. In less than 24 hours (on average) the coating becomes tack-free and hard. B1 and B2 were achieved in the burning test of paints of these formulations applied to pine or wood fiberboard.

Example 1 Mixture of 68 parts by weight of ^(R) Maprenal MF920 25 parts by weight of 90% by weight of ^(R) Knapsack phosphate MOE and 10% by weight of ^(R) Knapsack purified component MS.

Example 2 Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.8 parts by weight of ^(R) Knappsack phosphate MOE 80% by weight and ^(R) Knappsack purified component MS 20% by weight .

Example 3 Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.9 parts by weight of ^(R) Knappsack phosphate MOE 70% by weight and ^(R) Knappsack purified component MS 30% by weight .

Examples 1-3 were replaced with 68 parts by weight of ^(R) Maprenal MF920
Similar results were obtained when repeated using 0 parts by weight of ^(R) Maprenal VMF3921w.

Example 4 Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.9 parts by weight of 80% by weight of ^(R) Knappsack phosphate MOE and 20% by weight of ^(R) Knappsack purified component MIS .

Example 5 Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.8 parts by weight of 70% by weight of ^(R) Knappsack phosphate MOE and 30% by weight of ^(R) Knappsack purified component MIS .

Example 6 : Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.9 parts by weight of 90% by weight of ^(R) Knappsack phosphate MOE and 10% by weight of ^(R) Knappsack purified component MIS .

Examples 4-6 were replaced with 68 parts by weight of ^(R) Maprenal MF920
Similar results were obtained when repeated using 0 parts by weight of ^(R) Maprenal VMF3921w.

Example 7 : Mixing of 68 parts by weight of ^(R) Maprenal MF920 26.1 parts by weight with 90% by weight of ^(R) Knappsack phosphate MOE and 10% by weight of ^(R) Knappsack phosphate MDIP Compound.

Example 8 : Mixing of 68 parts by weight of ^(R) Maprenal MF920 26.4 parts by weight with 80% by weight of ^(R) Knappsack phosphate MOE and 20% by weight of ^(R) Knappsack phosphate MDIP Compound.

Example 9 : Mixing of 68 parts by weight of ^(R) Maprenal MF920 28.7 parts by weight with 70% by weight of ^(R) Knappsack phosphate MOE and 30% by weight of ^(R) Knappsack phosphate MDIP Compound.

Example 10: Mixing of 68 parts by weight of ^(R) Maprenal MF920 26.4 parts by weight with 90% by weight of ^(R) Knappsack phosphate MOE and 10% by weight of ^(R) Knappsack phosphate MDB object.

Example 11: Mixing of 68 parts by weight of ^(R) Maprenal MF920 27.9 parts by weight with 80% by weight of ^(R) Knappsack phosphate MOE and 20% by weight of ^(R) Knappsack phosphate MDB object.

Example 12: Mixing of 68 parts by weight of ^(R) Maprenal MF920 29.6 parts by weight with 80% by weight of ^(R) Knappsack phosphate MOE and 20% by weight of ^(R) Knappsack phosphate MDB object.

Similar results were obtained by repeating Examples 7-12 using 60 parts by weight of ^(R) Maprenal VMF3921w instead of 68 parts by weight of ^(R) Maprenal MF920.

Example 13: Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.3 parts by weight of 90% by weight of ^(R) Knappsack purified component MS and 10% by weight of ^(R) Knappsack purified component MIS .

Example 14: Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.4 parts by weight of 80% by weight of ^(R) Knappsack purified component MS and 20% by weight of ^(R) Knappsack purified component MIS .

Example 15: Mixture of 68 parts by weight of ^(R) Maprenal MF920 24.3 parts by weight with 70% by weight of ^(R) Knappsack purified component MS and 30% by weight of ^(R) Knappsack purified component MIS .

Example 16: Mixture of 68 parts by weight of ^(R) Maprenal MF920 25.5 parts by weight of 90% by weight of ^(R) Knapsack purified component MS and 10% by weight of ^(R) Knapsack phosphate MDIP .

Example 17 Mixture of 68 parts by weight of ^(R) Maprenal MF920 26.7 parts by weight of 80% by weight of ^(R) Knappsack purified component MS and 20% by weight of ^(R) Knappsack phosphate MDIP .

Example 18: Mixture of 68 parts by weight of ^(R) Maprenal MF920 28.0 parts by weight of 70% by weight of ^(R) Knappsack purified component MS and 30% by weight of ^(R) Knappsack phosphate MDIP .

Example 19: Mixture of 68 parts by weight of ^(R) Maprenal MF920 25.7 parts by weight of 90% by weight of ^(R) Knapsack purified component MS and 10% by weight of ^(R) Knapsack phosphate MDB .

Example 20: Mixture of 68 parts by weight of ^(R) Maprenal MF920 27.2 parts by weight of 80% by weight of ^(R) Knappsack purified component MS and 20% by weight of ^(R) Knappsack phosphate MDB .

Example 21: Mixture of 68 parts by weight of ^(R) Maprenal MF920 29.0 parts by weight of 70% by weight of ^(R) Knappsack purified component MS and 30% by weight of ^(R) Knappsack phosphate MDB .

Example 22 Mixture of 68 parts by weight of ^(R) Maprenal MF920 30.1 parts by weight of 90% by weight of ^(R) Knappsack phosphate MDE and 10% by weight of ^(R) Knappsack purified component MS .

Example 23: Mixture of 68 parts by weight of ^(R) Maprenal MF920 30.1 parts by weight with 80% by weight of ^(R) Knappsack phosphate MDE and 20% by weight of ^(R) Knappsack purified component MS .

Example 24: Mixture of 68 parts by weight of ^(R) Maprenal MF920 29.3 parts by weight with 70% by weight of ^(R) Knapsack phosphate MDE and 30% by weight of ^(R) Knapsack purified component MS .

[0085] Similar results were obtained when Examples 13 to 24 were repeated using 60 parts by weight of ^(R) Maprenal VMF3921w instead of 68 parts by weight of ^(R) Maprenal MF920.

Example 25: 60 parts by weight of ^(R) Maprenal MF3921w 27 parts by weight of ^(R) Knappsack phosphate MDE 7 parts by weight of ^(R) Knappsack phosphate MDIP

Example 26: 60.0 parts by weight of ^(R) Maprenal MF920 24.0 parts by weight of ^(R) Knappsack phosphate MDE 6.0 parts by weight of ^(R) Knappsack phosphate MDIP 3.0 parts by weight ^(R) Aerosil R816 7.0 parts by weight of ^(R) Mistrofil 500.

Example 27: 60.0 parts by weight of ^(R) Maprenal MF920 27.1 parts by weight of ^(R) Knappsack phosphate MDE 6.8 parts by weight ^(R) Knappsack phosphate MDIP 0.6 parts by weight ⁽ IPIP ^{) R)} Knappsack phosphate 122 3.0 parts by weight of ^(R) Aerosil R816 7.2 parts by weight of ^(R) Mistrofil 500.

Example 28 Mixing of 60 parts by weight of ^(R) Maprenal MF3921w 34.5 parts by weight with 75% by weight of ^(R) Knapsack phosphate MDE and 25% by weight of ^(R) Knapsack phosphate MDIP object.

Example 29 Mixing of 80 parts by weight of ^(R) Maprenal VMF 3921w 44.6 parts by weight with 85% by weight of ^(R) Knappsack phosphate MDE and 15% by weight of ^(R) Knappsack phosphate MDIP object.

Example 30 Mixing of 80 parts by weight of ^(R) Maprenal MF3921w 46.5 parts by weight with 70% by weight of ^(R) Knapsack phosphate MDE and 30% by weight of ^(R) Knapsack phosphate MDIP Material 9.6 parts by weight of ^(R) Mistrofil 500 4 parts by weight of heat-treated silica.

Other examples of the foamable flameproof paint of the present invention are shown in Tables 1 to 11. All formulations achieved B1 or B2 in the burn test.

Table 1: ┌────────────┬─────────────────────┐ │ component │ parts by weight │ │ │ Example 31 Example 32 Example 33 │ ├────────────┼─────────────────────┤ │ ^(R) Maprenal VMF 3921w │ 80 80 80 │ ├────────────┼─────────────────────┤ │ MDE: MDIP ^*) 85:15 │ 44.6 44.7 44.1 │ ├────────────┼─────────────────────┤ │ ^(R) Mistrofil 500 │ 8 9.2 10.4 │ └────────────┴─────────────────────┘ *) MDE: MDIP 85:15 It means a mixture of 85% by weight of ^(R) Knapsack phosphate MDE and 15% by weight of ^(R) Knapsack phosphate MDIP. This description also applies to the table below.

Table 2: ┌────────────┬─────────────────────┐ │ component │ parts by weight │ │ │ Example 34 Example 35 Example 36 │ ├────────────┼─────────────────────┤ │ ^(R) Maprenal MF 390 │ 75 80 80 │ ├────────────┼─────────────────────┤ │ MDE: MDIP 80: 20 │ 37.5 40 40 │ ├────────────┼─────────────────────┤ │ ^(R) Mistrofil 500 │ 13.5 17 20.8 │ └────────────┴─────────────────────┘Table 3: ┌─────── ─────┬─────────────────────┐ │ component │ parts │ │ │ example 37 example 38 example 39 │ ├─── ^{────────┼─────────────────────┤ │ (R) Maprenal VMF 3291w} │ 60 60 60 │ ├────── │ │MDE: MDIP 75:25 │ 34.5 34.5 34.5 │ ├──────── │ │ ^(R) Mistrofil 500 │ 7.8 6 6.9 │ └─────────── ─┴─────────────────────┘Table 4: ┌────────────┬───────── │ │ Component │ Example (parts by weight) │ │ │ 40 41 42 43 44 45 │ ├────────────┼──── │ │ ^(R) Maprenal VMF 3291w │ 50 80 80 75 75 60 │ ├────────────┼─── ───────────────── │ │MDE: MDIP 80:20 │ 28.3 46 46 42.4 42.3 33.5 │ ├────────────┼─────────────────── ──┤ │ ^(R) Mistrofil 500 │ 6.5 8 9.2 12.7 15.2 17.5 │ └────────────┴─────────────────── ──┘Table 5: ┌────────────┬─────────────────────┐ │ Ingredient │ Example (parts by weight ) │ │ │ 46 47 48 49 │ ├────────────┼─────────────────────┤ │ ^(R) Maprenal VMF 3291w │ 80 80 80 80 │ ├────────────┼─────────────────────┤ │ MDE: MDIP 80: 20 │ 45.4 45.3 45.2 45.2 │ ├────────────┼──────────┬──────────┤ │ │ 4 6 │ 8 10 │ │Highly dispersed silica │ ^(R) CAB-O-SIL TS5 30 │ ^(R) Aerosil OX-50 │ └────────────┴──────────┴──────────┘ This series of experiments ^(R) CAB-O-SIL TS530 (Manufacturer: CABOT)
(Hanau) was used. Similarly, ^(R) Aerosil OX-50 (manufacturer: Degussa AG) (high heat treated silicic acid) was used successfully.

Example 50 Mixture of 90 parts by weight of ^(R) Maprenal VMF 3921w 45.15 parts by weight of 80% by weight of ^(R) Knapsack phosphate MDE and 20% by weight of ^(R) Knapsack purified component MIS 7 parts by weight of ^(R) Mistrofil 500 0.9 part by weight of ^(R) Knapsack phosphate 122.

Table 6: ┌───────────────┬──────────────┐ │ component │ parts by weight │ │ │ Example 51 Example 52 │ ├───────────────┼──────────────┤ │ ^(R) Plastopal BTW │ 60 60 │ ├──── │ │MDE: MDIP 80:20 │ 31 30.4 │ ├─────────── │ │ ^(R) Mistrofil 500 │ 7.9 6.8 │ ├───────────────┼─── │ │ ^(R) Knapsack phosphate 122 │ 0.6 0.2 │ └───────────────┴───────── ─────┘ Table 7: ┌───────────────┬──────────────┐ │ Ingredients │ parts by weight │ │ │ execution Example 53 Example 54 │ ├───────────────┼──────────────┤ │ ^(R) Maprenal VMF 3291w │ 90 90 │ ├── │ │MDE: MIS 80:20 │ 45 45 │ ├───────── │ │ ^(R) Knapsack phosphate 122 │ 0.9 0.9 │ ├─────────────── │ │Highly dispersed silica ^(R) Aerosil OX 50 │ 9 10.8 │ └───────────────┴─── ───────────┘Table 8: ┌───────────────┬──────────────┐ │ Ingredient │ Parts by weight │ │ │ Example 55 Example 56 │ ├───────────────┼──────────────┤ │ ^(R) Maprenal VMF 3291w │ 80 80 │ │ │MDE: MDIP 80:20 │ 45.2 45.5 │ ├─────── │ │ ^(R) Mistrofil 500 │ 9.6 8 │ ├─────────────── │ │Highly dispersed silica ^(R) Aerosil R 972 │ 4.0 4.8 │ └───────────────┴─── ───────────┘Table 9: ┌────────────┬───────────────────── │ │ Component │ Example (parts by weight) │ │ │ 57 58 59 60 │ ├────────────┼────────────────── ───┤ │ ^(R) Maprenal VMF 3291w │ 75 75 75 75 │ ├────────────┼─────────────────── │ │MDE: MDIP 80:20 │ 42.6 42.5 42.4 42.5 │ ├────────────┼─────────────────────┤ │ ^(R) Knapsack phosphate 122│ 0.5 0.5 0.5 0.5 │ ├────────────┼─────────┬───────────┤ │ │ 7.5 9 │ 5.6 7.5 │ │ Highly dispersed silica │ ^(R) Aerosil OX-50 │ ^(R) CAB-O-SIL L 90 │ └────────────┴─────────┴─────── ────┘Table 10: │ │ Ingredient │ Example ( │ │ │ 61 62 63 64 │ ├────────────┼─────────────────────┤ │ ^{(R )} Maprenal VMF 3291w │ 75 80 80 80 │ ├────────────┼─────────────────────┤ │ MDE: MDIP 80:20 │ 42.4 40 45.2 42.4 │ ├─── ^{────────┼─────────────────────┤ │ (R) Mistrofil 500 │} 6.8 9.6 9.6 6.8 │ ├────── ──────┼─────────────────────┤ │ ^(R) Knapsack phosphate 122│ 0.5 0.6 1.8 0.5 │ ├────── ──────┼─────┬─────────┬─────┤ │ │ 3 │ 4 4 │ 7.5 │ │ Highly dispersed silica │ ^(R) CAB-O- │ ^(R) Aerosil R 972 │ ^(R) CAB-O-│ │ │SIL L 90 │ │SIL L 90 │ └────────────┴─────┴─── ──────┴─────┘ example ^{61~64, (R) Maprenal VMF 3291w} (R) instead of Maprenal MF920
And similar results were obtained.

Table 11 : ┌────────────┬─────────────────────┐ │ components │ Examples (parts by weight) ) │ │ │ 65 66 │ ├────────────┼─────────────────────┤ │ ^(R) Maprenal VMF 3291w │ 90 90 │ ├────────────┼─────────────────────┤ │ MDE: MDIP 80:20 │ 45 45 │ ├────────────┼─────────────────────┤ │ ^(R) Mistrofil 500 │ 8 9 │ ├── │ │ ^(R) Knapsack phosphate 122│ 1 1 │ ├──── ────────┼─────────┬───────────┤ │ │ 3.6 │ 5.2 │ │ Highly dispersed silica │ ^(R) Aerosil R 972 │ ^{( R)} Aerosil ^R 972 │ └─ ──────────┴─────────┴───────────┘ Example 67: 80 parts by weight of ^(R) Maprenal VMF3921w 45.2 wt Part by weight of a mixture of 80% by weight of ^(R) Knapsack phosphate MDE and 20% by weight of ^(R) Knapsack phosphate MDIP 4 parts by weight of titanium dioxide ( ^(R) Kronos 2300).

Example 68: Mixing of 80 parts by weight of ^(R) Maprenal VMF 3921w 45.2 parts by weight with 80% by weight of ^(R) Knappsack phosphate MDE and 20% by weight of ^(R) Knappsack phosphate MDIP Compound 0.9 parts by weight of ^(R) Knappsack phosphate 122 4 parts by weight of titanium dioxide ( ^(R) Kronos 2300).

The paints obtained according to Examples 67 and 68 are shiny, white and free of cracks.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Pilich Wolf-Dieter Germany, D-53879 Oiski Luchen, Kastanienweg, 17F term (reference) 4J038 DA141 DA161 EA011 JC22 KA03 KA08 KA09 MA08 MA10 NA15 PB05 PC02 PC06 PC07 PC08

Claims (15)

[Claims] 1. A foamable flame-retardant coating composition comprising 10 to 150 parts by weight of a synthetic resin aqueous dispersion and 10 to 80 parts by weight of a mixture of at least two different phosphoric acid partial esters. 2. A composition comprising 50 to 90 parts by weight of an aqueous synthetic resin dispersion, 20 to 60 parts by weight of a mixture of at least two different phosphoric acid partial esters and 1 to 80 parts by weight of other ingredients. Item 2. The foamable flameproof paint according to Item 1. 3. The foamable flame retardant paint according to claim 1, which comprises a mixture of three different phosphoric acid partial esters. 4. The foamable flameproofing paint according to claim 1, which comprises a mixture of four different phosphoric acid partial esters. 5. A mixture of four different phosphoric acid partial esters wherein a) a mixture of a monoalkyl phosphate and a dialkyl phosphate having the same alkyl group and b) an alkyl group which is the same but different from the alkyl group of a). The foamable flameproof paint according to claim 4, comprising a mixture of a monoalkyl phosphate and a dialkyl phosphate having a mixture thereof. 6. The foamable flameproof paint according to claim 1, wherein the synthetic resin aqueous dispersion is a nitrogen-containing synthetic resin dispersion. 7. The foamable flameproof paint according to claim 1, wherein the aqueous synthetic resin dispersion is a melamine- and / or urea-formaldehyde resin. 8. An aqueous dispersion of a synthetic resin comprising etherified melamine and / or
8. The foamable flameproof paint according to claim 1, which is a urea-formaldehyde resin. 9. The composition according to claim 1, wherein the other substance is a dispersant, a filler, a curing agent, a thixotropic agent,
A plasticizer, an acid donor, another flame retardant, a surface aid and / or a binder.
8. The foamable flameproof paint according to any one of the above items 8. 10. The foamable flameproof paint according to claim 1, wherein the other contained substance is a thixotropic agent and / or a filler. 11. The phosphoric acid partial ester has the formula: [Wherein, R ¹ and R ² are the same or different from each other and H, CH ₃ , C ₂ H ₅ , C ₃ H
_7, a _{C 4 H 9, C 5 H} 11, C 6 H 13, C 8 H 16 and / or CH ₂ -CH ₂ -OH, and R ¹ and R ² are not a hydrogen atom simultaneously. ] The foamable flameproof paint according to any one of claims 1 to 10, which is a compound represented by the formula: 12. The phosphorous content after curing is 1 to 15% by weight.
The foamable flameproof paint according to any one of the above. 13. The method according to claim 1, wherein the phosphorus content after curing is 5 to 10% by weight.
The foamable flameproof paint according to any one of the above. 14. The foamable flameproof paint according to claim 1, which is transparent after being applied and dried. 15. The method according to claim 1, for forming a coating film on an object made of wood, synthetic resin, building material, cellulosic material, rubber and metal, and impregnating fiber material and leather. Use of the paint according to one.