INTUMESCENT FLAME-RETARDANT CLEARCOAT FORMULATIONS

Abstract

The invention relates to intumescent flame-retardant clearcoat formulations containing 20% to 88.5% by weight of an aqueous synthetic resin formulation, 10% to 60% by weight of a phosphoric partial ester, 0.5% to 20% by weight of a polyol and 1% to 30% by weight of further ingredients, and to the use thereof.

Claims

1. An intumescent flame-retardant clearcoat formulation containing 20% to 88.5% by weight of an aqueous synthetic resin formulation, 10% to 60% by weight of a phosphoric partial ester, 0.5% to 20% by weight of a polyol and 1% to 30% by weight of further ingredients.

2. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, containing 30% to 75% by weight of an aqueous synthetic resin formulation, 20% to 50% by weight of a phosphoric partial ester, 3% to 15% by weight of a polyol and 2% to 20% by weight of further ingredients.

3. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, containing 40% to 60% by weight of an aqueous synthetic resin formulation, 30% to 40% by weight of a phosphoric partial ester, 5% to 10% by weight of a polyol and 5% to 15% by weight of further ingredients.

4. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, wherein the polyol is pentaerythritol, dipentaerythritol, tripentaerythritol and/or polycondensates of pentaerythritol and/or mixtures of pentaerythritol-based esters, glycerol, oligomeric glycerol, xylitol, sorbitol, mannitol, isomalt, lactitol, glucitol, threitol, erythritol, arabitol, inositol, glucosamine, polyvinyl acetate, polyvinyl alcohol and ethylene oxide-propylene oxide polyols.

5. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, wherein the polyol is sorbitol.

6. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, wherein the phosphoric partial ester is a composition corresponding to a mixture of mono- and diesters of orthophosphoric acid with one or more polyols, where the average hydroxyl group content of these polyols is at least 40% by weight, the molar monoester/diester ratio does not exceed 12:1 and the phosphorus content of the mixture is at least 10% by weight.

7. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, wherein the phosphoric partial ester is a composition corresponding to a mixture of optionally carboxylic anhydride-modified mono- and diesters of orthophosphoric acid with one or more polyols, where the average hydroxyl group content of these polyols is at least 40% by weight, the molar monoester/diester ratio does not exceed 12:1 and the phosphorus content of the mixture is at least 10% by weight.

8. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, wherein the aqueous synthetic resin formulation is a nitrogen-containing synthetic resin formulation.

9. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, wherein the aqueous synthetic resin formulation is a melamine-formaldehyde resin and/or urea-formaldehyde resin.

10. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, wherein the further ingredients are dispersants, fillers, curing agents, thixotropic agents, plasticizers, acid donors, further flame retardants, surface auxiliaries and/or binders.

11. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, having a phosphorus content after curing of 1% to 15% by weight.

12. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, having a phosphorus content after curing of 5% to 10% by weight.

13. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, which is transparent after application and drying.

14. The intumescent flame-retardant clearcoat formulation as claimed in claim 1, which is free of halogen.

15. The use of the clearcoat formulation as claimed in claim 1 for production of coatings of articles made of wood, wood materials, veneers, plastics, building materials, cellulose materials, rubber, metal and other materials, fabrics made of synthetic or natural fibers, and for impregnation of textiles and leathers and as an intumescent coating on polyolefins and as solder mask.

Description

EXAMPLE 1 (COMPARATIVE)

[0075]

TABLE-US-00001 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Budit ® 380 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 2

[0076]

TABLE-US-00002 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 3

[0077]

TABLE-US-00003 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 5.38 pbw Chinafill 100 2.0 pbw Exolit AP 422 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 4

[0078]

TABLE-US-00004 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 4.38 pbw Chinafill 100 3.00 pbw Exolit AP 422 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 5

[0079]

TABLE-US-00005 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 3.38 pbw Chinafill 100 4.00 pbw Exolit AP 422 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 6

[0080]

TABLE-US-00006 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% glycerol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 7

[0081]

TABLE-US-00007 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% inositol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

TABLE-US-00008 TABLE 1 Example 1 Name (comparative) 2 3 4 5 6 7 Amounts and type of 47.90 pbw 47.90 pbw 47.90 pbw 47.90 pbw 47.90 pbw 47.90 pbw 47.90 pbw aqueous synthetic resin Maprenal ® Maprenal ® Maprenal ® Maprenal ® Maprenal ® Maprenal ® Maprenal ® formulation (melamine- MF MF MF MF MF MF MF formaldehyde resin) 920w/75WA 920w/75WA 920w/75WA 920w/75WA 920w/75WA 920w/75WA 920w/75WA Foam-forming substance 32.65 pbw 32.65 pbw 32.65 pbw 32.65 pbw 32.65 pbw 32.65 pbw 32.65 pbw (partial phosphoric ester) Budit 380 Exolit 855 Exolit 855 Exolit 855 Exolit 855 Exolit 855 Exolit 855 Foam-forming substance 0 pbw 0 pbw 2.0 pbw 3.0 pbw 4.0 pbw 0 pbw 0 pbw (ammonium polyphosphate) Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Carbon-forming substance 9.23 pbw 9.23 pbw 9.23 pbw 9.23 pbw 9.23 pbw 9.23 pbw 9.23 pbw (carbohydrates) sorbitol sorbitol sorbitol sorbitol sorbitol glycerol inositol Reaction accelerator 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw p-toluene- p-toluene- p-toluene- p-toluene- p-toluene- p-toluene- p-toluene- sulfonic acid sulfonic acid sulfonic acid sulfonic acid sulfonic acid sulfonic acid sulfonic acid Modifier 7.38 pbw 7.38 pbw 5.38 pbw 4.38 pbw 3.38 pbw 7.38 pbw 7.38 pbw Chinafill Chinafill Chinafill Chinafill Chinafill Chinafill Chinafill Surface additive 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw BYK 333 BYK 333 BYK 333 BYK 333 BYK 333 BYK 333 BYK 333 pbw = parts by weight

EXAMPLE 8

[0082]

TABLE-US-00009 47.90 pbw Maprenal ® MF 921w/85WA 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 9

[0083]

TABLE-US-00010 32.90 pbw Maprenal ® MF 921w/85WA 15.00 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 10

[0084]

TABLE-US-00011 15.00 pbw Maprenal ® MF 921w/85WA 32.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 11

[0085]

TABLE-US-00012 47.90 pbw Resimene ® AQ-2610 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 12

[0086]

TABLE-US-00013 15.00 pbw Maprenal ® MF 921w/85WA 32.90 pbw Resimene ® AQ-2610 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 13

[0087]

TABLE-US-00014 32.90 pbw Maprenal ® MF 921w/85WA 15.00 pbw Resimene ® AQ-2610 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 14

[0088]

TABLE-US-00015 47.90 pbw Primere ® 70 0867L 32.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

TABLE-US-00016 TABLE 2 Example Name 8 9 10 11 Amounts and type of film- 47.90 pbw 15 pbw 32.90 pbw 47.90 pbw forming binder and blowing Maprenal ® MF Maprenal ® MF Maprenal ® MF Resimene ® agent (melamine- 921w/85WA 920w/75WA 920w/75WA AQ-2610 formaldehyde resin) 32.90 pbw 15 pbw Maprenal ® MF Maprenal ® MF 921w/85WA 921w/85WA Foam-forming substance 32.65 pbw 32.65 pbw 32.65 pbw 32.65 pbw (partial phosphoric ester) Exolit 855 Exolit 855 Exolit 855 Exolit 855 Foam-forming substance 0 pbw 0 pbw 0 pbw 0 pbw (ammonium polyphosphate) Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Carbon-forming substance 9.23 pbw 9.23 pbw 9.23 pbw 9.23 pbw (carbohydrates) sorbitol sorbitol sorbitol sorbitol Reaction accelerator 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw p-toluene- p-toluene- p-toluene- p-toluene- sulfonic acid sulfonic acid sulfonic acid sulfonic acid Modifier 7.38 pbw 7.38 pbw 7.38 pbw 7.38 pbw Chinafill Chinafill Chinafill Chinafill Surface additive 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw BYK 333 BYK 333 BYK 333 BYK 333 Example Name 12 13 14 Amounts and type of film- 15 pbw 32.90 47.90 pbw forming binder and blowing Maprenal ® MF Maprenal ® MF Primere ® 70 agent (melamine- 920w/75WA 920w/75WA 0867L formaldehyde resin) 32.90 pbw 15 pbw Resimene ® Resimene ® AQ-2610 AQ-2610 Foam-forming substance 32.65 pbw 32.65 pbw 32.65 pbw (partial phosphoric ester) Exolit 855 Exolit 855 Exolit 855 Foam-forming substance 0 pbw 0 pbw 0 pbw (ammonium polyphosphate) Exolit AP 422 Exolit AP 422 Exolit AP 422 Carbon-forming substance 9.23 pbw 9.23 pbw 9.23 pbw (carbohydrates) sorbitol sorbitol sorbitol Reaction accelerator 2.34 pbw 2.34 pbw 2.34 pbw p-toluene- p-toluene- p-toluene- sulfonic acid sulfonic acid sulfonic acid Modifier 7.38 pbw 7.38 pbw 7.38 pbw Chinafill Chinafill Chinafill Surface additive 0.5 pbw 0.5 pbw 0.5 pbw BYK 333 BYK 333 BYK 333 pbw = parts by weight

EXAMPLE 15

[0089]

TABLE-US-00017 47.90 pbw Maprenal ® MF 920w/75WA 41.88 pbw Exolit ® 855 0.00 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw Hypersal XT 782

EXAMPLE 16

[0090]

TABLE-US-00018 47.90 pbw Maprenal ® MF 920w/75WA 27.65 pbw Exolit ® 855 14.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw Hypersal XT 782

EXAMPLE 17

[0091]

TABLE-US-00019 37.90 pbw Maprenal ® MF 920w/75WA 42.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw Hypersal XT 782

EXAMPLE 18 (COMPARATIVE)

[0092]

TABLE-US-00020 57.90 pbw Maprenal ® MF 920w/75WA 12.65 pbw Exolit ® 855 9.23 pbw 70% sorbitol solution in water 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 19

[0093]

TABLE-US-00021 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 9.23 pbw Genamin ® Gluco 50 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 20

[0094]

TABLE-US-00022 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 4.00 pbw 70% sorbitol solution in water 5.23 pbw Genamin ® Gluco 50 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

EXAMPLE 21

[0095]

TABLE-US-00023 47.90 pbw Maprenal ® MF 920w/75WA 32.65 pbw Exolit ® 855 5.23 pbw 70% sorbitol solution in water 4.00 pbw Genamin ® Gluco 50 7.38 pbw Chinafill 100 2.34 pbw p-toluenesulfonic acid 0.5 pbw BYK 333

TABLE-US-00024 TABLE 3 Example 18 Name 15 16 17 (comparative) 19 20 21 Amounts and type of film- 47.90 pbw 47.90 pbw 37.90 57.90 47.90 pbw 47.90 pbw 47.90 pbw forming binder and Maprenal ® Maprenal ® Maprenal ® Maprenal ® Maprenal ® Maprenal ® Maprenal ® blowing agent (melamine- MF MF MF MF MF MF MF formaldehyde resin) 920w/75WA 920w/75WA 920w/75WA 920w/75WA 920w/75WA 920w/75WA 920w/75WA Foam-forming substance 41.88 pbw 27.65 pbw 42.65 pbw 12.65 pbw 32.65 pbw 32.65 pbw 32.65 pbw (partial phosphoric ester) Exolit 855 Exolit 855 Exolit 855 Exolit 855 Exolit 855 Exolit 855 Exolit 855 Foam-forming substance 0 pbw 0 pbw 0 pbw 0 pbw 0 pbw 0 pbw 0 pbw (ammonium polyphosphate) Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Exolit AP 422 Carbon-forming substance 0 pbw 14.23 pbw 9.23 pbw 9.23 pbw 9.23 pbw 4.0 pbw 5.23 pbw (carbohydrates)/amino sorbitol sorbitol sorbitol sorbitol Genamin sorbitol sorbitol alcohol Gluco 50 5.23 pbw 4.0 pbw Genamin Genamin Gluco 50 Gluco 50 Reaction accelerator 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw 2.34 pbw p-toluene- p-toluene- p-toluene- p-toluene- p-toluene- p-toluene- p-toluene- sulfonic acid sulfonic acid sulfonic acid sulfonic acid sulfonic acid sulfonic acid sulfonic acid Modifier 7.38 pbw 7.38 pbw 7.38 pbw 7.38 pbw 7.38 pbw 7.38 pbw 7.38 pbw Chinafill Chinafill Chinafill Chinafill Chinafill Chinafill Chinafill Surface additive 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw 0.5 pbw Hypersal XT Hypersal XT Hypersal XT BYK 333 BYK 333 BYK 333 BYK 333 782 782 782 pbw = parts by weight

[0096] Testing of the quality of the clearcoat formulations of the invention with regard to heat emission rate and transparency

[0097] Materials that are used on board rail vehicles and are applied to vertical surfaces indoors and to other surfaces must meet corresponding demands with regard to heat emission rate under the action of thermal radiation. The heat emission rate is ascertained by irradiating a specimen in a horizontal position. The procedure of testing and assessment of the results is based on standards ISO 5660-1 and DIN EN 45545-2.

[0098] The assessment criterion according to EN45545-2 for tests on a cone calorimeter is the MARHE value. This is the maximum of the average heat emission rate over the period of the measurement and is ascertained as the average from 3 individual tests. The MARHE value gives the corresponding hazard level (HL2<90 kW/m.sup.2; HL3<60 kW/m.sup.2).

[0099] An amount of 400 g/m.sup.2 of each intumescent formulation thus produced was applied to a solid spruce board (100×100×20 mm) and subjected to a heat emission test to ISO 5660-1 (cone calorimeter test). The MARHE value indicates the heat emission rate based on surface area (kW/m.sup.2) under the chosen test parameters. The lower the heat emission, the better the insulating effect of the intumescent coating.

[0100] Transparency

[0101] The ability of material to transmit light waves is referred to as transparency. A material is described as transparent if it is transparent to visible light having a wavelength in the range from 380 nanometres (nm) to 780 nm. Thus, a material, for instance window glass, is described as being transparent if it is possible to see what lies behind it relatively clearly. This is also true within the scope of the invention.

[0102] This gave the test results shown in table 4.

TABLE-US-00025 TABLE 4 Intumescent formulation MARHE value Visual test* from (kW/m.sup.2) Grade Blank: uncoated spruce wood 148 Example 1 (comparative) 75 5 Example 2 33 1 Example 3 4 2 Example 4 4 2 Example 5 5 3 Example 9 62 2 Example 10 66 1 Example 11 70 2 Example 14 68 2 Example 15 71 1 Example 3 45 2 Example 18 (comparative) 80 5 Example 19 40 2 *For the visual test, the respective intumescent formulation is applied in defined layer thickness to a test chart for visual assessment of hiding capacity to ISO 6504-3.

[0103] The assessment is made by a German school grade system, where grade 1 means “highest transparency, no haze” down to grade 6: “low transparency, significant haze”).

[0104] The clearcoat formulations of the invention using phosphoric partial esters (Exolit® 855 here) are all transparent and therefore of excellent suitability for production of effective transparent intumescent coatings.

[0105] In addition, the clearcoat formulations of the invention have only low heat emissions, as apparent from the MARHE values. Thus, the clearcoat formulations of the invention in the form of an intumescent coating have a good insulating effect.