GRANULATE MATERIAL AND ASSOCIATED COATING THAT IS LOW IN ODOR AND EMISSIONS, PARTICULARLY A CONSTRUCTION ELEMENT COATING, FOR EXAMPLE A FLOOR COATING, BASED ON A RADICAL POLYMERIZATION

Abstract

Granulate material fora radical chain-growth polymerization based coating formulation, adapted to minimize inhibition of resin polymerization by ambient air, composition of granulate material, coating formulation kit, and process for applying a radical chain-growth polymerization based coating formulation kit.

Claims

1. A granulate material for a radical chain-growth polymerization based coating formulation, adapted to minimize inhibition of resin polymerization by ambient air, comprising at least a granulate material having an average particle size d50 of between 0.1 and 2 mm, measured according to ASTM C136, selected from the group consisting of (i) apolar granulate materials having a contact angle with water of 35° or more, preferably of 55° or more, when measured according to the norm DIN 55660-2:2011-12, at least partially coated with at least one component C1, which is an accelerator and/or a radical initiator, wherein the amount of component C1 is more than 0.2 g/m.sup.2 of apolar granulate material surface area, or (ii) granulate materials coated with at least one component C1, which is an accelerator and/or a radical initiator, wherein the amount of component C1 is more than 4 g/m.sup.2 and mixtures thereof.

2. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 1, wherein the amount of component C1 of the apolar granulate materials (i) having a contact angle with water of 35° or more is less than 5 g/m.sup.2 of apolar granulate material surface area.

3. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 1, wherein the amount of component C1 of the granulate materials (ii) is less than 10 g/m.sup.2 of apolar granulate material surface area.

4. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 1, wherein the granulate material contains at least apolar granules and/or at least particles of granulate material which are at least partially coated with an apolar composition such as paraffin or wax.

5. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 4, wherein the at least present granulate material has a particle size d.sub.30 of between 0.4 and 0.8 mm and/or has a particle size d.sub.70 of between 0.8 mm and 1.2 mm, measured by ASTM C136.

6. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 4, wherein the apolar composition is selected from linear hydrocarbons of the general formula C.sub.nH.sub.2n+2, wherein n has a value of between 10 and 70, and an iso- and cycloalkanes/paraffins content of from 0 to 60%, microcrystalline wax, carnauba wax, beeswax, lanolin, whale oil, a polyolefin wax, ceresin, candelilla wax, and a mixture thereof.

7. A granulate material for a radical chain-growth polymerization based coating formulation, according to claim 1, wherein the component C1 contains at least an accelerator selected from tertiary amines, ammonium salts and mercaptans.

8. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 1, wherein the component C1 contains at least one initiator.

9. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 1, wherein the apolar composite granulate material is packaged in a bag, wherein at most 41.5% of the volume of the bag is air.

10. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 1, wherein the particles of granulate material are selected from quartz, metal carbides, sand, metal particles, marble, dolomite, glass, ceramics, or wherein the granules are polymeric granules.

11. (canceled)

12. A granulate material for a radical chain-growth polymerization based coating formulation according to claim 1, wherein the apolar granulate material is further coated with a desiccant in an amount of from 0.5 to 2 m %.

13. A composition of granulate material for a radical chain-growth polymerization based coating formulation, comprising at least one granulate material according to claim 1.

14. A composition of granulate material for a radical chain-growth polymerization based coating formulation according to claim 13, comprising a mixture of different apolar composite granulate materials.

15. A coating formulation kit comprising: At least one granulate material according to claim 1 having an average particle size d50 of between 0.1 and 2 mm, measured according to ASTM C136 One component C1 which is an accelerator and/or a radical initiator, A base coat kit, comprising at least one component C2 which is the same or is not the same as component C1, which is an initiator or accelerator, further comprising at least one liquid resin, said liquid resin comprising at least 30 m % of at least one vinyl group containing monomer, polymer or oligomer or a mixture thereof.

16. A coating formulation kit according to claim 15, wherein, in the present coating formulation kit, at least from 0.01 to 10 m %, of at least one accelerator, based on the mass of the liquid resin, is present, either on the apolar composite granulate material or in the base coat kit or both, further containing at least from 0.1 to 10 m %, preferably from 0.5 to 6.5 m % of at least one redox-initiating radical initiator based on the mass of the liquid resin, either on the granulate material (i), granulate material (ii) or in the base coat kit or all three.

17. (canceled)

18. A coating formulation kit according to claim 15, further comprising at least one additional kit selected among a primer kit, a topcoat kit or a combination of both.

19. (canceled)

20. A coating formulation kit according to claim 15, wherein the liquid resin has a vapor pressure of less than 0.1 kPa at 20° C.

21. A coating formulation kit according to claim 15, wherein the component C2, contains at least one initiator selected from, a perester, a per-ketal, acetylacetone peroxide, dilauroyl peroxide, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxy benzoate, tert-butyl peroxy isopropyl carbonate, 2,5-bis-(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,1-bis (tert-butyl peroxy) cyclohexane, 1,1-bis-(tert-butyl peroxy)-3,3,5-trimethyl cyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, bis-(4-tert-butylcyclohexyl) peroxide carbonate and mixtures thereof.

22. (canceled)

23. A coating formulation kit according to claim 15, wherein the base coat kit further contains at least one filler in an amount of 1 to 4 times the mass of the liquid resin.

24. (canceled)

25. A process for applying a radical chain-growth polymerization based coating formulation kit according to claim 15 onto a surface, the process comprising: (i) mixing components of the base coat kit (ii) applying the base coat onto the surface, (iii) distributing said at least one granulate material (i) or (ii) over the surface of the previously applied base coat mixture (iv) curing the base coat so as to form the coating on a surface.

26. A process for applying a radical chain-growth polymerization based coating formulation kit according to claim 25, wherein the surface is a substrate and wherein the application occurs within 60 minutes from the mixing of components of the base coat kit, at a thickness of 0.2 to 10 mm.

27.-30. (canceled)

Description

FIGURE

[0140] The one included FIGURE is a schematic overview of the self-regulating process according to the present invention to prevent oxygen inhibition in radical polymerization during application of cold curing coatings for coating construction elements.

[0141] In the FIGURE, the same reference numbers are assigned to the same or similar elements.

[0142] As can be inferred from the FIGURE, the present invention relates to a process for applying a coating 7 onto a substrate. The coating 7 contains granulate materials 1 and a liquid resin 4 with a less pronounced odor, less toxicity, a reduced flammability, faster curing and a better balance between labor time and curing time. These improvements may be found in the coating formulations 7 of the present invention, combined with the durable and efficient production of coating films with good chemical and physical properties.

[0143] 1. Granulate material 1 for a radical chain-growth polymerization based coating formulation 7 that is suitable for preventing inhibition 2 of resin polymerization by ambient air, comprising at least a granulate material 1 having an average particle size d50 of between 0.1 and 2 mm, selected from the group consisting of (i) apolar granulate materials 1 having a contact angle of 95° or more, when measured according to the norm IS015989:2004, at least partially coated with at least one component C1, which is an accelerator and/or initiator, wherein the amount of component C1 is between 0.2 and 5 g/m.sup.2 of apolar granulate material surface area, or (ii) granulate materials 1 coated with at least one component C1, which is an accelerator and/or initiator, wherein the amount of component C1 is sufficient to be suitable for enabling a resin polymerization which takes place faster than the inhibition by ambient conditions.

[0144] As can be seen, according to the present invention, it is possible to remedy at least part of the listed disadvantages by making available a granulate material 1 which can be used with different resin formulations, and which contributes to reducing odor and volatile organic components while simplifying the application of the floor coating formulation.

[0145] 2. As can be seen, the granulate material according to the present inventions has a contact angle of 35° or more, preferably of 55° or more when measured with water according to the norm DIN 55660-2:2011-12, giving rise to a difference in polarity with the different types of resins and making application easier; or the granulate material is coated 1 with at least one component C1, which is an accelerator and/or initiator, wherein the amount of component C1 is sufficient to be suitable for enabling a resin polymerization which takes place faster than the inhibition by ambient conditions 2.

[0146] The apolar granulate material contains at least apolar granules and/or at least particles of granulate material which are at least partially coated with an apolar composition such as paraffin or wax.

[0147] The component C2 is commonly used in an amount ranging from 0.1 to 10 m %, preferably from 0.5 to 6 m % based on the total mass of the mixture of the liquid resin. The effective amount is to be chosen so that after applying the granulate materials, an oxygen barrier is formed after limited reaction due to polymerization within 30 min after applying the granulate materials, preferably within 10 min. Moreover, the concentration should be chosen so that the coating has a processing time (=the available time for applying the coating before the granulate materials are to be spread over the liquid surface) of a few minutes to a matter of hours, preferably between 5 min to 200 min, even more preferably between 5 min and 60 min, most preferably between 5 min and 30 min.

[0148] When the component C2 contains at least one initiator, it is preferably selected from the group comprising peroxides such as a ketone peroxide, a diacyl peroxide, a perester, a per-ketal, and more preferably dibenzoyl peroxide and dilauroyl peroxide which may contain a form of plasticizer, and a mixture thereof.

[0149] When the component C2 contains at least one accelerator, it is preferably selected from the amine group, more preferably tertiary amines or ammonium salts and mercaptans.

[0150] Indeed, with known coating formulations, when the floor coating is applied onto an existing substrate, the first step is mixing the different components of the resin and applying the mixture in the form of a layer 4 onto the existing substrate. The mixture of the different components may also contain a filler, or the filler may be applied on top of the resin layer. Next, the granulate material is applied in the form of a layer of granulate material 5, which not only should be applied as carefully as possible, but also sufficiently quickly to allow the polymerization of the resin and prevent the inhibition of polymerization by contact with the ambient air 2. Failing this will result in a very sticky and fragile surface. The onset polymerization begins at the interface between the surroundings and the resin and forms a hardening layer 6.

EXAMPLES 1 TO 9

[0151] The starting granulated raw materials of examples 1 to 7 (see table 1 below) are preheated under continuous stirring from 60° C. to 100° C. Once this temperature had been reached, the hydrophobic additive (if present in the formulation) was added. Next, still under continuous stirring, the component C1 was added. Finally, still under continuous stirring, a desiccant was added. This mixture was cooled to room temperature under continuous stirring.

[0152] The granulated raw materials of example 8 are not preheated to avoid premature decomposing of the initiator into radicals. Next, component C1 (in this case the initiator) was added under continuous stirring. The water glass binder was then added, still under continuous stirring. The mixture continued to be stirred until the most of water was evaporated and the granulate materials no longer stuck together.

[0153] The granulated raw materials of example 9 are mixed together at room temperature until a homogenous mixture is obtained.

[0154] Their can be noticed that in case no hydrophobic additive is used as in example 6 and as such a lower contact angle is obtained, the amount of DHEPT required in order to obtain a functional granulate is significantly higher than in examples 1 to 5

TABLE-US-00001 TABLE 1 Hydrophobic Contact Granulated raw materials additive C1: accelerator or initiator Desiccant angle* Binder Ex. 1 Quartz gravel with 90% of all granule 0.5 m % Paraffin with 0.4 m % DHEPT (N,N-bis (2- 0.7 m % >50° / diameters comprised between 0.4 a melting point of hydroxyethyl)-p-toluidine) Fumed silica and 0.8 mm 52° C. Ex. 2 Quartz gravel with 90% of all granule 0.24 m % Paraffin with 0.24 m % DHEPT (N,N-bis (2- 0.24 m % >50° / diameters comprised between 0.8 a melting point of hydroxyethyl)-p-toluidine) Fumed silica and 1.2 mm 52° C. Ex. 3 Epoxy colored Quartz gravel with 0.5 m % Paraffin with 0.4 m % DHEPT (N,N-bis (2- 0.7 m % >50° / 90% of all granule diameters a melting point of hydroxyethyl)-p-toluidine) Fumed silica comprised between 0.4 and 0.8 mm 52° C. Ex. 4 Quartz gravel with 90% of all granule 0.5 m % Paraffin with 0.8 m % PTE (para-Toluidine, 0.7 m % >50° / diameters comprised between 0.4 a melting point of Ethoxylated) Fumed silica and 0.8 mm 52° C. Ex. 5 Silicon carbide with 90% of all 0.5 m % Paraffin with 0.4 m % DHEPT (N,N-bis (2- 0.7 m % >50° / granule diameters comprised a melting point of hydroxyethyl)-p-toluidine) Fumed silica between 0.6 and 1 mm 52° C. Ex. 6 Quartz gravel with 90% of all granule / 3 m % DHEPT 0.7 m %  <1° / diameters comprised between 0.4 Fumed silica and 0.8 mm Ex. 7 Ultra-high density polyethylene / 1.58 m % DHEPT (N,N-bis (2- 0.2 m % >35° / granules with 90% of all granule hydroxyethyl)-p-toluidine) Fumed silica diameters comprised between 0.4 and 0.8 mm Ex. 8 Quartz gravel with 90% of all granule / 2,3 m % /  <1° 1.5 m % diameters comprised between 0.4 component containing water- and 0.8 mm 50 m % Dibenzoyl peroxide glass with dicyclohexyl solution phthalate and silica) (CAS 1344- 09-8) Ex. 9 80 m % granulate materials from ex. 3 + / / / / 20 m % Epoxy colored Quartz gravel with 90% of all granule diameters comprised between 0.4 and 0.8 mm *measured according to DIN 55660-2: 2011-12

EXAMPLES 10-16: FLOOR COATING FORMULATION KIT FOR USE AT 20° C.

[0155] 6 floor coating formulation kits were prepared. They comprise 4 components: [0156] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0157] 98.9 m % DPGDA [0158] 0.1 m % accelerator, being DHEPT [0159] 0.5 m % CABOSIL TS 720 (anti deposit additive) [0160] b) a filler: [0161] 300 m %, relative to the liquid resin, of quartz flour M4 from the company Sibelco [0162] c) an initiator: [0163] 4 m %, relative to the liquid resin, containing 50 m % Dibenzoyl peroxide with dicyclophexyl phthalate and silica) [0164] d) a specific granulate material according to examples 1-5 and according to example 9. The granulate material was used at 3 kg/m.sup.2 of floor surface.

[0165] The floor coat was prepared according to the process of the invention. Specifically, a mixture was first made of the following components: 5 kg of component a, 15 kg component b and 0.2 kg of component C. This was carried out by adding those components together in a bucket and stirring for 2 min using a power drill with a paint stirrer. Next, this mixture was poured onto the surface to be coated, in this case a concrete floor to which an epoxy primer had already been applied. Then, the mixture was smoothed within 15 min using a skimmer, ensuring that the total thickness of the applied layer was between 3 and 4 mm. Next, the mixture was manually covered (filled in) with component D, with 3 kg of granulate material per m.sup.2 of coating surface being applied during covering (filling in). This is more than sufficient to ensure that no non-covered portions remain that are larger than 1 mm.sup.2. After a 1 hour wait, the coating was found to be cured with no sticky surface. Finally, any remaining loose granulate materials (the excess) are removed with a brush or vacuum cleaner. If so desired, the coating can be further finished with a topcoat; in this case, a topcoat based on epoxy resin was used.

EXAMPLES 17-22.—FLOOR COATING FORMULATION FOR USE AT 20° C.

[0166] 6 floor coating formulation kits were prepared. They comprise 4 components: [0167] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0168] i. 98.9 m % BDGMA [0169] i. 0.1 m % accelerator, being DHEPT [0170] b. 0.5 m % CABOSIL TS 720 (anti deposit additive) [0171] b) a filler: 300 m %, relative to the liquid resin, of quartz flour M4 from the company Sibelco [0172] c) an initiator: 4 m %, relative to the liquid resin, containing 50 m % Dibenzoyl peroxide with dicyclohexyl phthalate and silica) [0173] d) a specific granulate material according to examples 1-5 and according to example 9. The granulate material was used at 3 kg/m.sup.2 of floor surface

[0174] The floor coat was prepared according to the process of the invention to a layer thickness of 4 mm and curing in less than 60 min, with no sticky surface

EXAMPLE 23-29.—FLOOR COATING FORMULATION FOR USE AT 20° C.

[0175] 6 floor coating formulation kits were prepared. They comprise 4 components: [0176] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0177] 64.9 m % DPGDA, [0178] 20 m % HEMA, [0179] 15 m % polyvinyl acetate (low molecular mass), [0180] 0.1 m % DHEPT and [0181] 0.3 m % CABOSIL TS 720 (anti deposit additive) [0182] b) a filler: 200 m %, relative to the liquid resin, of quartz flour M4 from the company Sibelco [0183] c) an initiator: 4 m %, relative to the liquid resin, containing 50 m % Dibenzoyl peroxide with dicyclophexyl phthalate and silica [0184] d) a specific granulate material according to examples 1-5 and according to example 9. The granulate material was used at 3 kg/m.sup.2 of floor surface.

[0185] The floor coat was prepared according to the process of the invention to a layer thickness of 4 mm and curing in less than 60 min, with no sticky surface

EXAMPLES 30-36.—FLOOR COATING FORMULATION FOR USE AT 20° C.

[0186] 6 floor coating formulation kits were prepared. They comprise 4 components: [0187] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0188] 49.3 m % HEMA, [0189] 40 m % eberyl 230 from supplier Allnex (PU-acrylate) [0190] 10 m % lauryl methacrylate, [0191] 0.2 m % DHEPT [0192] 0.5 m % CABOSIL TS 720 (anti deposit additive) [0193] b) a filler: 200 m %, relative to the liquid resin, of quartz flour M4 from the company Sibelco [0194] c) an initiator: 4 m %, relative to the liquid resin, containing 50 m % Dibenzoyl peroxide with dicydohexyl phthalate and silica [0195] d) a specific granulate material according to examples 1-5 and according to example 9. The granulate material was used at 3 kg/m.sup.2 of floor surface.

[0196] The floor coat was prepared according to the process of the invention to a layer thickness of 4 mm and curing in less than 60 min, with no sticky surface

EXAMPLES 37-43.—FLOOR COATING FORMULATION FOR USE AT 20° C.

[0197] 6 floor coating formulation kits were prepared. They comprise 4 components: [0198] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0199] 48.9 m % HEMA [0200] 50 m % BDGMA [0201] 0.1 m % DHEPT [0202] 0.5 m % CABOSIL TS 720 (anti deposit additive) [0203] b) a filler: 200 m %, relative to the liquid resin, of quartz flour M4 from the company Sibelco [0204] c) an initiator: 4 m %, relative to the liquid resin, containing 50 m Dibenzoyl peroxide with dicyclohexyl phthalate and silica [0205] d) a specific granulate material according to examples 1-5 and according to example 9. The granulate material was used at 3 kg/m.sup.2 of floor surface.

[0206] The floor coat was prepared according to the process of the invention to a layer thickness of 4 mm and curing in less than 60 min, with no sticky surface

EXAMPLES 44-50.—FLOOR COATING FORMULATION FOR USE AT 20° C.

[0207] 6 floor coating formulation kits were prepared. They comprise 4 components: [0208] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0209] 59.8 m % DPGDA [0210] 40 m % polyvinyl acetate, characterized by a molecular weight Mw of 150 000 0.2 m % DHEPT [0211] b) a filler: 100 m %, relative to the liquid resin, of quartz flour M4 from the company Sibelco [0212] c) an initiator: 8 m %, relative to the liquid resin, containing 50 m % Dibenzoyl peroxide with dicyclohexyl phthalate and silica [0213] d) a specific granulate material according to examples 1-5 and according to example 9. The granulate material was used at 3 kg/m.sup.2 of floor surface.

[0214] The floor coat was prepared according to the process of the invention to a layer thickness of 4 mm and curing in less than 30 min, with no sticky surface

EXAMPLES 51-59.—FLOOR COATING FORMULATION FOR USE AT 20° C.

[0215] 6 floor coating formulation kits were prepared. They comprise 3 components:

[0216] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0217] 59.8 m % DPGDA [0218] 40 m % polyvinyl acetate, characterized by a molecular weight Mw of 150 000 [0219] 0.2 m % DHEPT

[0220] b) an initiator: 8 m %, relative to the liquid resin, containing 50 m % Dibenzoyl peroxide with dicyclohexyl phthalate and silica

[0221] c) a specific granulate material according to examples 1-7 and according to example 9. The granulate material was used at 3 kg/m.sup.2 of floor surface.

[0222] The floor coat was prepared according to the process of the invention to a layer thickness of 1 mm and curing in less than 30 min, with no sticky surface

EXAMPLE 60.—FLOOR COATING FORMULATION FOR USE AT 20° C.

[0223] A floor coating formulation kit was prepared. It comprise 4 components: [0224] a) a liquid resin, prepared by stirring until a homogenous mixture is obtained: [0225] 55.2 m % DPGDA [0226] 40 m % LMA [0227] 4.8 m % DHEPT [0228] b) a filler: 250 m %, relative to the liquid resin, of quartz flour M4 from the company Sibelco [0229] c) an initiator: 3.4 m % tov the mass of the liquid resin lauryl peroxide [0230] d) granulate material according to example 8 and was used at 3 kg/m.sup.2 of floor surface.

[0231] The floor coat was prepared according to the process of the invention to a layer thickness of 4 mm and curing in less than 60 min, with no sticky surface