LU500004B1 - PRODUCT FOR THE TREATMENT AND PROTECTION OF MINERAL SURFACES - Google Patents

Abstract

The invention relates to a concentrated product for the treatment and protection of mineral surfaces without fluorinated compounds, the concentrated product comprising, relative to its total weight, 50 to 69% by weight of a first emulsion of one or more (co ) self-crosslinking acrylic polymers, 20 to 29% by weight of a second emulsion comprising at least two compounds chosen from silanes, alkoxysilanes, siloxanes and organosiloxanes, 1 to 6% of one or more biocidal agents, as well as a ready-to-use product. The invention also relates to a method of manufacturing and a method of treating and protecting mineral surfaces. (Fig.2)

Description

PRODUCT FOR THE TREATMENT AND PROTECTION OF MINERAL SURFACES Technical field

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 say they do not allow all surfaces to be treated (at least with the same performance) or they only protect surfaces against certain causes of dirt or visual or structural degradation. Object of the invention

[0003] An object of the present invention is therefore to provide a product for the treatment and protection of mineral surfaces which has good general performance in terms of water-repellent, oleophobic, anti-moss, antifungal, bactericidal protection, etc., which offers a long maintenance-free effectiveness, which is easy to apply on a large number of mineral surfaces, such as stone, concrete, plaster, tile, brick, slate, terracotta, etc., which is colorless and free of fluorinated compounds and petroleum solvents. General description of the invention

In order to solve the problem mentioned above, the present invention proposes in a first aspect a concentrated product for the treatment and protection of mineral surfaces, without fluorinated compounds, the concentrated product comprising, relative to its total weight, 50 to 69% by weight of a first emulsion of one or more self-crosslinking acrylic (co)polymers; 20 to 29% by weight of a second emulsion comprising at least two compounds chosen from silanes, alkoxysilanes, siloxanes and organosiloxanes; and 1 to 6% of one or more biocidal agents. The first aspect also concerns a ready-to-use product for the treatment and protection of mineral surfaces without fluorinated compounds, comprising the concentrated product above, diluted with 1 to 5 volumes of water.

A second aspect of the invention relates to a process for manufacturing a concentrated product for the treatment and protection of mineral surfaces without fluorinated compounds, in which 50 to 69% by weight of a first emulsion of a or of several self-crosslinking acrylic (co)polymers; 20 to 29% by weight of a second emulsion comprising at least two compounds chosen from silanes, alkoxysilanes, siloxanes and organosiloxanes; and 1 to 6% of one or more biocidal agents, to form the concentrated product, the quantitative indications being expressed relative to the total weight of the concentrated product.

A third aspect of the invention proposes a method for treating and protecting mineral surfaces, in which a concentrated product according to the first aspect of the invention, preferably diluted beforehand with 1 to 5 volumes of water (mixtures product: water from 1: 1 to 1: 5), respectively a ready-to-use product for the treatment and protection of mineral surfaces without fluorinated compounds, is applied to a mineral surface to be protected and left to crosslink and dry preferably for at least least 12 to 36 hours.

The self-crosslinking acrylic (co)polymer(s) are advantageously selected from (meth)acrylic acid polymers, alkyl (meth)acrylate polymers, functionalized alkyl (meth)acrylate polymers, (meth)acrylate polymers alkoxysilane acrylate or mixtures thereof. It may, for example, be a self-crosslinking acrylic (co)polymer with a high glass transition temperature (Tg) which confers significant chemical and mechanical resistance to the protective coating. Preferably, the self-crosslinking acrylic (co)polymer can be pure and uncoupled acrylic polymer having a particle size of about 70 μm. Such a polymer will advantageously dry by coalescence and crosslink alone to increase its performance. As a variant, the invention also provides for partial or total substitution of the high-Tg self-crosslinking acrylic (co)polymers by low-Tg or core-shell type acrylic (co)polymers, by styrene-acrylic copolymers, by styrene-butadiene copolymers and/or by alkyds. In the context of this text, a high glass transition temperature is generally a glass transition temperature greater than or equal to 50°C,

while a low glass transition temperature is a temperature below 50°C.

The first emulsion is preferably an emulsion containing 40 to 60% by weight, particularly preferably approximately 50% by weight, of active material ((co)self-crosslinking acrylic polymers) in water. In this context, it should be noted that it is possible to use as the first emulsion an emulsion having a higher or lower active ingredient content, but it is then necessary to adapt the quantities appropriately.

[0009] Advantageously, the second emulsion comprises disiloxane (as one of the siloxanes), preferably the second emulsion is an emulsion containing 40 to 60% by weight, particularly preferably around 50% by weight, of active ingredient (silanes, alkoxysilanes, siloxanes and organosiloxanes) in water. It should be noted in this context that it is possible to use as second emulsion an emulsion having a more or less high content of active ingredient, but it is then necessary to adapt the quantities appropriately.

[0010] Advantageously, the second emulsion can be an emulsion of the SILRES® BS type, for example SILRES® BS 4004, SILRES® BS 3003, SILRES® BS 1001 and/or SILRES® BS Creme N, preferably SILRES® BS 1001 (Wacker Chemie AG).

[0011] The biocidal agent(s) are generally chosen from isothiazolinones; in particular methylisothiazolinone, chloromethylisothiazolinone, benzisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone and/or butylbenzisothiazolinone; 3-iodo-2-propynyl butylcarbamate; quaternary ammonium compounds, in particular (C12-C16)alkyldimethylbenzylammonium chlorides (CAS 68424-85-1); zinc pyrithione; or mixtures thereof. Particularly suitable biocidal agents are in particular benzisothiazolinone (1,2-benzisothiazol-3(2H)-one), methylisothiazolinone (2-methyl-4-isothiazolin-3-one) and dichlorooctylisothiazolinone (4,5-dichloro- 2-octyl-2H-isothiazol-3-one). The addition of quaternary ammonium compounds, in particular alkyl(C12-C16)dimethylbenzylammonium chlorides, additionally allows a virucidal effect, for example against influenza viruses, coronaviruses, in particular SARS-CoV-2, etc. .

The advantages of the product (concentrated or diluted) according to the invention are in particular:

[0013] Powerful waterproofing agent for roofs, facades, walls, floors and furniture. Can be used outdoors and indoors.

[0014] 4-in-1 product: water repellent, anti-green deposits, anti-stain, mineralization properties

[0015] Self-cleaning technology e efficiency 5 years without maintenance e easy to apply with tracer effect e colorless and without petroleum solvent e stone, concrete, plaster, tile, brick, slate, terracotta...

[0016] Powerful waterproofing agent resistant to water, fungi, grease and stains with a remineralising effect, reinforcing the stone against infiltration.

[0017] Protects porous materials against the penetration of rainwater and thus eliminates the harmful effects due to infiltration, acid rain, erosion, freeze/thaw cycle, formation of moss, green deposits and lichens, efflorescence, etc.

[0018] Anti-stain properties which permanently limit the penetration of all types of dirt, even greasy dirt. Facilitates support maintenance.

[0019] Non-film-forming impregnation product. It is colorless after application, it does not modify the nature of the treated support. Very good resistance to U.V, it does not yellow. Brief description of the drawings

Other features and characteristics of the invention will emerge from the detailed description of some advantageous embodiments presented below, by way of illustration. The appended figures show: FIG. 1: nine samples 21 days after application of the products (see below), Fig. 2: these new samples 77 days after application of the products, and

Fig. 3: a graph representing the absorption of water by samples treated (test pieces) with a product according to the invention and untreated (control) over time.

Examples

The present invention proposes an invisible protection solution making it possible to reduce the penetration of water into the coatings so as to minimize the development of microorganisms on the surface of the coatings.

The experiments below were carried out on nine samples of coatings of different colors. The surface of each sample was delimited into 3 zones, including 2 protected and one unprotected, serving as a control in the center.

[0023] In view of the average porosity of the samples and the performance sought, the products tested are as follows:

[0024] - Product 1 (comparative): invisible protection for porous to moderately porous materials from the ProtectGuard range marketed by Guard Industrie

[0025] - Product 2 (ready-to-use product according to the present invention): invisible protection

[0026] Composition of Product 2 Product 2 Product 2 Component; I. (concentrate) (ready to use, PAE) Second emulsion (SILRES® BS 24% 6% 1001) Biocide Pot (comprising 1,2- benzisothiazol-3(2H)-one and 1.72% 0.43% zinc salts of pyridine-1-oxy-2-thiol) Biocide Film (comprising dichlorooctylisothiazolinone, 0.68% 0.17% butylcarbamate of 3-iodo-2-

propynyl, methylisothiazolinone, and chloromethylisothiazolinone)

[0027] TEST 1: VISUAL OBSERVATION / AESTHETIC RENDER

[0028] Coated supports: Parex; preparation of supports: dust removal; products tested: Product 1 and Product 2 (PAE); method of application: brush, saturation

[0029] COMMENTS:

[0030] The substrates are treated and observed the day after application.

[0031] The aesthetic criteria are: + The homogeneity of the appearance of the surface - The presence of a satin finish in the case of Product 2. The protections are invisible. The satin appearance provided by Product 2 is slight due to the surface texture and is only visible under certain inclinations of light.

[0032] TEST 2: WASHING RESISTANCE TEST

[0033] TEST PROTOCOL:

The test consists of simulating rain for several weeks using a programmed water supply. The samples are placed almost horizontally so as to allow greater exposure and an acceleration of the phenomena observed in vertical exposure.

[0035] The cycles are as follows: + Simulation of rain for 16 hours + Drying outside for 8 hours

[0036] A follow-up of the condition of the surfaces is carried out by photographs in order to assess the effectiveness of the protections tested.

[0037] PREPARATION OF SAMPLES:

The samples are divided into 3 bands: < Left band: Product 2 (PAE) * Untreated band, serving as control in the center * On the right, zone treated with Product 1.

[0039] FIG. 1 shows the nine samples 21 days after application of the products and FIG. 2 shows these nine samples 77 days after application of the products.

[0040] The microorganisms which develop on the materials tested are dark in color and therefore more visible on the light-colored samples.

[0041] On the dark-colored samples, it is the absorption of water which is visible by the change in color of the samples becoming dark under the influence of the water which impregnates them.

[0042] It is visible that significant water resistance is provided by Product 2, the formulation of which is particularly focused on water resistance.

[0043] On the unbleached and yellow samples, the development of microorganisms is clearly visible and the area treated with Product 2 is spared.

[0044] Product 2 is therefore a solution suitable for the coatings tested with the aim of drastically reducing their water absorption and, thus, significantly delaying the development of micro-organisms.

Product performance table 2 (PAE) Nature of the test Method used Value I Lo Physical properties of the Density 1.0 + 0.02 product. pH 85+05 Color Milky Solubility in water Total

Nature of the test Method used Value Nowe armies ____| Stability of the product within [Internal method |4 weeks in an oven at |Product: stable after 4 the closed jar (viscosity, 40°C weeks of ageing. sedimentation) and Expiry date: 12 months from the date of manufacture, in original unopened packaging.

Vapor permeability |NF EN ISO 7783- SD - SD untreated control: of water 2 (0.05+/-0.02) m ITV = (91+/-4) % Water absorption per DIN 53.495 Laboratory test at 21 Porous concrete: capillarity Internal method [73°C Efficiency = 92% at 24 hours The results - Porous terracotta: of absorption depend p' on the porosity of the support Efficiency = 60% at 24 hours. - Moderately porous terracotta Efficiency = 70% at 24h Resistance to stains | NF EN ISO Terracotta: domestic 10545-14 and NF Pa x i EN ISO 16301 Water Resistance to 4H: 5 Internal method Olive oil Resistance to 24H: 5 ( 0: minimum score Wine Resistance to 24H: 5 / 5: Resistance to optimal limestone) moderately porous: Water Resistance to 4H: 5 Olive oil Resistance to 4H: 4 Wine Resistance to 4H: 3 Porous concrete Water Resistance to 4H: 5 Olive oil Resistance to 4H: 4 Wine Resistance to 4H: 4 Resistance to abrasion ISO 11998: Terracotta Performance intact when dry (scotch brite) x; ; water Dry test with Limestone Concrete abraser Reduced performance with pad equipped with an abrasive oil and wine. m=> Recommended re-application m=> 200 cycles of a=> Simulation of observations of these effects. foot traffic

Nome Faramötres | Durability test: Internal method: |[Durable Protective facade coatings: WASHING Different samples Untreated areas: x colors/composition . oC are placed in darkened due to exterior with water impregnation and inclination at 45° appearance of dirt and subject to organics on the surface. alternations of Protected areas: Remains rain (lighter spraying and absence of water at night) and drying development (day, development except weather conditions dirt to the contrary) Durability test: ISO 11341 Concrete Durable protection: SOLARBOX z; . The Performances preserved samples undergo, for 1000 hours, rain cycles (sprinkling of water until the sample is covered). Then intense sunlight (action of a Xenon lamp) Safety properties |NA Harm No Toxicity No Flammability No Explosivity No Transport labeling [No Suitability for contact EN 1186-3 Migration, through the |Inert to global food migration; .. [Product film 2, of aqueous and fatty simulants A product film |. ; z simulating; x; ; 2 is immersed Non-inert to migration for 72 hours at 20° acid simulant in a substitution simulant, or for 10 days at 40° in 3% acetic acid or 10% ethanol ISO virucidal activity 21702:2019 Virus eradication of 197.12% of viruses tested Vaccine eradicated after 2 hours Algaecide activity NF EN 15458 Contamination by algae |No algal proliferation of treated tiles

Nature of the test Method used Value Norm [Parameters | Properties Test of Water absorption by a permeability |No change meaning permeability to support in mortar of the quantity of water the liquid water according to |plaster-lime treated has absorbed between 1h and 5h the standard saturation of the support uptake; absorption by NF EN 1603 a treated support 2.4 times less than by an untreated support (Fig. 3)

[0046] USE OF PRODUCT 2 ACCORDING TO THE INVENTION

Can be used outdoors on porous floors, facades, walls and roofs. Ideal for all types of materials: natural or reconstituted stone, concrete, plaster, brick, terracotta, slate, cement, interlocking paving stone, etc.

[0048] CONSUMPTION

The consumption depends on the porosity of the material.

The following values are given as an indication: 6 to 8 m? / liter

[0051] IMPLEMENTATION

[0052] Preparation of the support:

[0053] Apply the product to a clean, dust-free, degreased and dry surface. It is advisable to remove black marks, pollution or dirt invading the materials, as well as traces of efflorescence, laitance or veils of cement.

[0054] Application:

[0055] Use the ready-to-use product in its pure state: do not dilute. Shake the packaging well before use and carry out a preliminary test. The support must be impregnated until saturation in two to four coats "wet on wet". It is advisable not to overload the support, remove any excess before drying. For vertical surfaces, apply from bottom to top. Protected drying: 24 hours. Maximum efficiency obtained after 7 days.

[0056] APPLICATION TOOLS

[0057] Apply with a low-pressure sprayer, roller or brush.

[0058] MAINTENANCE

[0059] Household stains can be cleaned with clear water or with a neutral pH cleaner.

[0060] ENVIRONMENT

[0061] Respectful of the environment and ecological: without petroleum solvents and non-hazardous. More than 90% biodegradable. VOC < 2 g/l.

[0062] TECHNICAL DATA

Physical state at 20° C.: liquid; color: milky; smell: light; pH: 8 +

0.5; boiling point: 100°C; density: 1.0 + 0.02; water solubility [vol/vol]: total; flash point [°C]: not applicable.

[0064] RECOMMENDATIONS

[0065] Only treat surfaces previously cleaned of all atmospheric pollution and all stains. Do not dilute or mix with any other product.

[0066] Do not apply on organic, metallic and impermeable materials. Frames and windows must be protected. Accidental drips and stains should be cleaned immediately with water.

[0067] The product may slightly accentuate the color (satin effect). Always carry out a test on the support to be treated before application.

For perfect application and effective protection, the product must be shaken and used imperatively when the temperature of the substrates is between 5°C and 30°C.

[0069] Do not apply in rainy or very hot weather. Air temperature between 5°C and 30°C.

Claims (11)

Claims 1. Concentrated product for the treatment and protection of mineral surfaces without fluorinated compounds, the concentrated product comprising, relative to its total weight, 50 to 69% by weight of a first emulsion of one or more acrylic (co)polymers self-crosslinking, 20 to 29% by weight of a second emulsion comprising at least two compounds chosen from silanes, alkoxysilanes, siloxanes and organosiloxanes, 1 to 6% of one or more biocidal agents. 2. Concentrated product for the treatment and protection of mineral surfaces according to claim 1, in which the first emulsion is an emulsion with 40 to 60% by weight of active ingredient in water. 3. Concentrated product for the treatment and protection of mineral surfaces according to claim 1 or 2, in which the self-crosslinking acrylic (co)polymer(s) are selected from (meth)acrylic acid polymers, alkyl (meth)acrylate polymers , functionalized alkyl (meth)acrylate polymers, dalkoxysilane (meth)acrylate polymers, or mixtures thereof. 4. Concentrated product for the treatment and protection of mineral surfaces according to any one of claims 1 to 3, in which the second emulsion is an emulsion with 40 to 60% by weight of active ingredient in water. 5. Concentrated product for the treatment and protection of mineral surfaces according to any one of claims 1 to 4, in which the second emulsion comprises disiloxane. 6. Concentrated product for the treatment and protection of mineral surfaces according to any one of claims 1 to 5, in which the biocidal agent or agents are chosen from isothiazolinones; in particular methylisothiazolinone, chloromethylisothiazolinone, benzisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone and/or butylbenzisothiazolinone; 3-iodo-2-propynyl butylcarbamate; quaternary ammonium compounds, in particular alkyl(C12-C16)dimethylbenzylammonium chlorides; zinc pyrithione; or their mixtures, in particular 1,2-benzisothiazol- 3(2H)-one, 2-methyl-4-isothiazolin-3-one and/or 4,5-dichloro-2-octyl-2H-isothiazol-3-one 7. Ready-to-use product for the treatment and protection of mineral surfaces without fluorinated compounds, comprising the concentrated product for the treatment and protection of mineral surfaces according to any one of claims 1 to 6 diluted with 1 to 5 volumes of water, preferably with about 3 parts water. 8. A method of manufacturing a concentrated product for the treatment and protection of mineral surfaces without fluorinated compounds, according to any one of claims 1 to 6, in which the first emulsion of one or more (co)polymers is mixed self-curing acrylics; the second emulsion comprising at least two compounds chosen from silanes, alkoxysilanes, siloxanes and organosiloxanes; and the biocidal agent(s), to form the concentrated product. 9. Process for the treatment and protection of mineral surfaces, in which a concentrated product for the treatment and protection of mineral surfaces according to any one of claims 1 to 6 or preferably a ready-to-use product for treatment and protection of mineral surfaces without fluorinated compounds according to claim 7, is applied to a mineral surface to be protected and left to crosslink and dry preferably for at least 12 to 36 hours. 10. Treatment and protection process according to claim 9, in which application is made by impregnating the mineral surface until saturation in one to four layers, preferably by “wet on wet” application. 11. Treatment and protection method according to claim 9 or 10, in which the application is made with a low-pressure sprayer, roller or brush.