Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • 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
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• the present invention therefore relates firstly to the synthesis of cationic dispersions in the presence of maleimide copolymers and in particular styrene-maleic anhydride imidized, but also the application of these dispersions in the field of coatings and processing of the paper.
• French patent application FR 99/07910 describes the synthesis of cationic dispersions in the presence only of styrene / imidized maleic anhydride copolymers used in an amount of 20 to 60% by weight relative to the monomers. This patent also describes the application of these dispersions for internal bonding or surface bonding of paper and cardboard.
• French patent application FR 00/03031 also describes the use of these same cationic dispersions in the field of coatings or surface treatments of various substrates, giving the coating good resistance to water and alkaline hydrolysis, an effect which reinforces and inhibits the migration of water-soluble substances from the substrate to the surface of the coating.
• the present invention differs from the prior art in that it uses a combination of imidized styrene / maleic anhydride copolymers and cationic co-surfactants, which makes it possible to minimize the level of imidized SMA involved and to achieve a higher dry extract that was difficult to achieve with the imidized SMA alone, while retaining good control of the particle sizes and good stabilization of the dispersion, including after prolonged storage. It has also been found that, surprisingly, the use of this cationic surfactant does not modify the good properties in the various application fields already mentioned.
• the cationic dispersions thus obtained have a higher dry extract, small particle sizes, and very high stability even after prolonged storage at temperature, after freeze-thaw cycles or after mechanical shearing.
• the hydrophobicity, the resistance to alkaline hydrolysis, as well as the insulating or reinforcing properties of such emulsions are preserved compared to the emulsions not containing cationic surfactants.
• the present invention also relates to the field of paper bonding and in particular to bonding agents and more particularly to bonding agents based on a cationic aqueous dispersion of hydrophobic polymers.
• a good bonding agent is desired for all papers, especially writing printing papers, label papers, recycled papers and packaging papers.
• surface bonding agent means an agent applied to the surface of the papers, generally in conjunction with starch, using a size press; on the other hand, by internal bonding is meant an agent added with the fibers in the wet part of papermaking.
• a good surface bonding agent allows paper manufacturers to achieve good water resistance 'of their paper by reducing and even eliminating an internal bonding which requires a larger amount of product that a bonding surface . It also makes it possible to obtain good surface properties of the paper, which are particularly important for obtaining good printability properties of the papers.
• the present invention also relates to the field of surface treatment of various materials, in particular to the surface treatment of wood, building materials and steel and, more particularly, to the insulating and protective coating, preventing migration of water-soluble compounds present on the surface and within the material towards the surface of the coating.
• compositions used for the surface treatment of materials can be aqueous or based on organic solvents.
• aqueous formulations despite their practical and ecological advantages, comes up against the problem of migration of water-soluble coloring substances present on the surface and in the material to be coated. On contact with an aqueous formulation, these water-soluble substances dissolve and rise to the surface.
• an aqueous system such as a latex paint
• the tannins are extracted from the substrate and migrate to the surface, which they color unaesthetically.
• the coloring manifests itself through successive layers, unless an insulating layer blocks the ascent of the coloring substance.
• the aqueous dispersions of the present invention make it possible to block the migration of all these water-soluble substances which can be colored, by the surface pretreatment of the substrates concerned by a pretreatment composition comprising the defined aqueous dispersion according to the present invention. This use in pretreatment of substrates is carried out before the protective or decorative coating of this substrate.
• the present invention also relates to another important aspect in the fields of coatings, in general, and in the field of painting, in particular, but also in other fields such as those of inks and varnishes, leather or even textiles, namely obtaining maximum resistance to alkaline hydrolysis, in order to limit the deterioration of the coating under the action of alkaline cleaning solutions for example or under the action of an alkaline substrate such as concrete for example .
• the application of a solvent system solves the various problems; with a water system, the formulator must select all the constituents (binders, pigmentation, additives and solvents) in order to optimize the insulating power of the coating. These choices are often made at the expense of other application properties, such as ease of application, open time, appearance, gloss, adhesion, so that the final result is only ' moderately satisfactory while only partially ensuring the objective of blocking the rise of water-soluble.
• the present invention finally relates to the field of surface treatment, particularly to the treatment reinforcing the surfaces of porous substrates.
• the buildings are also made up of very varied supports such as cement, concrete, plaster or wood, and therefore require printing in aqueous or solvent phase "universal or multifond".
• EP-A1-0 644 205 describes a process for obtaining very thin latex of particles (less than 100 nm and preferably between 5 and 40 nm), having solid levels, rather low of the order of 25%, and its use in various fields related to coatings (preservation of wood, product of waterproofing, stationery product, etc.).
• This document is based mainly on the fine particle size of the latex, the application part being substantially exemplified in terms of penetration 'in the wood, and textile processing.
• Rhodopas Ultrafine like Ultrafine PR 3500, manufactured and marketed by Rhodia, have virtues in terms of particle size, penetration and rheology. Therefore, they are applied to the areas of consolidation of chalky funds, blocking of saline lifts.
• the process for obtaining the aqueous dispersion according to the invention consists of an emulsion polymerization from an imide derivative (II) of a copolymer based on maleic anhydride.
• imide derivative (II) of a copolymer based on maleic anhydride.
• the synthesis of these derivatives based on the reaction of a diamine and a polymer (I) based on maleic anhydride is described in American patent US-A-3,444,151. Briefly, the derivatives i ides are obtained by reaction between a polymer (I) and a tertiary primary diamine, for example dimethylpropylene diamine (DMAPA) preferably by a bulk process.
• DMAPA dimethylpropylene diamine
• the amine derivatives used in this invention are preferably those of type I described in American patent US Pat. No. 3,444,151, that is to say those in which a diamine reacts completely on the anhydride function with a molar ratio of 1 to 1.
• copolymers having anhydride or acid functions residual, resulting from an amine fault reaction is also possible.
• Polymer I can be a copolymer or terpolymer consisting of maleic anhydride and hydrophobic monomers chosen from alpha-olefins, unsaturated ethylenic aromatics, vinyl ethers or allyl ethers.
• the preferred copolymer of the invention is a copolymer of styrene and maleic anhydride (SMA) with a styrene on Anhydride maleic 1/1 to 6/1, preferably from 2/1 to 4/1.
• the number-average molecular mass of the emulsifying copolymer is between 500 and 20,000, preferably between 2000 and 5000.
• the rate of imidization of said copolymer can be between 50 and 100%.
• Said copolymer can be imidized for example with dimethylpropylene diamine.
• the mass percentage of this oligomer in the final dry extract is between 10% and 40%, preferably between 20% and 30%.
• Polymer I is preferably selected from copolymers of styrene and maleic anhydride having acid numbers ranging from 500 to 200 mg KOH / g and commecialisés by Cray Valley under the name ® SMA 1000, SMA ® 2000 , SMA ® 3000, SMA ® EF30, and SMA ® EF40 and SMA ® EF60. After imidization, the copolymer is then placed in aqueous solution, neutralized with an acid to give a cationic emulsifying oligomer. The acid used will preferably be a weak volatile acid such as ethanoic or methanoic acid. These imidized copolymers (II) are also sold by the company Cray Valley under the names of SMA XlOOOi, SMA X2000i, SMA X30001 and SMA X4000i.
• the imidized copolymer (II) will be combined with a traditional cationic cosurfactant (III) chosen without limitation from alkyl dimethyl alkyl ammonium chlorides, such as alkyl dimethyl benzyl chlorides ammonium, distearyl dimethyl ammonium chloride or lauryl trimethyl ammonium chloride, among the alkyl trimethyl ammonium methosulphates such as ricinoylamidopropyl trimethyl ammonium methosulphate, or among the alkyl dimethylamines.
• alkyl dimethyl alkyl ammonium chlorides such as alkyl dimethyl benzyl chlorides ammonium, distearyl dimethyl ammonium chloride or lauryl trimethyl ammonium chloride
• alkyl trimethyl ammonium methosulphates such as ricinoylamidopropyl trimethyl ammonium methosulphate, or among the alkyl dimethylamines.
• the cationic emulsion is then synthesized using conventional polymerization technologies in emulsion, in an aqueous solution having a proper amount, preferably from 30 to 50% 'based on the monomers, of the cationic emulsifier (II) described above , which is therefore associated with the cationic surfactant (III) generally used at a rate of 0.1 to 5% by weight, preferably from 0.5 to 3%, relative to the monomers, in the presence of a usual radical initiation system and a mixture of ethylenically unsaturated monomers, for example composed of styrene and (meth) acrylic esters.
• only the cationic surfactant (III) is introduced at the start of polymerization, while the cationic polymeric surfactant (III) is introduced in a second step.
• the radical initiator can be a water-soluble initiator, such as ammonium, potassium or sodium persulfates, optionally combined with an agent of the sodium metabisulfite type or alternatively a hydrogen peroxide or a hydroperoxide such as tertiary hydroperoxide. butyl, combined with a reducing agent such as ascorbic acid or sodium formaldehyde sulfoxylate.
• This initiator can also be organosoluble like azo derivatives, such as azobisobutyronitrile or organic peroxides.
• the polymerization temperature is between 30 ° C and 100 ° C, preferably between 60 ° C and 90 ° C and will be adapted to the priming system used.
• the monomers are chosen in particular so as to obtain the desired glass transition temperature (Tg), but also the polarity, functionality or degree of crosslinking sought.
• Tg glass transition temperature
• This Tg can be between -70 ° C and 100 ° C, preferably between 0 ° C and 50 ° C.
• the monomers will be chosen from rrtethyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate and more generally the
• alkyl (meth) acrylates of formula:
• vinyl acetate vinyl acetate, styrene, versatic esters, acrylic acid, methacrylic acid, acrylamide, ethylene glycol dimethacrylate, etc.
• the cationic dispersions of the invention have a dry extract of between 30% and 50%, preferably between 40% and 50% and a particle size of between 50 nm and 300 nm, in particular between 50 nm and 200 nm, with an average particle size preferably less than 100 nm. They have very good compatibility with the starches capable of being used in the size press and this even at high temperature, whether these are native starches, weakly anionic starches or cationic starches. They have a low viscosity, preferably less than 100 mPa.s for a dry extract of up to 50%. They have a very good 'stability over time, a very good mechanical stability and very good resistance to freeze-thaw cycle.
• treated papers very good hydrophobicity and this at treatment rates much lower than those of an equivalent anionic emulsion. They make it possible in particular to treat surface-type test liner papers intended for cardboard packaging where very good hydrophobicity of the papers is required. They also make it possible, inter alia, to use starch and cationic pigments during the surface treatment of the paper and to obtain very good inkjet printability.
• the particles present in printing inks are in fact generally anionic and will be more easily fixed to the surface of the paper if cationic components are present.
• the present invention therefore also relates to the use of dispersions according to the invention with other bonding agents such as starch for the surface bonding of paper and cardboard.
• the dispersion and the starch can be taken in a mass ratio ranging from 5 to 50%.
• the invention also relates to the use of the dispersions according to the invention in formulation in the surface treatment of metals, paper, glass, wood, building materials, such as concrete or plaster, plastic, leather and textiles.
• Said treatment can consist of the application of an insulating and / or protective coating based on said formulation, to prevent the migration of water-soluble compounds, which can be colored, present on the surface and / or within substrate material, towards the surface of the final coating.
• Said substrate including wood, 'plaster, concrete, steel or leather.
• the aqueous solution obtained has a concentration of SMA X4000i of approximately 20%.
• the dissolution of the SMAi can optionally be carried out directly in the polymerization reactor in the preliminary stage to the polymerization.
• This example describes the synthesis of a cationic dispersion according to the process of the invention.
• a double-jacketed glass reactor with a capacity of 2 liters, equipped with central stirring, a condenser, a temperature probe and a device for continuously introducing a solution of initiator, and a mixture or a preemulsion of monomers.
• 27.60 g of demineralized water are introduced, 645 g of aqueous solution comprising 20% of X4000i (equivalent to 30% of SMA X4000i in the dry final product), and 7.5 g of 50 RTM Rewoquat (40% solution in 'water, commercialized by Witco) and the reaction medium at 85 ° C.
• An ammonium persulfate solution is also prepared by dissolving 0.6 g of ammonium persulfate in 30 g of demineralized water, a solution of 5.57 g of tert.-butyl hydroperoxide at 70% in demineralized water, a solution of ascorbic acid by dissolving 3.90 g of ascorbic acid in 75 g of demineralized water and a mixture of monomers composed of 138 g of styrene and 162 g of butyl acrylate.
• the reaction medium is at 85 ° C., 5% of the mixture of monomers and the ammonium persulfate solution are fed, and the reaction is left to react for 15 minutes at 85 ° C.
• the ascorbic acid solution is then introduced into the reactor and the separate and simultaneous introduction of the tert.-butyl hydroperoxide solution and the mixture of monomers is then carried out over a period of 4 hours, with stirring and maintaining the temperature at 85 ° C.
• the reaction medium is then kept stirring for two additional hours at 85 ° C, then cooled to room temperature, filtered through a 100 ⁇ cloth, and drained to result in dispersion 2 which has the following characteristics:
• This latex has excellent storage stability including at 60 ° C, freeze-thaw stability (greater than 2 cycles) and good shear stability (12,000 revolutions / minute).
• This example describes the synthesis of a cationic dispersion according to a variant of the process of the invention.
• a double-jacketed glass reactor with a capacity of 2 liters, equipped with central stirring, a condenser, a temperature probe and a device for continuously introducing a solution of initiator and a mixture or a preemulsion of monomers
• 118.50 g of demineralized water are introduced, 7.5 g of Rewoquat RTM 50 (40% solution in water sold by the company Witco) and the reaction medium is brought to 85 ° C.
• An ammonium persulfate solution is also prepared by dissolving 0.6 g of ammonium persulfate in 15 g of demineralized water, a solution of 5.57 g of tert.-butyl hydroperoxide at 70% in demineralized water, a solution of ascorbic acid by dissolving 3.90 g of ascorbic acid in 30 g of demineralized water and a mixture of monomers composed of 138 g of styrene and 162 g of butyl acrylate.
• reaction medium When the reaction medium is at 85 ° C., 2% of the mixture of monomers and of the ammonium persulfate solution are fed, and the mixture is left to react for 15 minutes at 85 ° C.
• the ascorbic acid solution is then introduced into the reactor, and the separate and simultaneous introduction of the tert.-butyl hydroperoxide solution, the mixture of monomers and various quantities is then carried out (see Table below). ) of 20% SMA X4000i solution, over a period of 4 hours, with stirring and maintaining the temperature at 85 ° C.
• reaction medium is then kept stirring for two additional hours at 85 ° C, then cooled to room temperature, filtered through a 100 ⁇ m cloth, and drained to lead to dispersions which have the following characteristics:
• latexes exhibit excellent storage stability including at 60 ° C., freeze-thaw stability (greater than 2 cycles) and good shear stability (12,000 revolutions / minute).
• reaction medium is at 85 ° C.
• 5% of the mixture of monomers and of the ammonium persulfate solution are fed, and the mixture is left to react for 15 minutes at 85 ° C.
• the ascorbic acid solution is then introduced into the reactor, and the separate and simultaneous introduction of the tert.-butyl hydroperoxide solution, the mixture of monomers and various quantities is then carried out (see Table below). below) of 20% SMA X4000i solution, over a period of 4 hours, with stirring and maintaining the temperature at 85 ° C. 0
• the reaction medium is then kept stirring for two additional hours at 85 ° C, then cooled to room temperature, filtered through a 100 ⁇ m cloth, and drained to give dispersions which have the following characteristics: 5
• This example describes the synthesis of a cationic dispersion in the presence of an anionic cosurfactant of the sulfosuccinate type.
• An ammonium persulfate solution is also prepared by dissolving 0.6 g of ammonium persulfate in 30 g of demineralized water, a solution of 5.57 g of tert.-butyl hydroperoxide at 70% in demineralized water, a solution of ascorbic acid by dissolving 3.90 g of ascorbic acid in 75 g of demineralized water and a mixture of monomers composed of 138 g of styrene and 162 g of butyl acrylate.
• reaction medium When the reaction medium is at 85 ° C., 5% of the mixture of monomers and of the ammonium persulfate solution are fed, and the reaction is left to react for 15 minutes at 85 ° C.
• the ascorbic acid solution is then introduced into the reactor, and the separate and simultaneous introduction of the tert.-butyl hydroperoxide solution, of the monomer mixture, is carried out over a period of 4 hours, with stirring. and maintaining the temperature at 85 ° C.
• the reaction medium is then kept stirring for two additional hours at 85 ° C, then cooled to room temperature, filtered through a 100 ⁇ m cloth, and drained to result in dispersion 5 which has the following characteristics:
• This latex therefore has a significantly larger particle size and very poor storage stability since flocculation is observed after a few days of storage at room temperature.
• a paper of writing printing type (grammage of 80 g / m 2 ) which has not undergone any internal bonding is treated on the surface using a laboratory size press:
• This example shows the good behavior of the bonding agents according to the invention for the surface treatment of printing and writing papers as regards their resistance to water and to the penetration of ink.
• Acceptable writing print paper must have a Cobbeo less than 30 and an HST greater than 100.
• the writing paper is glued to the surface with a solution containing:
• a first layer of the treatment or coating to be tested is applied to a Merbau board. These coatings are shown in Table 4 below.
• a layer of standard aqueous paint is applied as a finish, which has no tannin blocking power.
• a more or less marked yellow color of the top coat can be observed in the minutes that follow. This coloration can be assessed visually or by calorimetry by measuring the difference in color compared to the finish paint applied on a neutral support.
• the latex to be tested is applied to the Leneta card in order to obtain a dry film 3 mm thick, and left to dry for 2 hours before applying to the surface of the film for 10 minutes, a drop of demineralized water or a drop of 2% aqueous sodium hydroxide solution.
• the deterioration of the film is then noted qualitatively by assigning a rating ranging from 0 (destroyed film) to 5 (non-damaged film).
• the flouring base consists of a mixture of calcium carbonates and titanium oxide (Durcal 10 and Ti02 RL 68) dispersed in a cellulosic thickener solution based on Natrosol 250 HR at 2%, which is applied by spraying. on a range of agglopan (fiber cement) in increasing thickness. Different thicknesses are produced: 20, 50, 100 and 150 ⁇ m.
• the primer consisting of latex not formulated with a brush and with refusal (in excess), which is applied in different dilutions: 12%, 6%, 3%, 1.5%.
• the primer in the reference solvent phase marketed by the company La Seigneurie under the name of Impriderme P is also applied, a non-chalky bottom space without primer also being kept for reference.
• the deterioration of the film is evaluated by a rating from 0 (poor) to 10 (excellent), depending on the rate of residual adhesion of the paint film and its degree of deterioration:
• the rating is the average value of all the measurements made at a given dilution, knowing that 3 measurements were made for the four thicknesses of flouring background.
• the substrate is a prefabricated plaster tile with a smooth (slightly shiny) and cohesive surface.
• the primer is applied by brush and refusal (in excess) in 1 pass, at different dilutions
• the system After 24 hours of drying, the system is completed by applying a layer of matt or glossy paint identical to the paints mentioned above, and the adhesion is tested in the same way as on floury background.
• the rating is the average value of all 3 measurements made at a given dilution.

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  • 2001-07-12 FR FR0109279A patent/FR2827293A1/fr active Pending
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