Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes

Definitions

• the present invention relates to novel coating compositions, especially exterior and interior paint compositions. These compositions may be used in various applications such as water-based paint, casting products, lazure paints, impregnations, semi-thick coating (STC) or paints for facades.
• STC semi-thick coating
• the prior art does not indicate any coating composition that is capable of being correctly and adequately crosslinked by condensation, into an elastomer or a crosslinked product, which gives the final application, for example in the form of paint, an increased wet scrub resistance (WSR), a beading effect and a water impermeability that are satisfactory.
• WSR wet scrub resistance
• One of the main objects of the present invention is therefore to provide a novel aqueous silicone coating dispersion giving the final application an effective waterproofing, that is to say an increased wet scrub resistance (WSR), a water impermeability, a water vapor permeability and a beading effect which are satisfactory.
• WSR wet scrub resistance
• the invention relates to an aqueous silicone dispersion, containing one or more polyorganosiloxanes (POSs) intended to be crosslinked or having been crosslinked by elimination of water or alcohol, according to the polycondensation mechanism taking place, advantageously, at ambient temperature.
• POSs polyorganosiloxanes
• the present invention also relates to one method amongst others for preparing aqueous silicone emulsions and dispersions, especially of the type of those according to the invention.
• aqueous silicone emulsions have appeared that are intended to be used as raw materials in the manufacture of paints, STCs or mastics, and containing one or more silicone oils that can be crosslinked into elastomers by condensation.
• the aim of such emulsions is to completely or partly substitute the organic polymer binders conventionally employed to date, especially in paints.
• VOCs harmful products
• the curing time of the silicones of the emulsion must not be too long after application.
• the crosslinked product or elastomer which forms must have suitable mechanical properties (hardness, elasticity, abrasion resistance) adapted to the application in question.
• a paint must be easy to apply in the form of a film by known means: by brush, roller, spraying, immersion, etc.
• the paints and also the polymer binders that they contain, in particular the silicones, crosslink correctly so as to produce a hard elastomer film.
• this film must not be tacky, so as to prevent dust from sticking to it. Imperfect curing of the paint film also has the deleterious repercussion of reducing its durability and its resistance to external environmental or biological attack.
• the novel aqueous silicone dispersion that can be used especially in the formulation of paints, developed and being the subject of the present invention, is mainly composed of:
• the catalyst is preferably a catalytic tin compound, generally an organotin salt, preferably introduced in the form of an aqueous emulsion.
• organotin salts that can be used are described, in particular, in the work by Noll, Chemistry and Technology of Silicones, Academic Press (1968), page 337.
• reaction product of an alkyl silicate or of an alkyl trialkoxysilane with dibutyltin diacetate may also be suitable.
• a tin II salt can be used, such as SnCl 2 or stannous octoate.
• the preferred tin salts are tin bischelates (EP-A-147 323 and EP-A-235 049), diorganotin dicarboxylates and, in particular, dibutyltin or dioctyltin diversatates (British Patent GB-A-1 289 900), dibutyltin or dioctyltin diacetate, dibutyltin or dioctyltin dilaurate or the hydrolysis products of the aforementioned species (e.g. the diorganostannoxanes and polystannoxanes).
• the aqueous silicone dispersion according to the invention does not have a polycondensation catalyst and is mainly composed of:
• the aqueous dispersion is in the form of an oil-in-water emulsion.
• this dispersion is durably stable and that it satisfies the assigned objectives of improving the WSR, of ease of preparation and of use, of selective barrier to exchanges of water in liquid form or vapor form, of safety/nontoxicity and of improving the beading effect of the paint based on this dispersion.
• Crosslinking in an emulsion makes it possible to increase, in situ, the average molecular weight of the resin (A) and its viscosity.
• the hydroxylated resin (A) Before its crosslinking, the hydroxylated resin (A) has a sufficiently low weight-average molecular weight M w and therefore, in fact, a sufficiently low viscosity in order to be able to be emulsified. It is not necessary to first dilute this resin in a solvent in order to be able to emulsify it according to conventional procedures.
• this dispersion according to the invention comprises, after crosslinking, a silicone crosslinked product or elastomer that has improved mechanical properties (especially abrasion resistance), without using toxic and dangerous solvents.
• the constituents (A), (B), (C), (S) and (D) of the dispersion are defined in the present text through their initial chemical structure, that is to say the structure that characterizes them before emulsification. This is because, from the moment that they are in an aqueous medium, they are converted by hydrolysis/condensation and their structure then becomes difficult to define.
• the main constituent of the dispersion on the basis of weight is the polyorganosiloxane resin (A).
• the hydroxyl groups of this resin are preferentially borne by the T units, but a hydroxyl substitution of the M and/or D and/or optionally Q units is not excluded.
• the level of hydroxylation is expressed in % by weight. According to this mode of expression, the minimum hydroxylation is, preferably, equal to 0.05%. In practice, it is greater than or equal to 0.3% and more preferably still between 0.5% and 3%.
• this level of hydroxylation is sufficient to guarantee correct crosslinking that conforms to the expected level.
• siloxane units M, D, T and Q are defined as follows:
• each OH group is borne by a silicon atom belonging to a D, T or Q unit.
• These resins are products of condensation (monocondensation or polycondensation, heterocondensation or homocondensation) of monomers, oligomers, or POS polymers bearing condensable groups, preferably of hydroxyl type.
• the polyorganosiloxane resin (A) comprises, before emulsification:
• the polyorganosiloxane resin (A) is a liquid polyorganosiloxane resin of T(OH), DT(OH), DQ(OH), DT(OH), MQ(OH), MDT(OH), MDQ(OH) type or mixtures thereof, and preferably MDT(OH), DT(OH) or mixtures thereof.
• the water-soluble hydroxylated alkylaminosilane (C) is aminopropyltrihydroxysilane.
• the water-soluble hydroxylated alkylaminosilane (C) is present up to 15% by weight relative to the total weight of the dispersion, preferably present up to 10% and even more preferably between 0.5 and 7% by weight.
• the epoxy-functionalized polyorganosiloxane (B) of the aqueous silicone dispersion according to the invention comprises at least one epoxy-functional radical Y, linked to the silicon via a divalent radical containing from 2 to 20 carbon atoms and possibly containing at least one heteroatom, preferably oxygen, bearing at least one epoxy unit, Y preferably being chosen from the following radicals:
• the epoxy-functionalized polyorganosiloxane (B) is composed of units of formula (V) and terminated by units of formula (VI) and/or composed of units of formula (V) represented below:
• the organofunctional groups Y′ of the epoxy type are chosen from the following formulae:
• the epoxy-functionalized polyorganosiloxane (B) may be either linear or cyclic.
• cyclic polyorganosiloxanes When they are cyclic polyorganosiloxanes, these are composed of units (II) which may be, for example, of the dialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiloxanes have a viscosity of around 1 to 5000 mPa ⁇ s.
• a surfactant (S) is used in the dispersion according to the invention, it is preferably a nonionic surfactant.
• anionic surfactants may optionally be used.
• alkali metal salts of sulfonic or alkylsulfuric aromatic hydrocarbon-based acids mention may be made of the alkali metal salts of sulfonic or alkylsulfuric aromatic hydrocarbon-based acids and the preferred nonionic surfactants are polyoxyethylenated alkylphenols or polyoxyethylenated fatty alcohols.
• the amount of surfactant that can be used is that commonly employed for emulsification as described, in particular, in U.S. Pat. No. 2,891,920.
• nonionic preferably, ionic or amphoteric surfactants may be employed alone or mixed together.
• the dispersion according to the invention comprises from 30 to 90%, preferably from 30 to 60% by weight of water per 70 to 10%, preferably 70 to 40%, by weight of nonaqueous phase.
• a second subject of the invention relates to a method of preparing an aqueous silicone dispersion, that can be used especially in the formulation of paints, characterized in that it comprises the following essential, successive or non-successive steps:
• a third subject of the invention relates to an aqueous formulation, which can be used especially in the formulation of paints, comprising:
• the final subject of the invention relates to a paint, characterized in that it comprises:
• the paint according to the invention may be applied, for example, to facades in accordance with the customary techniques.
• it may be applied to the surfaces by any suitable means such as by brushing, spraying, etc.
• the surfaces on which the coating composition according to the invention can be applied are of diverse nature: for example, metal such as aluminum, wood, cement, brick, with or without prior coating with an adhesion primer.
• One variant consists in mixing two emulsions in step 2, one containing the polyorganosiloxane resin (A) and the other the epoxy-functionalized polyorganosiloxane (B).
• the constituents used vary depending on the case.
• a paint applied inside or outside must be able to be cleaned easily without being degraded.
• the binding power of the polymer that is to say its ability to ensure the cohesion of the assembly, is a determining factor.
• a means of quantifying this property consists in evaluating the wet scrub resistance of a paint.
• This procedure (standard NF EN 1062-3, February 1999) specifies a method for determining the liquid water permeability of paint products and similar products, applied to exterior masonry and concrete. This method can be applied to the paint products and coating systems for porous supports such as for example: bricks, concrete and render.
• the coatings for exterior masonry and concrete play an important part in preventing the penetration of runoff water in the porous mineral supports. This criterion is evaluated by means of high-porosity mineral blocks where one of the faces is coated with the coating or the coating system. The test piece is immersed in water, under set conditions and the test pieces are weighed at regular time intervals. The liquid water permeability is determined by the change in mass when the change in mass is directly proportional to the square root of the time interval.
• the slope of the linear part of the curve is the liquid water transmission coefficient W in kg/m 2 ⁇ t 1/2 in hours.
• W the liquid water transmission coefficient
• W it is necessary to divide the increase in the weight by the surface area, in m 2 , or to divide the slope by the surface area.
• the surface area will be the surface area not covered by paraffin. Normally, W is calculated for a period of 24 hours. If the part of the curve is obtained before 24 hours, the number of hours must be indicated as an index of W (e.g. W 6 ).
• PVC pigment volume capacity
• the water absorption is influenced by compounds that are volatile and soluble in water. In practice, these compounds may evaporate from the coating during its exposure to the outside or be washed away by rain, the coating must undergo an “accelerated” aging before the determination of its liquid water absorption (two washes instead of the three expected in the conventional procedure).
• the slope of the linear part of the curve is W, the liquid water transmission coefficient in kg/(m 2 ⁇ t 1/2 ).
• W the liquid water transmission coefficient in kg/(m 2 ⁇ t 1/2 ).
• W is calculated for a period of 24 hours. If the linear part of the curve is obtained before 24 hours, the number of hours must be indicated as an index of W (e.g. W 6 ). Plot the water absorption curve in kg/m 2 as a function of ⁇ square root over (time) ⁇ . A straight line is obtained. The slope is equal to the transmission coefficient W. For each coating studied, the average and the standard deviation of W 24 will be calculated and presented.
• Table 1 The values in Table 1 are expressed as % by weight relative to the total weight of the emulsion.
• the average diameter is measured using a Malvern Master sizer 2000/Hydro 2000G particle size analyzer.
• the dispersions according to the invention make it possible to obtain W 24 values that allow them to be classed as paints having a low liquid water permeability.
• the paints according to the invention have, after application and drying, an acceptable beading effect for the desired application.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Dispersion Chemistry (AREA)
• Paints Or Removers (AREA)
• Silicon Polymers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 2005
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