Product for the treatment and protection of mineral surfaces

Abstract

The invention relates to a mineral surface treatment and protection composition, the composition comprising, relative to its total weight, the following components: (a) 45 to 55% by weight of a urethane-modified alkyd emulsion, preferably a self-emulsified urethane-modified alkyd emulsion without surfactant, particularly preferably a self-emulsified urethane-modified alkyd emulsion without surfactant comprising 40 to 60% by weight of oil as a modifying agent relative to the urethane-modified alkyd emulsion, (b) 1 to 4% by weight of one or more organic powdered mattifying agents, preferably one or more powdered thermosetting material mattifying agents, (c) 0.01 to 0.2% by weight of a water-soluble, ethoxylated, nonionic fluorinated surfactant, preferably based on short-chain molecules containing 6 fluorinated carbon atoms, and (d) water.

Description

Title of the invention: Product for the treatment and protection of mineral surfaces technical field

[0001] The present invention relates to a product for the treatment and protection of mineral surfaces. State of the art

[0002] Although there are many products for treating or even protecting the surface of mineral materials, particularly in the field of construction, many of these only provide a partial solution, that is to say, they do not allow the treatment of all surfaces (at least with the same performance) or they only protect surfaces against certain causes of soiling or visual or structural degradation.

[0003] Moreover, the yield of conventional products expressed in m2 per quantity of product is often modest, for example well below 10 m2 / l.

[0004] Finally, all too often these products are largely derived from fossil raw materials, with the associated environmental and health impacts. Object of the invention

[0005] An object of the present invention is therefore to propose a mineral surface treatment and protection product which has good general performance in terms of stain protection, which is suitable for a large number of different mineral surfaces, such as stone, concrete, artificial stone, etc., which allows good yield in application and which is preferably mostly of renewable origin, respectively bio-based. General description of the invention

[0006] In order to solve the problem mentioned above, the present invention proposes, in a first aspect, a composition for the treatment and protection of mineral surfaces, the composition comprising, in relation to its total weight, the following components:

[0007] a) 45 to 55% by weight of a urethane-modified alkyd emulsion, preferably a self-emulsified urethane-modified alkyd emulsion without surfactant, particularly preferably a self-emulsified urethane-modified alkyd emulsion without surfactant comprising 40 to 60% by weight of oil as a modifying agent relative to the urethane-modified alkyd emulsion,

[0008] b) 1 to 4% by weight of one or more organic mattifying agents in powder form, preferably one or more mattifying agents in powder form of thermosetting material,

[0009] c) 0.01 to 0.2% by weight of a water-soluble, ethoxylated, nonionic fluorinated surfactant, preferably based on short-chain molecules containing 6 fluorinated carbon atoms, and

[0010] d) water, up to 100% by weight of the composition.

[0011] Surprisingly, although the composition can be used on a wide variety of mineral surfaces, such as stone, concrete, artificial stone, etc., the inventor has demonstrated significantly superior effectiveness in terms of stain-resistant properties. Unlike most conventional mineral surface treatment and protection compositions, which generally have a dry extract content between 2 and 10% by weight, the compositions according to the invention have a considerably higher dry extract content. In fact, the compositions according to the invention generally have a dry extract content exceeding 40% by weight, preferably exceeding 45% by weight, and particularly exceeding 50% by weight.

[0012] In addition, the aesthetic appearance after treatment of mineral surfaces is generally preserved, or even improved by the rather semi-film-forming properties giving a colorless matte, or even satin, appearance.

[0013] After application and drying, the combination of components a) and component b), i.e. the combination of the urethane-modified alkyd emulsion and the mattifying agent contained in the compositions, in addition to the interesting effect on the aesthetic appearance, also offers an advantageous anti-slip effect to the treated mineral surfaces.

[0014] Advantageously, the composition according to the invention comprises 48 to 52% by weight of component a), 1.5 to 2.5% by weight of component b) and 0.07 to 0.13% by weight of component c).

[0015] A significant advantage of the present compositions is their high application yield compared to known mineral surface treatment and protection compositions. The yield is generally at least 5 m² / l, preferably at least 10 m² / l, and in particular up to 20 m² / l or even more.

[0016] Another notable advantage of the compositions of the present invention is that their components can be largely of renewable origin. Indeed, the compositions according to the invention are generally bio-based at more than 35% by weight, preferably at more than 40% by weight, in particular at more than 45% by weight, or even at more than 50% by weight, measured on the dry extract.

[0017] Furthermore, after application and drying, the compositions of the invention are considered as a sacrificial anti-graffiti coating which dissolves upon cleaning with the sprayed graffiti.

[0018] Finally, the compositions according to the invention exhibit excellent abrasion resistance and, above all, excellent stain resistance even after abrasion.

[0019] Component a), that is, the urethane-modified alkyd emulsion, is Preferably a self-emulsified urethane-modified alkyd emulsion without surfactant. Advantageously, this will be a self-emulsified urethane-modified alkyd emulsion without surfactant comprising 40 to 60% by weight of oil as a modifying agent relative to the urethane-modified alkyd emulsion, for example compositions such as SYNAQUA® 2070 or SYNAQUA® 4856 offered by ARKEMA, or mixtures thereof.

[0020] Component b) may comprise or consist of one or more organic powdered matting agents, preferably one or more powdered thermosetting material matting agents, in this case poly-condensed plastic. The d50 particle size of these powders is preferably between 2 and 12 µm, more preferably between 3 and 10 µm, in particular between 3.5 and 8 µm. The d90 particle size of these powders is preferably between 4 and 20 µm, more preferably between 5 and 18 µm, in particular between 6 and 15 µm. Particularly suitable examples of components b) are Deuteron® MK, Deuteron® MK-F, and Deuteron® MK-F6 from DEUTERON GmbH, 28832 Achim, Germany, in particular Deuteron® MK.

[0021] [Tables 1] Deuteron® MK MK-F MK-F6 Bulk density approx. 150 150 120 g / L Density approx. 1.4 1.4 1.4 Particle size d50 approx. 6.3 4.6 3.5 µm Particle size d90 approx. 13.8 10.6 6.5 µm Appearance Fine white powder

[0022] As component c), at least one water-soluble, ethoxylated, nonionic fluorinated surfactant is used, preferably based on short-chain molecules containing 6 (per)fluorinated carbon atoms. These components are nonionic. Examples of such components include Hexafor 672, Hexafor® 675, Hexafor® 676, Hexafor® 678, or Hexafor® 678-W from Maflon, 24060 Castelli Calepio, Bergamo, Italy, in particular Hexafor® 678 or Hexafor® 678-W.

[0023] A second aspect of the invention relates to a method for treating and protecting mineral surfaces, in which a mineral surface treatment and protection composition according to the invention is applied to a mineral surface to be protected and preferably allowed to dry for at least 15 to 30 minutes, for example, for 20 minutes at 20°C. Good effectiveness will generally be achieved within 48 hours, and full effectiveness will be obtained after 1 to 2 weeks. The application can be carried out in a manner known per se, but it is generally done with a roller or a brush, preferably with a roller. Brief description of the drawings

[0024] Other features and characteristics of the invention will become apparent from the detailed description of some advantageous examples presented below, by way of illustration, with reference to the attached photos.

[0025] Figures [1] and 2 show a stain test without and after abrasion of the support. Examples

[0026] The mineral surface treatment and protection compositions according to the invention have been subjected to various tests in order to evaluate their properties.

[0027] In this case, they are characterized by the following properties: • Superior stain-removing effectiveness compared to all other tested products • Aesthetic appearance: colorless matte - very light satin • Very good yield 1 1 = 5 to 20 m2 • Universal product: stone, concrete, artificial stone, ... • Preferably bio-based, at least approximately 50%, or even approximately 53%, on the dry extract (excluding water). With water, generally over 70% • Very high content of active ingredients: approximately 50% • Anti-slip properties • Very good abrasion resistance • Application by roller • Sacrificial anti-graffiti

[0028] Spot tests

[0029] In order to test the stain-resistant effectiveness of the compositions according to the invention, drops of oil, water and red wine were deposited and left on polished marble, raw marble, honed granite, raw granite, honed limestone and raw limestone supports for one day and evaluations (1 - very visible stains to 5 - no visible stains) were carried out at the times indicated in the following table:

[0030] [Tables2] SUPPORT Polished marble Raw marble Honed granite Raw granite Honed limestone Raw limestone OIL 24H 5 5 5 5 5 5 4H 5 5 5 5 5 5 1H 5 5 5 5 5 5 15' 5 5 5 5 5 5 5 5 5 1' 5 5 5 5 5 5 WATER 24H 5 5 5 5 5 5 4H 5 5 5 5 5 5 1H 5 5 5 5 5 5 15' 5 5 5 5 5 5 5 5 5 5 1' 5 5 5 5 5 5 5 WINE 24H 5 4 5 5 5 5 4H 5 5 5 5 5 5 1H 5 5 5 5 5 5 15' 5 5 5 5 5 5 5' 5 5 5 5 5 5 1' 5 5 5 5 5 5

[0031] It is observed that all the tests were successful and the compositions according to the invention protect the different types of supports very effectively.

[0032] Comparative pendulum sliding measurements

[0033] For this test, which is carried out according to standard EN 13036-4:2011, the pendulum test method is used. This simple device reliably and accurately reproduces the coefficient of dynamic friction (CFD) of a heel on a floor surface. A person's heel is the part of the foot that begins to slide first in the most situations involving slipping on the ground.

[0034] The device is actuated by a swinging arm that rubs against a flat surface. The swinging arm is fitted with a rubber pad that strikes and slides against the surface over a predefined contact distance.

[0035] The arm is placed in a horizontal position with a rod. Once released, it swings and as soon as it strikes the surface, the friction decelerates the arm, which moves a certain distance and places the rod on a measuring scale. The more slippery the surface, the farther the swinging arm will travel.

[0036] [Tables3] Average pendulum slip values ​​SMOOTH SURFACE LIMESTONE Dry sample Wet sample Untreated sample 18 1 Sample according to the invention 28 18 Average pendulum slip values ​​RAW SURFACE LIMESTONE Dry sample Wet sample Untreated sample 24 0 Sample according to the invention 27 22

[0037] It is observed that the results after treatment with a composition according to the invention are generally good, with an acceptable slip potential, and significantly better than in the absence of treatment.

[0038] Stain tests after abrasion

[0039] In order to test the stain-resistant effectiveness of the compositions according to the invention even after a certain time after application, i.e. after a certain amount of wear by abrasion, drops of oil, water and red wine were deposited and left on polished marble, raw marble, honed granite, raw granite, honed limestone and raw limestone supports for one day and evaluations (1 - very visible stains to 5 - no visible stains) were carried out at the times indicated in the following table:

[0040] [Tables4] STAINS EXPOSURE BEFORE ABRASION ABRASION PAD TRAFFIC 1000 cycles ABRASION CLEANING BRUSH 200 cycles WATER 4h 5 5 1h 5 5 15 min 5 5 5 min 5 5 OIL 24h 5 5 4h 5 5 1h 5 5 15 min 5 5 5 min 5 5 WINE 24h 5 5 4h 5 5 1h 5 5* 15 min 5 5* 5 min 5 5* *very slight halo

[0041] The application is illustrated in [Fig.1] on a section without abrasion (in the center), with abrasion with the pad (on the left) and with abrasion with the brush (on the right) and [Fig.2] shows the result after 24 hours.

[0042] It is observed that all the tests were successful and the compositions according to the invention protect very effectively even after abrasion tests.

[0043] Emission of volatile organic compounds (VOCs)

[0044] The test chamber is made of stainless steel. A multi-stage air cleaning is carried out before loading the chamber, and a dry run of the empty chamber is performed.

[0045] The chamber operating parameters are as described in the test method section. (EN 16516, ISO 16000-9, internal method no.: 71M549811).

[0046] All test results are calculated as specific emission rate and as concentration in air extrapolated in the European reference room (EN 16516, AgBB, EMICODE, Ml and Indoor Air Comfort).

[0047] Volatile organic compound emissions are tested by collecting an air sample from the outlet of the test chamber through Tenax TA tubes after the specified storage time in the ventilated test chamber. The analysis is performed by ATD-GC / MS using an HP-5 column (30 m, 0.25 mm ID, 0.25 µm film).

[0048] The eight substances are identified if present. Quantification above 2 pg / m3 is performed using the TIC signal and authentic response factors.

[0049] Total volatile organic compounds (TVOCs) are calculated by adding together all individual VOCs with a concentration > 2 pg / m3. TVOCs are expressed in toluene equivalents as defined in EN 16516 and similar to ISO 16000-6.

[0050] Preparation of the test sample

[0051] The sample was homogenized and applied to a glass plate.

[0052] Number of coats: 2; quantity of application, g / m2: 100; drying time, min: 20.

[0053] Comparison with the limit values ​​of French regulations concerning VOCs

[0054] [Tables5] CAS No. Conc. at 28 days of the sample according to the invention pg / m³ Class C pg / m³ Class B pg / m³ Class A pg / m³ Class A+ pg / m³ TCOV - 240 >2000 <2000 < 1500 < 1000 Formaldehyde 50-00-0 28 > 120 < 120 <60 < 10 Acetaldehyde 75-07-0 <3 >400 <400 <300 <200 Toluene 108-88-3 <2 >600 <600 <450 <300 Tetrachloroethylene 127-18-4 <2 >500 <500 <350 <250 Ethylbenzene 100-41-4 <2 > 1500 < 1500 < 1000 <750 Xylene 1330-20-7 <2 >400 <400 <300 <200 Styrene 100-42-5 <2 >500 <500 <350 <250 2-Butoxyethanol 111-76-2 <2 >2000 <2000 < 1500 < 1000 1,2,4-Trimethylbenzene 95-63-6 <2 >2000 <2000 < 1500 < 1000 1,4-Dichlorobenzene 106-46-7 <2 > 120 < 120 <90 <60

[0055] As can be seen, the level of volatile organic compound emissions is very low and the products according to the invention meet at least the standards of class A for the French labeling of volatile pollutant emissions from construction products.

[0056] Intrinsic aerobic biodegradability: Dissolved organic carbon (DOC) disappearance test (ZAHN-WELLENS) - OECD 302 B -

[0057] Principle: A mixture containing the test substance, mineral nutrients, and a relatively large proportion of activated sludge in aqueous medium is agitated and aerated at 20-25°C in the dark or under diffuse light for up to 28 days. The biodegradation process is monitored by measuring the Dissolved Organic Carbon over time.

[0058] Inoculum: Activated sludge sampled at the Rouen wastewater treatment plant on 15 / 10 / 2021. Bacterial flocs were recovered after centrifugation and resuspension in the test medium. The ratio between the inoculum (as TSS) and the test substance (as COD) is between 2.5:1 and 4.0:1 in the test bottles.

[0059] Sample: according to the present invention

[0060] - Storage method: room temperature

[0061] - Method of preparing test solutions: dilutions.

[0062] Results: Percentage biodegradation rate as a function of time (experimental data):

[0063] [Tableauxô] Day 0 1 4 7 14 20 27 28 Plateau Control Reference 0 < 10 16.1 85.9 97.4 97.3 100 100 100% E1 according to the invention 0 50.9 91.2 93.4 97.6 97.8 96.9 96.3 97% E2 according to the invention 0 50.2 91.5 93.5 97.5 97.8 97.3 97.3 97% Toxicity control (TOX) 0 22.6 51.2 94.8 99.1 99.1 98.8 98.9 99% Abiotic control (ABIO) 0 < 10 < 10 < 10 < 10 < 10 < 10 < 10 < 10%

[0064] El and E2 correspond to two test concentrations meeting the test start criteria (replicates).

[0065] The tests were therefore carried out in duplicate with differences in results of less than 20%, in accordance with the validity criteria set by the OECD guidelines. The toxicity control (TOX) demonstrates biodegradability greater than 35%, indicating the absence of toxicity of the sample towards the inoculum. The abiotic control (ABIO) shows no significant abiotic degradation of the sample under the test conditions (<10%).

[0066] OECD guidelines have established a biodegradation threshold of 20% above which a substance demonstrates intrinsic primary biodegradability and a threshold of 70% above which a substance demonstrates intrinsic ultimate biodegradability. For this analysis, the test substance exhibits 90% to 100% biodegradation within 28 days.

[0067] Samples El and E2 using compositions according to the invention demonstrated "intrinsic ultimate biodegradability without pre-adaptation" (and therefore also "intrinsic primary biodegradability") according to OECD criteria extrapolated to a formulated or mixed product.

[0068] In conclusion, the mineral surface treatment and protection compositions according to the present invention exhibit superior stain-resistant efficacy, good anti-slip properties, very good abrasion resistance, very low level of volatile organic compound emissions and excellent biodegradability.

Claims

Demands

1. A mineral surface treatment and protection composition, the composition comprising, relative to its total weight, the following components: a) 45 to 55% by weight of a self-emulsified, surfactant-free, self-emulsified urethane-modified alkyd emulsion comprising 40 to 60% by weight of oil as a modifying agent relative to the urethane-modified alkyd emulsion, b) 1 to 4% by weight of one or more mattifying agents in powdered thermosetting material, c) 0.01 to 0.2% by weight of a water-soluble, ethoxylated, nonionic fluorinated surfactant, preferably based on short-chain molecules containing 6 fluorinated carbon atoms, and d) water, up to 100% by weight of the composition.

2. Composition according to claim 1, comprising 48 to 52% by weight of component a), 1.5 to 2.5% by weight of component b) and 0.07 to 0.13% by weight of component c).

3. Composition according to claim 1 or 2, having a dry extract greater than 40% by weight, preferably greater than 45% by weight, in particular greater than 50% by weight.

4. Composition according to any one of claims 1 to 3, which is bio-based at more than 35% by weight, preferably at more than 40% by weight, in particular at more than 50% by weight, measured on the dry extract.

5. A method for treating and protecting mineral surfaces, wherein a mineral surface treatment and protection composition according to any one of claims 1 to 4 is applied to a mineral surface to be protected and preferably allowed to dry for at least 15 to 30 minutes.

6. A method for treating and protecting mineral surfaces according to claim 5, wherein the application is done by roller or brush, preferably by roller.