TW419513B - Intumescent, flame-retardant coating compositions - Google Patents

Abstract

The invention relates to imtumescent, flame-retardant coating compositions 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.

Description

4 19513 ___ ^ __ 5. Description of the invention (1) The flame retardant coating compositions based on solvent-containing adhesives and including chlorinated paraffins as their flame retardant components are known (Bhatnagar and Vergnaud in Fire Safety Journal 4 (3), 163-7 and Paintindia 32 (1) 3-6, 14; 1982). One disadvantage of this type of system is that it emits solvent vapors during drying and releases corrosive and toxic halogen-containing combustion gases in the event of a fire. US-A 4, 1 66 · 743 reveals expandable coatings The composition includes a film-forming agent | ammonium pyrophosphate, at least one substance that will carbonize when exposed to heat, a dispersant, a salt containing crystal water, an expansion agent, and if necessary | In this type of composition, the film-forming agent can be an aqueous dispersion of polyvinyl acetate or a copolymer of vinyl acetate / dibutyl maleate, and the suitable carbonizing substances are dicyandiamide and pentaerythritol. Or melamine. In addition to water, suitable dispersants are ethyl acetate, butyl acetate, xylene or toluene, and 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 examples of carbonizing substances are pentaerythritol and starch, while guanidines, melamine and chlorinated paraffins are all It is classified as a bulking agent (Spumific agents). One of the disadvantages of the above-mentioned expandable coating compositions is that they contain organically-bonded halogens in the expansion agent and / or the material that is carbonized when exposed to heat. Toxic gas. In addition, DE 4 3 4 3 6 6 8 A1 mentions that the paper size of this paper is applicable to the Chinese National Standard (CNS) 戍 4 ^^ 2 (2I0X297 mm) _4- (诮 Read the precautions on the back before copying the book page)

ΊT 4 195 13 at B7 V. Description of the invention (2) Flame retardant coating composition, which includes a film-forming adhesive, ammonium pyrophosphate, at least one substance which will carbonize when exposed to heat, an expansion agent, and, If necessary, dispersants and additives. DE 43 43 669 A1 describes an expandable flame-retardant coating composition having a similar composition but without ammonium pyrophosphate. However, the existing systems can only reach a short insufficient life. Another proposal is to use an aqueous flame retardant coating composition in which a polyhydric alcohol-based phosphoric acid partial ester is used as an acid donor and a carbonizing substance (E P 0 5 5 6 3 5 0 B1). The disadvantage of this example is that the polyhydric alcohol-based phosphoric acid partial ester is very complicated to prepare on an industrial scale and cannot be obtained in large quantities. In addition, the service life of the existing system is only a few minutes. Β The last to be mentioned, EP 0 4 1 7 4 9 0 B1 refers to phosphate esters and their salts, molding ingredients and containing Their coating compositions, their use of phosphate esters and their salts as dispersants, and solids coated with them. Overall, the prior art proposed on the one hand formulations that contain halogens and thus release toxic and corrosive gases in the event of a fire. On the other hand, halogen-free systems are proposed, but their service life is very short and in some cases these products cannot achieve sufficient hardening. For some systems, there are problems associated with their technical manufacturing; for others, their applications are small. Therefore, an object of the present invention is to provide an expandable coating composition which does not contain halogen, has a sufficient service life and does not need to be added. 2 丨 0X297 mm) · 5-I: -I: ------, ----- Ί1Τ: ------ Quan (诮 Please read the precautions on the back and then write this page) 4 195 13 B7 V. Description of the invention (3) Hardening) The material can form a completely hardened product. (Please read the note on the back first and then on this page) This objective is achieved by the expandable flame-retardant coating composition of the category described at the beginning of this article, which composition includes 10 to 150 parts by weight A synthetic resin aqueous dispersion with a mixture of 10 to 80 parts by weight containing at least two different phosphate moieties. Preferably, the expandable flame-retardant coating composition comprises 50 to 90 parts by weight of a synthetic resin aqueous dispersion and 20 to 60 parts by weight of a mixture containing at least two different phosphate partial esters. Of these, 1 to 80 parts by weight of the other component 3 is preferred, and there is a mixture containing 3 different phosphate moieties. Particularly preferred is a mixture containing 4 different phosphate partial esters. In particular, the expandable flame-retardant coating composition includes (a) a monoalkyl phosphate and a dialkyl phosphate having the same alkyl group. Mixtures, and (b) a mixture of phosphate-alkyl esters and dialkyl phosphates having the same alkyl group but different from those in a). The phosphate partial esters are preferably monomethyl ester, monoethyl ester, Propyl ester, monoisopropyl ester, monobutyl ester, monoisobutyl ester, monopentyl ester, monoisopentyl ester, monohexyl ester, monooctyl ester, mono (2-ethylhexyl ester), monoethylene glycol ester, Dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, diisobutyl, dipentyl, dihexyl, dioctyl, di (2-ethylhexyl) and / or Paper Standards: Applicable to China Standards (CNS > A4 (210X297mm) -6-Α7 Β7 4 195 13) 5. Description of the invention (4) or diethylene glycol esters and their mixtures. The synthesis The resin aqueous dispersion is preferably a nitrogen-containing synthetic resin dispersion. The synthetic resin aqueous dispersion is preferably a melamine-formaldehyde and / or urea-formaldehyde resin. The synthetic resin aqueous dispersion is particularly preferably an etherified melamine-formaldehyde and / or urea-formaldehyde resin. The above-mentioned melamine resin used according to the present invention is usually melamine and formaldehyde in a ratio of 1: 1 to 1: 6 (melamine: formaldehyde). ) The reaction product of Molby. The melamine-formaldehyde resin may also be in the form of an etherified alcohol having a chain length of 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms. Other components are preferred For dispersants, additives, hardeners, shakers, plasticizers, acid donors, other flame retardants, surface aids and / or adhesives < For the purposes of the present invention, 1 colorant " ( colorants) means, for example, those colorants contained in R ^ jmpp's Chemie Lexikon, 9lh Edition, 1992, page 1237. This term includes organic and inorganic, natural and synthetic colorants, in other words, pigments and dyes. When a coloring material is used, the expandable flame-retardant coating composition of the present invention is usually transparent (light-transmitting). By adding concrete, especially talc and other materials, the coating composition may also have a good appearance. The selection of appropriate coloring materials, especially inorganic pigments, may also be made into a white, expandable, nonflammable coating composition that has a color when dry, preferably white. This paper is standard. [Guild] 6 4 specifications (2 丨 0 > < 297 mm) —: -I: ------ i -----— ΐτ: ------ Quan (read the first Note for reprinting this page) 4 195 13 'A7 B7 5. Description of the invention (5) Particularly preferred, these other components are shakers and / or additives. Those phosphate esters are preferred For those who have the following formula ο ο — Ρ — ο

Η 2 R ο R

f '; r " .ir 屮 ^^; ¥-^ m Diluted by 仃 卬 V where R1 and R2 can be the same or different and are Η, CH3 * C2H5, C3H7, C4H9' C5H11, CeHl3, CeHl6 and / or CH2-CH2OH, but both are not hydrogen at the same time. The novel mixture containing at least two different phosphate moieties usually comprises 2 to 98% by weight of one phosphate moiety and 98 to 2 wt% of another different phosphate moieties. It is preferable to use one of 10 to 90% by weight and another phosphate partial ester of 90 to .10% by weight. In the case of a mixture containing three different phosphate moieties, the ratio is usually (2 to 98): (4:96): (4: 96)% by weight. In the case of a mixture containing four different phosphate moieties, the ratio of mixture a) to mixture b) is (98 to 2): (2 to 98)% by weight and preferably (10 to 90): (90 to 10)% by weight. For the mixtures in a) and b) respectively, the ratio of the phosphoric acid-alkyl ester to the dialkyl phosphate is (2 to 98): (98 to 2)% by weight, preferably (10 to 90): ( 90 to 10)% by weight. This paper size applies to the standard of the Chinese storehouse {CNS) 8 4 specifications (210X 297 mm) -8-(Please read the precautions on the back before coping with this page) '1T 4 19513 W A7 -___________ B7__ 5. Description of the invention (6) Examples of dispersants that can be used for solids are phosphoric acid- (polyethylene glycol) -carbonate, mono (polyethylene glycol) aryl phosphate, di (polyethylene glycol) alkyl phosphate, and / Or bis (polyethylene glycol) aryl phosphate and their mixtures. The expandable flame-retardant coating composition has a phosphorus content of 1 to 15% by weight after hardening. The phosphorus content of the expandable flame-retardant coating composition after hardening is preferably 4 to 10% by weight. The invention also proposes the use of the coating composition of the invention to produce a coating on wood, plastic, building materials, cellulosic materials, rubber and metal, and to impregnate textiles and leather. The invention is illustrated by the following examples, in which the following substances are used. ® Maprenal MF 9 2 0 ® Maprenal MF 9 2 0 (Vianova Resins) is an unplasticized but methyl etherified melamine-formaldehyde resin. Bismuth ·· 中 中 成 c ^-^ m · 1 · Suppressing noises. ^ 印 y (诮 Read the precautions on the back before writing this page)

® Maprenal VMF 3 9 2 1 W ® Maprenal VMF 3 9 2 1 W (Vianova Resins) is a melamine-formaldehyde resin that has not been plasticized but is methyl-etherified.

® Plastopal BTW This is a flexible urea-formaldehyde resin containing urethane functionality and methanol etherified (manufacturer: BASF). The standard of this paper applies to the national standard of China -9- Α7 Β7 4195ί3 V. Description of the invention (7) (Please read the notes on the back before writing this page)

® Knapsack Phosphors a ureester MDB It is a mixture of phosphate-ethyl and phosphate-diethyl.

® Knapsack Phosphorsaureester MDIP is a mixture of monoisopropyl phosphate and diisopropyl phosphate. ® Knapsack Phosphorsaureester " 122 This dispersant is a mixture of phosphoric acid- (polyethylene glycol) alkyl ester and di (polyethylene glycol) alkyl phosphate.

® Knapsack Reinigerkomponente MIS This detergent is a mixture of phosphoric acid-isopropyl ester, phosphoric acid-methyl ester, and phosphoric acid.

® Knapsack Phosphorsaureester MOE This is a mixture of phosphate-ethyl ester and phosphoric acid.

® Knapsack Reinigerkomponente MS This detergent is monomethyl phosphate.

® Knapsack Phosphorsaureester MDB This is a mixture of phosphate-butyl ester and dibutyl ether. This paper size applies to Chinese national standards (CNS > A4 specifications (2 丨 0X297mm> -10- 4 195 t S A7 B7) V. Description of the invention (8) The above products ® Knapsack Phosphorsaureester and ® Knapsack Reinigerkomponente are all by Clariant GmbH , Werk

(诮 Please read the precautions on the back first, then Eqiao page J

E ® Mistrofil by Knapsack 5 0 0 This is a commercial talc * ® Aerosil R 8 16 This is the high temperature oxidized sand obtained by Degussa AG. The ingredients are mixed with each other in the order described in the examples and applied to pine or cardboard. And dried, and its expansion behavior was measured. The order in which the ingredients are applied is arbitrary and depends on their desired coating thickness and other conditions (viscosity, substrate, service life, etc.). Other suitable substances are explained in individual examples. The coating compositions obtained according to the following examples are transparent, smooth and free of cracks * and have an average service life of more than 24 hours. After less than 24 hours (on average), the coated coating composition is non-sticky and hard. "Bin and B have reached B 1 and B in these formulations when tested on pine and cardboard Classification level of 2 and so on. Example 1 6 8 parts by weight ® Maprenal MF 9 2 0 2 5 5 parts by weight with 90% by weight ® Knapsack

Phosphorsaureester M0E and 10% by weight ® Knapsack This paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm) -11-4 195 13 A7 B7 V. Description of the invention (9)

Mixture of Reinigerkomponente MS < Read the notes on the back before filling in this page j Example 2 6 8 parts by weight ® Maprenal MF 920 2 4. 8 parts by weight with 80% by weight ® Knapsack

Mixture of Phosphorsaureester M0E and 20% by weight ® Knapsack Reinigerkomponente MS Example 3 6 8 parts by weight ® Maprenal MF 9 2 0 24 · 9 parts by weight with 70 knapsack

Mixture of Phosphorsaureester MOE and 30% by weight ® Knapsack Reinigerkomponente MS with 60 parts by weight of ® Maprenal VMF 3 9 2 1 w Substituting 6 8 parts by weight of ® Maprenal MF 920 and repeating Examples 1 to 3 gave similar results. Example 4 6 8 parts by weight ® Maprenal MF 920 2 4. 9 parts by weight with 80% by weight ® Knapsack

Mixture of Phosphorsaureester M0E and 20% by weight ® Knapsack Reinigerkomponente MIS Example 5 This paper size applies the Chinese Standard (CNS) A4 specification (210X297 mm) -12 · A7 4 195 13 B7 V. Description of the invention (1〇 ) 6 8 parts by weight of ® Maprenal MF 920 2 4. 8 parts by weight of 70% by weight ® Knapsack

Mixture of Phosphorsaureester MOE and 30% by weight ® Knapsack Reinigerkomponente MIS Example 6 6 8 parts by weight ® Maprenal MF 9 2 0 2 4. 9 parts by weight with 90% by weight ® Knapsack

Mixture of Phosphorsaureester M0E and 10% by weight ® Knapsack Reinigerkomponente MIS Example 7 6 8 parts by weight ® Maprenal MF 9 2 0 26. 1 parts by weight with 90 weight Knapsack

Mixture of Phosphorsaureester MOE and 10% by weight ® Knapsack PhosphorsSureester MDIP Example 8 6 8 parts by weight ® Maprenal MF 9 2 0 26 _ 4 parts by weight with 80% by weight Knapsack

Mixture of PhosphorsSureester M0E and 20% by weight ® Knapsack Phosphorsaureester MDIP Example 9 This paper is sized in accordance with China Standard (CNS) A4 (2 丨 〇 × 2ί »7mm) -13-(诮 Read the note on the back first (Notes on this page)

、 1T nailed to the center of the Shanghai Department i;-; T ^ hT · eliminate in harmony. ^ 卬 t 419513 A7 B7 V. Description of the invention (11) 6 8 parts by weight of Maprenal MF 9 2 0 (诮 Read the first Note the re-dome sheet) 28. 7 parts by weight containing 70% by weight ® Knapsack PhosphorsSureester MOE and 30% by weight ® Knapsack PhosphorsSureester MDIP Example 1 0 6 8 parts by weight of Maprenal MF 9 2 0 2 6. 4 weights for children with 90 weight ® Knapsack

Mixture of Phosphorsaureester M0E and 10% by weight ® Knapsack PhosphorsSureester MDB Example 1 1 6 8 parts by weight of Maprenal MF 920 2 7 9 parts by weight with 80% by weight ® Knapsack Phosphors Sureester Μ 0 E and 2 0 weight? 6 ® K n a p s a c k PhosphorsSureester MDB Mixture Example 1 2 6 8 parts by weight ® Maprenal MF 920 29. 6 parts by weight with 80 weight Knapsack Phosphorsaureester M0E and 20 weight? 6 ® Knapsack PhosphorsSureester MDB mixture uses 60 parts by weight of ® Maprenal VMF 3 9 2 1 w instead of 6 8 parts by weight of ® Maprenal MF 920 Repeat Example 7 This paper is suitable in size; ϊϋNational Standard (CNS) A4 specification (2 丨 0X297 mm) ~. 14- 4 195 J 3 A7 B7 V. Description of the invention (12) to 1 2 get similar results. Example 1 3 6 8 parts by weight ® Maprenal MF 9 2 0 2 4. 3 parts by weight with 90% by weight ^ Knap sack

Mixture of Reinigerkomponente MS and 10% by weight ® Knapsack Reinigerkomponente MIS Example 1 4 6 8 parts by weight ® Maprenal MF 9 2 0 2 4. 4 parts by weight with 80% by weight ® Knapsack

Mixture of Reinigerkomponente MS and 20% by weight ® Knapsack Reinigerkomponente MIS Example 1 5 6 8 parts by weight ® Maprenal MF 9 2 0 2 4. 3 parts by weight with 70 weight? 6 ® Knapsack

Mixture of Reinigerkomponente MS and 30% by weight ® Knapsack Reinigerkomponente MIS Example 1 6 * 6 8 parts by weight ® Maprenal MF 920 2 5.5. 5 parts by weight with 90% by weight ® Knapsack

Reinigerkomponente MS and 10% by weight ® Knapsack This paper is suitable for Λ] Medium S National Standards (CNS M4 Specification (2) 0X297 mm) -15- {诮 Read the precautions on the back before dying this page)

• IT A7 B7 4 »95 13 V. Description of the invention (13)

Mixture of Phosphorsaureester MDIP Example 1 7 6 8 parts by weight of Maprenal MF 9 2 0 26. 7 parts by weight with 80% by weight of Knapsack Reinigerkomponente MS and 20% by weight of Knapsack PhosphorsSureester MDIP Example 1 8 6 8 parts by weight of Maprenal MF 9 2 0 2 8. 0 parts by weight with 7 ◦ wt% ® Knapsack

Mixture of Reinigerkomponente MS and 30% by weight ® Knapsack PhosphorsSureester MDIP Example 1 9 6 8 parts by weight ® Maprenal MF 9 2 0 2 5. 7 parts by weight with 90 weight Knapsack

Mixture of Reinigerkomponente MS and 10% by weight ® Knapsack Phosphorsaureester MDB Example 2 0 6 8 parts by weight ® Maprenal MF 9 2 0 27. 2 parts by weight with β0 Knapsack Reinigerkomponente MS and 2 0% by weight ® Knapsack paper Zhang scale is applicable to China National Standard (CNS) A4 (210X297 mm) -16- (诮 Please read the precautions on the back before filling out this page)

* 1T 195 13 at B7 I-I -.I-,---5. Description of the invention (14)

Mixture of Phosphorsaureester MDB Example 2 1 6 8 parts by weight of ® Maprenal MF 920 29.0 parts by weight of 70% by weight of Knapsack Reinigerkomponente MS and 30% by weight of Knapsack PhosphorsSureester MDB Example 2 2 6 8 Parts by weight of Maprenal MF 9 2 0 3 0. 1 parts by weight with 90% by weight i ® Knapsack

Mixture of Phosphorsaureester MDE and 10% by weight ® Knapsack Reinigerkomponente MS Example 2 3 6 8 parts by weight ® Maprenal MF 9 2 0 30. 1 parts by weight with 80% by weight ® Knapsack PhosphorsSureester MDE and 2 0% by weight ® Knapsack Reinigerkomponente MS Mixture Example 2 4 6 8 parts by weight of Maprenal MF 920 29. 3 parts by weight with 70 weight Knapsack

Phosphorsaureester MDE and 30% by weight ® Knapsack This paper has a common Chinese standard (CNS) A4 size (210X297 mm) -17- (谙 Please read the precautions on the back before filling in this page)

、? T A7 B7 4J95,3 V. Description of the invention (彳 5)

Reinigerkomponente MS Mixture {阅读 Read the notes on the back before filling this page) Use 60 parts by weight of Maprenal VMF 3 9 2 1 w instead of 6 8 parts by weight of Maprenal MF 9 2 0 Repeat Example 1 Similar results were obtained from 3 to 2 4 "Example 2 5 6 8 parts by weight of Maprenal MF 3 9 2 1 w

2 7 parts by weight ® Knapsack PhosphorsSureester MDE 7 parts by weight ® Knapsack Phosphorsaureester MDIP Example 2 6 60. 〇 parts by weight ® Maprenal MF 9 2 0

24. 〇 parts by weight ® Knapsack PhosphorsSureester MDE

6.0 parts by weight ® Knapsack Phosphorsaureester MDIP 3.0 parts by weight ® Aerosil R 8 1 6 7. 0 parts by weight ® Mistrofil 5 0 0 9: " · 部 中 ^^: 1,-and .. ^ 1. Consumer cooperation ^ fl, y Example 2 7

6 0 parts by weight ® Maprenal MF 9 2 0 2 7 · 1 parts by weight ® Knapsack PhosphorsSureester MDE

6.8 parts by weight ® Knapsack Phosphors a ureester MDIP 0.6 parts by weight ® Knapsack Phosphorsaureester 122 3. 0 parts by weight ® Aerosil R 8 16 7. 2 parts by weight ® Mistrofil 5 0 0 paper Standard Shizhou Chinese Family Standard (CNS) A4 specification (210X297 mm) -18-

Decay: 屮 部 屮 " ^ " And 卩 η1νί 于 合 竹 h 卬 V 4195 13 A7 B7 V. Description of the invention (16) Example 2 8 6 0 Parts by weight of Maprenal VMF 3 9 2 1 w 3 4 5 parts by weight with 75% by weight ® Knapsack

Mixture of PhosphorsSureester.MDE and 25% by weight ® Knapsack Phosphorsaureester MDIP Example 2 9 8 0 parts by weight ® Maprenal VMF 3 9 2 1 w 44. 6 parts by weight with 8 5 weight Knapsack

PhosphorsSureester MDE and 15% by weight! ® Knapsack PhosphorsSureester MDIP Mixture Example 3 0 8 0 parts by weight ® Maprenal VMF 3 9 2 1 w 46.5 parts by weight with 70 weight Knapsack

Mixture of Phosphors ^ ureester MDE and 30% by weight ® Knapsack PhosphorsSureester MDIP 9.6 parts by weight ® Mistrofil 5 0 0 4 parts by weight of highly dispersible silicon oxide The other expandable flame-retardant coating composition of the present invention Examples are listed in Tables 1 to 11. Each formulation achieved a B 1 or B 2 rating in the combustion test. This paper has been scaled to the Chinese National Standard (CNS) A4 (210X297 mm) -19-(谙 Read the precautions on the back before writing this page)

1T ί 95 ί 3 Α7 Β7 V. Description of the invention (17) Table 1: Component weight parts Example 3 1 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 is 85 wt% Knapsack Phosphorsaureester 85: 15 MDE and 15 wt% Knapsack

Mixture of PhosphorsSureester MDIP ° This indication is similarly applied to the following tables (诮 Please read the notes on the back before filling this page)

, 1T A " Ministry of Foreign Affairs ^^^^^^^^^^^ 54 Table 2: Component weight parts Example 34 Example 35 Example 36 ® Maprenal MF 920 75 80 80 MDE: MDIP 37.5 40 40 80 : 20 ® Mistrofil 500 13.5 17 20.8 Λ The paper size is suitable for the National Standard of China (CNS) A4 (2 丨 0X29? Mm)-20-4 ^ 95 13 Λ7 B7 V. Description of the invention (18) Table 3: Component weight parts Example 37 Example 38 Example 39 ® Maprenal VMF 392 1 w 60 60 60 MDE: MDIP 34.5 34.5 34.5 75:25 ® Mistrofil 500 7.8 6 6.9 > 30 Table 4: Ingredients by weight parts Example Example Example Example Example 40 41 42 43 44 45 ® Maprenal VMF 3921 w 50 80 80 75 75 60 MDEiMDIP 28.3 46 46 42.4 42.3 33.5 80:20 ® Mistrofil 500 6.5 8 9.2 12.7 15.2 17.5 The paper size is suitable for China National Standards Corporation (CNS) A4 size (210X297 mm) -21-4 f 95 1 3 a7 B7 V. Description of the invention (19) Table 5: Composition Parts by weight Example 46 Example 47 Example 48 Example 49 ® M aprenal VMF 3921 w 80 80 80 80 MDE: MDIP 45.4 45.3 45.2 45.2 80:20 Highly dispersible silica 4 6 8 10 ® CAB-0-SIL TS 530 ® Aerosil OX-50 (" Read the precautions on the back first Write this page again} h: " 部 屮 AKn, and h π 消 钤 合 钤., 1 卬 * '?,' In this series of experiments, the highly dispersible silica used was ® CAB-0-SIL TS 530 (available from CABOT, Hanau, Germany) .® Aerosil 〇χ-50 (high temperature silicon oxide from Degussa AG) can also be used successfully. Example 5 9 9 parts by weight of Maprenal VMF 3 9 2 1 w 4 1 · 1 5 parts by weight with 80% by weight ® Knapsack

Mixture of Phosphorsaureester MDE and 2 0% by weight ⑧ Knapsack Reinigerkomponente MIS 1 1. 7 parts by weight ® Mistrofil 5 0 0 〇 · 9 parts by weight ® Knapsack Phosphorsaureester 122 This paper is oriented towards the Chinese National Standard (CNS) A4 (2 丨 0X2? 7 public gold> -22-4195 13 V. Description of the invention (2〇) Table 6: Composition weight parts Example 5 1 Example 52 ® Plastopal BTW 60 60 MDEiMDIP 31 30.4 80:20 ® Mistrofil 500 7.9 6.8 ® Knapsack Phosphorsaureester 122 0.6 0.2

(Please read the precautions on the back of this page before you go to this page. J Table 7: Composition weight parts Example 53 Example 54 ® Maprenal VMF 392 1 w 90 90 MDE: MIS 45 45 80:20 ⑬ Knapsack Phosphorsaureester 122 0.9 0.9 High Dispersion Silica 9 10.8 ® Aerosil OX 50 This paper is suitable for Chinese national standards (CNS > A4 size (210X297 mm) -23-^ 19513 B7 V. Description of the invention (21) 九 # 部 屮 定 " η '· = · ^ Κτ.Consumption in combination with bamboo ;; " y Table 8: Composition weight parts Example 55 Example 56 ® Maprenal VMF 3921 w 80 80 MDE: MDIP 45.2 45.5 80:20 ® Mistrofil 500 9.6 8 High Dispersion Silica 4.0 4.8 ® Aerosil R 972 (Please read the precautions on the back first and then the fiT page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) -24-4 Post 13 5 、 Explanation of the invention (22) A7 B7 Type:. &Quot; illt ^ <! 'ITri.hl_i /; ^ s ^ "; it. ^ Irf Table 9: Component weight parts Example Example Example Example 57 58 59 60 ® Maprenal VMF 3921 75 75 75 75 w MDE: MDIP 42.6 42.5 42.4 42.5 80:20 ® Knapsack 0.5 0.5 0.5 0.5 Phosphorsaureester 1 22 High-dispersion silica 7.5 9 5.6 7.5 ® Aerosil OX-50 ® CAB-O-SIL L90 (Read the precautions on the back first and then write this page)- D-The paper scale is suitable for the national standard of China Park (CNS > A4 specification (210X297mm) -25-4 195 13 v A7 B7 V. Description of the invention (23) Table 1 〇: Example of composition weight parts Examples Example 61 62 63 64 ® Maprenal VMF 3921 w 75 80 80 80 MDE: MDIP 42.4 40 45.2 42.4 80:20 ® Knapsack 0.5 0.6 1.8 0.5 Phosphorsaureester 122 High-dispersion silica 3 4 4 3 ® CAB-0 -® Aerosil ® Aerosil ® CAB-0 · SIL L90 R 972 R 972 SIL L90

(诮 Read the precautions on the back before filling out this page J

41T ^ " Ministry 呔 ^^ · ^ ·· ^ 5 Eliminate the problem " 卬 * ';,: Use ® Maprenal MF 9 2 0 instead of ® Maprenal VMF 3 9 2 1 w Repeat Examples 6 1 to 6 4 got similar results. This paper is described in the national standard (CNS) Α4 specification (2Ι0χ 297 mm) -26- 4 ί 95 1 3 a? Β7-___________ · V. Description of the invention (24) 1 Table composition parts by weight Example 65 Example 66 ® Maprenal VMF 392 1 w 90 90 MDE: MDIP 45 45 80:20 ® Mistrofil 500 8 9 ® Knapsack 1 1 Phosphors ^ ureester 122 High Dispersion Silicon Oxide 3.6 ® Aerosil R 972 5.2 ® Aerosil R 972 (I read the precautions on the back first, and then use this page) Example 6 7 " y part ^^-Γ wan and h ^; /; 于 合 竹. ^ ° '"'] 8 0 Weight Servings of® Maprenal VMF 3 9 2 1 w 45.2 parts by weight with 80 weight Knapsack

Mixture of Phosphorsaureester MDE and 20% by weight ® Knapsack PhosphorsSureester MDIP 4 parts by weight of titanium dioxide (® Kronos 2 3 0 0) Example 6 8 This paper size applies to the Central Park National Standard (CNS) A4 specification (210X297 mm) 27-195 13 A7 B7 V. Description of the invention (25) 8 0 parts by weight of ® Maprenal VMF 3 9 2 1 w 4 5. 2 parts by weight containing 80% by weight ® Knapsack

Mixture of PhosphorsSureester MDE and 20% by weight ® Knapsack Phosphors3ureester MDIP 0 9 parts by weight of ® Knapsack PhosphorsSureester 12 2 4 parts by weight of titanium dioxide (® Kronos 2 3 0 0) Coating composition obtained according to Examples 6 7 and 6 8 All are smooth, white and without cracks. (诮 Please read the precautions on the back first, and then copy this page) '—Book. ^, Mining Department 屮,-); ^. ^-^. 卜' ..1 Xiaoguanghezhu.- ;; 卬; ^ This paper Music standard Shizhou medium store standard (CNS) A4 specification (2I0X297 mm) -28-

Claims (1)

4 'Zhengchongj repairs the patent scope Annex A: Patent Application No. 87 1 1 9039 Chinese Patent Application Amendment (Please read the precautions on the back before filling this page) Republic of China 8 8 1 February Amendment 1 An intumescent, flame-retardant coating composition comprising a mixture of 10 to 150 parts by weight of a synthetic resin aqueous dispersion and 10 to 80 parts by weight of a mixture containing at least two phosphate partial esters different from the following formula , 1 2 R o RIII ο — P — ο II ο where R1 and R2 can be the same or different and are Η, CH3, CsH5, C 3 Η 7 'C 4 Η 9' C 5 Η 1 1 'C 6 Η 1 3 'CsHl6 and / or CH2_CHzOH, but they are not hydrogen at the same time. 2. The expandable flame-retardant coating composition as described in the first patent application scope, which includes 50 to 90 parts by weight of a synthetic resin aqueous dispersion printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and 20 To 60 parts by weight containing a mixture of at least two different phosphate moieties, and 1 to 80 parts by weight of other ingredients. 3. The expandable flame-retardant coating composition as described in the scope of claims 1 or 2 of the patent application, which comprises a mixture containing three different phosphate partial esters. This paper size applies to China National Standard (CNS) A4 specifications < 210 X 297 mm) -1-0088 FU ABCS Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and applied for patent scope 4. If the scope of patent application The expandable, non-flammable coating composition of item 2 comprising a mixture containing 4 different phosphate moieties. 5. The expandable flame-retardant coating composition according to item 4 of the patent application, wherein the mixture containing 4 different phosphate partial esters includes (a) a phosphate-alkyl ester and a dialkyl phosphate having the same alkyl group Mixtures thereof, and (b) a mixture of phosphoric acid-esters and dialkyl phosphates having the same alkyl group but different from those of a). 6. The expandable flame-retardant coating composition according to the scope of the patent application, wherein the synthetic resin aqueous dispersion is a nitrogen-containing synthetic resin dispersion 0. The expandability, such as the scope of the patent application, No. 1 A flammable coating composition, wherein the synthetic resin aqueous dispersion is a melamine-formaldehyde and / or urea-formaldehyde resin. 8. The expandable flame-retardant coating composition according to item 1 of the application, wherein the synthetic resin aqueous dispersion is an etherified melamine-formaldehyde and / or urea-formaldehyde resin. 9. The expandable flame-retardant coating composition as described in the scope of patent application No. 1, wherein the other components are dispersant 'hardener', hardening agent, plasticizer, acid donor, other flame-retardant Agents, surface aids and / or adhesives. 10. The swellable flame-retardant coating composition 1 according to the scope of the patent application, wherein the other components of the shake modifier and / or the filler. 1 1. If you expand the inflammable flame-retardant coatings under the scope of the patent application (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 4 195 Μ Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and a Consumer Cooperative. VI. Patent application composition 'The hardened phosphorus content is 1 to 15% by weight. 12. The expandable flame-retardant coating composition according to item 1 of the patent application scope, wherein the phosphorus content after curing is 5 to 10% by weight. 1 3. The expandable flame-retardant coating composition as described in the scope of patent application No. 1 is transparent after coating and drying. 14. The coating composition according to item 1 of the scope of patent application, which is used to produce a coating on wood, plastic, construction materials, cellulose materials, rubber or metal, or can be used to impregnate textiles or leather . (Please read the precautions on the back before filling in this purchase) Order ---------- line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 4 'Zhengchongj repairs the patent scope Annex A: Patent Application No. 87 1 1 9039 Chinese Patent Application Amendment (Please read the precautions on the back before filling this page) Republic of China 8 8 1 February Amendment 1 An intumescent, flame-retardant coating composition comprising a mixture of 10 to 150 parts by weight of a synthetic resin aqueous dispersion and 10 to 80 parts by weight of a mixture containing at least two phosphate partial esters different from the following formula , 1 2 R o RIII ο — P — ο II ο where R1 and R2 can be the same or different and are Η, CH3, CsH5, C 3 Η 7 'C 4 Η 9' C 5 Η 1 1 'C 6 Η 1 3 'CsHl6 and / or CH2_CHzOH, but they are not hydrogen at the same time. 2. The expandable flame-retardant coating composition as described in the first patent application scope, which includes 50 to 90 parts by weight of a synthetic resin aqueous dispersion printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and 20 To 60 parts by weight containing a mixture of at least two different phosphate moieties, and 1 to 80 parts by weight of other ingredients. 3. The expandable flame-retardant coating composition as described in the scope of claims 1 or 2 of the patent application, which comprises a mixture containing three different phosphate partial esters. This paper size applies to China National Standard (CNS) A4 specifications < 210 X 297 mm) -1-