Mineral surface treatment and protection product

Abstract

The invention relates to a composition for treating and protecting mineral surfaces, 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 surfactant-free self-emulsified urethane-modified alkyd emulsion, particularly preferably a 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 powdered organic matting agents, preferably one or more powdered thermoset material matting agents, (c) 0.01 to 0.2% by weight of a water-soluble, ethoxylated, non-ionic fluorinated surfactant, preferably based on short-chain molecules containing 6 carbon atoms fluorinated, and (d) water.

Description

Title of the invention: Product for treating and protecting mineral surfaces Technical field

[0001] The present invention relates to a product for treating and protecting 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, i.e. they do not allow all surfaces to be treated (at least with the same performance) or they only protect surfaces against certain causes of soiling or visual or structural degradation.

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

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

[0005] An object of the present invention is therefore to provide a product for treating and protecting mineral surfaces which has good general performance in terms of anti-stain protection, which is suitable for a large number of different mineral surfaces, such as stone, concrete, artificial stone, etc., which allows good application performance and which is preferably predominantly of renewable origin, respectively biosourced. General description of the invention

[0006] In order to solve the above-mentioned problem, the present invention provides in a first aspect, a composition for treating and protecting mineral surfaces, the composition comprising, relative to its total weight, the following components:

[0007] a) 45 to 55% by weight of a urethane-modified alkyd emulsion, preferably a surfactant-free self-emulsified urethane-modified alkyd emulsion, particularly preferably a surfactant-free self-emulsified urethane-modified alkyd emulsion comprising 40 to 60% by weight of oil as modifying agent relative to the urethane-modified alkyd emulsion,

[0008] b) 1 to 4% by weight of one or more powdered organic matting agents, preferably one or more powdered thermoset material matting agents,

[0009] c) 0.01 to 0.2% by weight of a water-soluble ethoxylated non-ionic 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 large number of different mineral surfaces, such as stone, concrete, artificial stone, etc., the inventor was able to demonstrate a much higher effectiveness in terms of anti-stain properties. Unlike most conventional mineral surface treatment and protection compositions having a dry extract generally between 2 and 10% by weight, the compositions according to the invention have a significantly higher dry extract. Indeed, the compositions according to the invention generally have a dry extract greater than 40% by weight, preferably greater than 45% by weight, or even in particular greater than 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, matt, 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 matting agent contained in the compositions, in addition to the interesting effect on the aesthetic appearance, even 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] An important advantage of the present compositions is that they have a high application yield compared to known mineral surface treatment and protection compositions. The application yield, i.e. the effective yield for a complete application of the composition in two layers, is generally at least 5 m2 / l, preferably at least 10 m2 / l, 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, the definitions concerning renewable origin being those of the standard EN 16575:2014. Indeed, the compositions according to the invention are generally biosourced at more than 35% by weight, preferably more than 40% by weight, in particular more than 45% by weight, or even more than 50% by weight, measured on the dry extract on the basis of a balance of biosourced materials and non-biosourced materials [mass of biosourced materials / (mass of biosourced and non-biosourced materials) expressed in % by weight]. The determination of the biosourced content of the dry extract can be done in particular using the method based on the material balance according to EN 16785-2:2018. Alternatively, the bio-based carbon content according to EN 16640:2017 of the dry extract is generally more than 32%, preferably more than 37%, in particular more than 42%, or even more than 47%.

[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), i.e. the urethane-modified alkyd emulsion, is preferably a self-emulsified, surfactant-free urethane-modified alkyd emulsion. Advantageously, it will be a self-emulsified, surfactant-free urethane-modified alkyd emulsion comprising from 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 provided by ARKEMA, or mixtures thereof.

[0020] Component b) may comprise or consist of one or more powdered organic matting agents, preferably one or more matting agents made of powdered thermoset material, in this case polycondensed plastic. The particle size d50 of these powders is preferably between 2 and 12 pm, more preferably between 3 and 10 pm, in particular between 3.5 and 8 pm. The particle size d90 of these powders is preferably between 4 and 20 pm, more preferably between 5 and 18 pm, in particular between 6 and 15 pm. 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. [Tables 1] ]Deuteron® MK MK-F MK-F6 Bulk density approx. 150 150 120 g / 1 Density approx. 1.4 1.4 1.4 Particle size d50 approx. 6.3 4.6 3.5 pm Particle size d90 approx. 13.8 10.6 6.5 pm Appearance Fine white powder

[0021] As component c), at least one water-soluble, ethoxylated, non-ionic fluorinated surfactant is used, preferably based on short-chain molecules containing 6 (per)fluorinated carbon atoms. These components are generally non-ionic. 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.

[0022] A second aspect of the invention relates to a method for treating and protecting mineral surfaces, in which a composition for treating and protecting mineral surfaces according to the invention is applied to a mineral surface to be protected and allowed to dry preferably for at least 15 minutes 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 is generally carried out by roller or brush, preferably by roller. Brief description of the drawings

[0023] Other features and characteristics of the invention will emerge from the detailed description of some advantageous examples presented below, by way of illustration, with reference to the attached photos.

[0024] [Fig.l] and 2 show a stain test without and after abrasion of the support. Examples

[0025] The compositions for treating and protecting mineral surfaces according to the invention were subjected to various tests in order to evaluate their properties.

[0026] In this case, they are characterized by the following properties: • Superior stain-repellent effectiveness to all products tested • Colorless matte aesthetic appearance - very light satin • Very good application yield: 1 1 = 5 to 20 m2 (two coats) • Universal product: stone, concrete, artificial stone, etc. • Bio-sourced preferably at least about 50% by weight, or even about 53% by weight, on the dry extract (excluding water). With water, generally more than 70% by weight • Very high content of active ingredients: approximately 50% • Very high dry extract approximately 23 to 24% • Anti-slip properties • Very good abrasion resistance • Roller application • Sacrificial anti-graffiti Spot tests

[0027] In order to test the anti-stain effectiveness of the compositions according to the invention, drops of oil, water and red wine were placed and left on marble supports. polished, rough marble, honed granite, rough granite, honed limestone and rough limestone, 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: [Table2] 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 5 5 5 5 5 r 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 5 5 5 5 1' 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

[0028] It is noted that all the tests were successful and the compositions according to the invention protect the different types of supports very effectively.

[0029] Comparative measurements of pendulum slippage

[0030] For this test, which is carried out according to standard EN 13036-4:2011, the method of The pendulum test, which is a simple device that reliably and accurately reproduces the dynamic coefficient of friction (DCF) of a heel on a floor surface. A person's heel is the part of the foot that begins to slide first in most slip-on situations.

[0031] The device is operated by a swing arm which rubs on a flat surface. The swing arm is mounted with a rubber pad which strikes and slides on the surface according to a predefined contact distance.

[0032] The arm is placed in a horizontal position with a stick. Once released, it swings and as soon as it hits the surface, the friction decelerates the arm which moves a certain distance and places the stick on a measuring scale. The more slippery the surface, the further the swinging arm will go. [Tables 3] Average pendulum slipperiness values ​​SMOOTH SURFACE LIMESTONE Dry sample Wet sample Untreated sample 18 1 Sample according to the invention 28 18 Average pendulum slipperiness values ​​ROUGH SURFACE LIMESTONE Dry sample Wet sample Untreated sample 24 0 Sample according to the invention 27 22

[0033] It is noted 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. Stain tests after abrasion

[0034] In order to test the anti-stain effectiveness of the compositions according to the invention even after a certain time after application, therefore after a certain wear by abrasion, drops of oil, water and red wine were deposited and left on supports made of polished marble, rough marble, honed granite, rough granite, honed limestone and rough limestone, 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: [Tables 4] STAINS EXPOSURE BEFORE ABRASION ABRASION PAD TRAFFIC 1000 cycles ABRASION BRUSH CLEANING 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

[0035] The application is illustrated in [Fig.l] on a section without abrasion (center), with pad abrasion (left) and with brush abrasion (right) and [Fig.2] shows the result after 24 hours.

[0036] It is noted that all the tests were successful and the compositions according to the invention protect very effectively even after the abrasion tests.

[0037] Emission of volatile organic compounds (VOCs)

[0038] The test chamber is made of stainless steel. A multi-stage air cleaning is performed before loading the chamber, and a blank check of the empty chamber is performed.

[0039] The operating parameters of the chamber are as described in the test method section. (EN 16516, ISO 16000-9, internal method no.: 71M549811).

[0040] All test results are calculated as specific emission rate and as air concentration extrapolated to the European reference room (EN 16516, AgBB, EMICODE, Ml and Indoor Air Comfort).

[0041] Volatile organic compound emissions are tested by taking an air sample from the test chamber outlet through Tenax TA tubes after the specified storage time in the ventilated test chamber. Analysis is performed by ATD-GC / MS using an HP-5 column (30 m, 0.25 mm ID, 0.25 pm film).

[0042] The eight substances are identified if present. Quantification above 2 pg / m3 is performed using the TIC signal and authentic response factors.

[0043] Total volatile organic compounds (TVOC) are calculated by adding all individual VOCs with a concentration > 2 pg / m3. TVOC is expressed in toluene equivalents as defined in EN 16516 and similar to ISO 16000-6. Preparation of the test sample

[0044] The sample was homogenized and applied to a glass plate.

[0045] Number of coats: 2; application quantity, g / m2: 100; drying time, min: 20.

[0046] Comparison with the limit values ​​of French regulations on VOCs [Tables 5] 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 TVOC - 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

[0047] As can be seen, the level of emissions of volatile organic compounds is very low and the products according to the invention meet at least the class A standards for French labeling of volatile pollutant emissions from construction products.

[0048] Aerobic intrinsic biodegradability: Dissolved organic carbon (DOC) disappearance test (ZAHN-WELLENS) - OECD 302 B -

[0049] Principle: A mixture containing the test substance, mineral nutrients and a relatively large proportion of activated sludge in an aqueous medium is stirred and aerated at 20-25°C in the dark or under diffused light for up to 28 days. The biodegradation process is monitored by measuring the Dissolved Organic Carbon over time.

[0050] Inoculum: Activated sludge collected from the Rouen WWTP on 10 / 15 / 2021. Recovery of bacterial flocs after centrifugation and resuspension in the test medium. The ratio between the inoculum (in MES) and the test substance (in COD) is between 2.5:1 and 4.0:1 in the test bottles.

[0051] Sample: according to the present invention

[0052] - Storage mode: room temperature

[0053] - Method of preparing test solutions: dilutions.

[0054] Results: Percentage biodegradation rate as a function of time (experimental data): [Tables] 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% El 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%

[0055] E1 and E2 correspond to two test concentrations meeting the test start criteria (replicates).

[0056] 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) shows a biodegradability greater than 35% indicating an absence of toxicity of the sample with respect to the inoculum. The abiotic control (ABIO) shows no significant abiotic degradation of the sample under the test conditions (<10%).

[0057] The OECD guidelines set a threshold of 20% biodegradation beyond which the substance demonstrates intrinsic primary biodegradability and a threshold of 70% beyond which the substance demonstrates intrinsic ultimate biodegradability. For this analysis, 90% to 100% biodegradation of the test substance is observed within 28 days.

[0058] Samples E1 and E2 using compositions according to the invention demonstrated “intrinsic ultimate biodegradability without preadaptation” (and therefore also “intrinsic primary biodegradability”) according to OECD criteria extrapolated to a formulated or mixed product.

[0059] In conclusion, the compositions for treating and protecting mineral surfaces according to the present invention exhibit superior anti-stain effectiveness, good anti-slip properties, very good abrasion resistance, a very low level of emission of volatile organic compounds and excellent biodegradability.

Claims

Claims

1. Composition for treating and protecting mineral surfaces, 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 surfactant-free self-emulsified urethane-modified alkyd emulsion, particularly preferably a 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 powdered organic matting agents, preferably one or more powdered thermoset material matting agents, c. 0.01 to 0.2% by weight of a water-soluble ethoxylated non-ionic fluorinated surfactant, preferably based on short-chain molecules containing 6 fluorinated carbon atoms, and d.water, the bio-sourced carbon content according to standard EN 16640:2017 of the dry extract of the composition being more than 32%.

2. A 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, having a biosourced carbon content according to standard EN 16640:2017 of the dry extract of more than 37%, preferably more than 42%, in particular more than 47%.

5. A composition according to any one of claims 1 to 4, having an application yield of at least 5 to 20 m2 / l for the application of two coats.

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

7. Method for treating and protecting mineral surfaces according to claim 6, in which the application is carried out by roller or brush, preferably by roller.