WO2014191573A1 - Binder for coatings including a function for binding formaldehyde in air - Google Patents

Binder for coatings including a function for binding formaldehyde in air Download PDF

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Publication number
WO2014191573A1
WO2014191573A1 PCT/EP2014/061355 EP2014061355W WO2014191573A1 WO 2014191573 A1 WO2014191573 A1 WO 2014191573A1 EP 2014061355 W EP2014061355 W EP 2014061355W WO 2014191573 A1 WO2014191573 A1 WO 2014191573A1
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WO
WIPO (PCT)
Prior art keywords
function
polymer
binder according
weight
binder
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PCT/EP2014/061355
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French (fr)
Inventor
Matthieu Olivier SONNATI
Laure-Hélène GUILLEMOT
Pierre Bernard CHEVALIER
Olivier Jacques CHOULET
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Ecoat
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Ecoat filed Critical Ecoat
Priority to EP14732099.8A priority Critical patent/EP3004266A1/en
Publication of WO2014191573A1 publication Critical patent/WO2014191573A1/en

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Classifications

    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters

Definitions

  • Binder for coating comprising a fixing function of formaldehyde of air
  • the present invention relates to a coating binder comprising a formaldehyde-fixing function of air.
  • Formaldehyde is a pollutant that is very common in indoor air. It comes from different sources such as furniture, carpets, household cooking, upholstery, cigarette smoke, plywood, melamine panels, etc. Since 2004, it has been classified as a carcinogen by IARC (International Agency for Research against Cancer). Formaldehyde causes irritation and inflammation of the eyes, respiratory tract and skin. It can also have neurological consequences that result in increased fatigue, migraines, nausea and vertigo. The main solution proposed to date are filters placed in rooms to be cleaned and through which the circulating air is cleared of formaldehyde present.
  • the present invention relates to a coating binder comprising a polymer carrying at least one formaldehyde-fixing function for reacting with formaldehyde present in the air to covalently fix it.
  • the binder has the advantage of permanently and irreversibly fixing the formaldehyde of the air. Fixation is covalent. There is no subsequent rejection of formaldehyde, particularly because the binder is stable. Indeed, the binder comprises a high molecular weight polymer limiting its migration or its modification over time. The binder is a non-volatile compound.
  • the binder according to the invention is easily integrable with different coating formulations.
  • a coating such as for example paint is a particularly present in the habitat which allows to have paint surfaces and therefore important active surfaces while being non-invasive.
  • the invention relates to a binder for coating comprising a polymer carrying at least one formaldehyde scavenger function for reacting with formaldehyde present in the air to covalently fix it.
  • the binder is such that:
  • the fixing function is a function acetoacetate grafted by transesterification on at least one hydroxyl function of a polymer
  • the acetoacetate function is grafted at a level of 1% to 50% by weight, preferably 7% to 25% relative to the weight of the polymer,
  • the fixing function is a hydrazide function grafted by condensation of hydrazine on at least one carboxylic function of a polymer
  • the fixing function is a hydrazide function grafted by reaction of a polyhydrazide with at least one carbonyl (ketone or aldehyde) function of a polymer,
  • the fixing function is a formaldehyde-fixing comonomer carrying at least one acetoacetate function such as AAEM added to acrylic monomers,
  • the comonomer (s) bearing the acetoacetate functionality are introduced at a level of from 1% to 50% by weight, preferably from 7% to 25% by weight, of the total weight of the polymer;
  • the polymer is chosen from polymers obtained by polycondensation such as polyesters, alkyds, polyurethanes, polyamides or polymers obtained by polyaddition such as polyacrylates, polyvinylalcohols or epoxy resins,
  • the alkyd polymer comprises at least one unsaturated fatty acid or not, introduced in a mass quantity strictly greater than 0% by weight and less than or equal to 70% by weight, preferably between 10 and 50% by weight,
  • the alkyd polymer has a molecular weight in weight ranging from 10,000 to
  • the alkyd polymer has an acid number of between 1 and 140, preferably from 10 to 40,
  • the alkyd polymer has an OH number of between 1 and 170, preferably of 25 to 80,
  • the acrylic polymer has a molecular weight in weight ranging from 50,000 to 1,000,000, preferably between 100,000 and 300,000,
  • the acrylic polymer has a glass transition temperature of between -10 ° C. and 60 ° C., preferably between 0 ° C. and 40 ° C.,
  • the coating is a paint or varnish or a stain or a glazer.
  • Another subject of the invention relates to a coating comprising a binder such as described above.
  • Another subject of the invention relates to a process for purifying air, characterized in that a coating comprising a binder as described above is applied and the formaldehyde-fixing function reacts with formaldehyde present in the air. and covalently fixes it.
  • the binder for coating according to the invention is intended to fix the formaldehyde of the air.
  • formaldehyde is meant air, formaldehyde in the free gaseous state.
  • the air is preferentially air inside a house or a building.
  • the binder comprises a polymer chosen from polymers obtained by polycondensation such as polyesters, alkyds, polyurethanes, polyamides or polyaddition-based polymers such as polyacrylates, polyvinylalcohols or epoxy resins. Combinations of these types of binders can be envisaged.
  • the formaldehyde fixing function is an alkyl acetoacetate (formula 1).
  • the polymer is preferably a polymer obtained by polycondensation, preferably a polyester or alkyd. This fixing function is preferably grafted to the polymer by transesterification on a hydroxyl group of the polymer.
  • the formaldehyde scavenger function is a hydrazide function (Formula 2).
  • the polymer is preferably a polymer obtained by polycondensation, preferably a polyester or an alkyd.
  • the hydrazide group is added by reacting hydrazine on the carboxyl groups of the polymer.
  • the formaldehyde fixing function is a dihydrazide function.
  • the polymer is preferably a polymer obtained by polycondensation, preferably an alkyd. Preferably an excess of dihydrazide such as adipic acid dihydrazide reacts with the carbonyl groups of a polymer containing a ketone group.
  • the formaldehyde fixing function of the air is a comonomer bearing at least one acetoacetate function such as, for example, acetoacetoxyethyl methacrylate (AAEM) (formula 3).
  • the polymer is preferably a polymer obtained by polyaddition, preferably an acrylic. The comonomer is preferentially added to a composition of acrylic monomers commonly used in coating binders.
  • the polymer is a polyester obtained by polycondensation between at least one polyol, preferably of greater than or equal to 2, preferably greater than 3, and at least one polyacid, preferably of functionality greater than or equal to 2, and modified by oils or fatty acids in the case of alkyds and possible monoacids.
  • the polyester polymer can be obtained by any conventional method of manufacturing polyester polymers, either by “melting” or “solvent” process.
  • one of the characteristics of these alkyd polymers is the presence in them of at least one unsaturated fatty acid or not, introduced in a mass quantity strictly greater than 0% by weight and less than or equal to 70% by mass, preferably between 10% and 10% by weight. and 50% by weight.
  • the alkyd polymer according to the invention has the following additional characteristics: a weight-average molecular weight ranging from 10,000 to 250000, preferably from 20000 to 90000 and an acid number of between 1 and 140, preferably from 10 to 20, and an index of OH between 1 and 170, preferably from 25 to 80.
  • the polyol used to synthesize alkyds is chosen from hydroxyl-functional polyols greater than or equal to 2, preferably greater than 3, such as, for example and without limitation, butylene diol, diethylene glycol, dipropylene glycol, dipentaerythritol, ethylene glycol, glycoltriethylene, glycol, glycerol, hexane diol, neopentyl glycol, methyl glucoside, pentaerythritol, pentane diol, polyethylene glycol of molecular weight between 300 and 6000 g.
  • hydroxyl-functional polyols greater than or equal to 2, preferably greater than 3, such as, for example and without limitation, butylene diol, diethylene glycol, dipropylene glycol, dipentaerythritol, ethylene glycol, glycoltriethylene, glycol, glycerol, hexane diol, neopentyl glycol, methyl
  • mol "1 propylene glycol, propane-1,3-diol, butane-1,4-diol, sorbitol, isosorbide, xylitol, xylose, benzene-1,2-diol, benzene -1,4-diol, benzene-1,3-diol, triethylene glycol, trimethylolpropane, trimethylolethane, a sugar and cellulose derivatives. Mixtures of these polyols can also be envisaged.
  • the polyacid used to synthesize alkyds is chosen from carboxyl-functional polyacrylic acids of greater than or equal to 2, such as, for example and without limitation, adipic acid or azelaic acid.
  • carboxyl-functional polyacrylic acids of greater than or equal to 2, such as, for example and without limitation, adipic acid or azelaic acid.
  • anhydrides equivalent to the previously described polyacids may also be used, alone or as a mixture.
  • oils and fatty acids are chosen from oils and fatty acids comprising a carbon chain of C8 to C32, preferentially C14 to C22.
  • the fatty acid used to synthesize alkyds is chosen from conjugated or unsaturated unsaturated fatty acids, such as, for example and without limitation, 2-ethylhexanoic acid, linoleic acid, linolenic acid, pinoleic acid, oleic acid, pelargonic acid, alpha-eleostearic acid, alpha-licanic acid, ricinoleic acid, dehydrated ricinoleic acid, vernolic acid.
  • the fatty acid may also be chosen from saturated fatty acids, such as, for example and without limitation, stearic acid. Mixtures of these fatty acids may also be contemplated.
  • the oil used to synthesize alkyds is chosen from conjugated or unsaturated unsaturated oils, such as, for example and without limitation, sunflower oil, linseed, soybean oil, dehydrated castor oil or not, coconut oil. , cotton, tall oil, tung, oitica, soya, sunflower, safflower safflower, grapeseed, olive, palm, flax, perilla, walnuts, carnation .
  • the oil may also be chosen from saturated oils, such as, for example and without limitation, palm oil, hydrogenated castor oil, rapeseed oil, tallow oil, corn oil. Mixtures of these oils can also be considered.
  • the monoacid used to synthesize alkyds is chosen from non-fatty carboxylic mono acids, such as, for example and without limitation, benzoic, butanoic, para-tert-butylbenzoic, propanoic, pentanoic, abietic, rosin, furoic acids, hexanoic, octanoic, decanoic, trans-2-butenoic, 2-oxopropanoic and 4-oxopentanoic. Mixtures of these monoacids can also be envisaged.
  • non-fatty carboxylic mono acids such as, for example and without limitation, benzoic, butanoic, para-tert-butylbenzoic, propanoic, pentanoic, abietic, rosin, furoic acids, hexanoic, octanoic, decanoic, trans-2-butenoic, 2-oxopropanoic and 4-oxopentanoic. Mixtures of these mono
  • a ketone or aldehyde functionality may be added to the polymer by esterification between an acid and an alcohol.
  • the acid used to graft the aldehyde or ketone functionality on the alkyd polymer may be chosen from oxocarboxylic acids, such as, for example and without limitation, acetoacetic acid, 4-oxopentanoic acid, 2-oxopropanoic acid, 4-oxo-octadeca-9,1 1, 13-trienoic acid, dimethyl-keto-caproic acid, methylene acetoacetic acid, ethylidene acetoacetic acid.
  • oxocarboxylic acids such as, for example and without limitation, acetoacetic acid, 4-oxopentanoic acid, 2-oxopropanoic acid, 4-oxo-octadeca-9,1 1, 13-trienoic acid, dimethyl-keto-caproic acid, methylene acetoacetic acid, ethylidene acetoacetic acid.
  • the alcohol used to graft the aldehyde or ketone functionality on the alkyd polymer can be selected from hydroxyketones or hydroxyaldehydes, such as, for example and as non- limiting example, the hydroxyacetone, hydroxybenzaldehyde, 3-hydroxybutanone) and 2 - hydroxy-1, 2-di (phenyl) ethanone).
  • the hydrazide functionality for fixing the formaldehyde is grafted by reaction between the ketone or aldehyde function described above and a polyhydrazide obtainable from carboxyl-functional polyacrylic acids greater than or equal to 2, such as, for example, and non-limiting, adipic acid, azelaic acid, citric acid, diglycolic acid, fumaric acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, maleic acid succinic acid, tartaric acid, sebacic acid, trimellitic acid, terephthalic acid, pyromellitic anhydride, dimer fatty acids, 2,5-furandicarboxylic acid, acid 3, 4-furandicarboxylic and abietic diacid.
  • carboxyl-functional polyacrylic acids greater than or equal to 2
  • the polyhydrazide is introduced at a level of 1% to 50% by weight of the total mass of polymer, preferably between 7% and 25% by mass, ensuring that the molar ratio of polyhydrazide / ketone or aldehyde function is strictly greater than 0, 5 and less than or equal to 1.
  • the hydrazide functionality for fixing the formaldehyde is grafted by condensation between the carboxylic functions of the alkyd and hydrazine.
  • the acetoacetate functionality for fixing the formaldehyde is grafted by transesterification of the free hydroxyl functions of the alkyd with alkylacetoacetates such as t-butyl acetoacetate, ethyl acetoacetate, methyl acetoacetate, isobutyl acetoacetate, isopropyl acetoacetate, n- propyl acetoacetate or n-butyl acetoacetate.
  • the acetoacetate function is grafted at a level of 1% to 50% by weight, preferably 7% to 25% relative to the mass of the alkyd.
  • the alkyd polymer grafted with the functionalities for fixing the formaldehyde undergoes a final stage of dilution into a solvent or dispersion in an aqueous medium or emulsification in order to become the binder according to the invention.
  • the solvent dilution is at a temperature below the evaporation temperature of the solvent.
  • the solvent may be chosen from solvents such as, for example and without limitation, white spirit, Dowanol, isobutanol or solvents of natural origin.
  • the emulsification is preferably carried out in the presence of nonionic and / or anionic surfactants. Emulsification methods are known to those skilled in the art and are therefore not described here.
  • the acrylic polymers are obtained by radical polymerization of acrylic monomers, for example and without limitation: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethyl hexyl acrylate, 2 ethyl hexyl acrylate, 2-ethyl hexyl methacrylate, isoprene, octyl acrylate, octyl methacrylate, iso octyl acrylate, iso octyl methacrylate, glycidyl methacrylate.
  • Comonomers containing unsaturation may be introduced, for example and without limitation: styrene, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, vinyl
  • the functionality for fixing the formaldehyde is grafted onto the polymer by addition of comonomers having the acetoacetate function.
  • the comonomer can be for example and without limitation: 2- (acetoacetoxy) ethyl methacrylate (AAEM), 2- (acetoacetoxy) ethyl acrylate (AAEA), 2- (acetoacetoxy) propyl methacrylate, 2- (acetoacetoxy) propylacrylate.
  • the acrylic polymer containing acetoacetate functions is synthesized in emulsion via a latex.
  • a radical initiator, a catalyst and surfactants are needed.
  • the initiator may be chosen from hydrogen peroxide, ammonium persulfate, dibenzoyl peroxide, 2,24-azobisisobutonitrile, azonitrile derivatives, etc.
  • the catalyst is a metal derivative capable of decomposing the initiator.
  • the acrylic polymer according to the invention has the following additional characteristics: a weight-average molecular weight ranging from 50,000 to 1,000,000, preferably between 100,000 and 300,000, and / or a glass transition temperature of between -10 ° C. and 60 ° C., preferably between 0 ° C and 40 ° C.
  • the glass transition temperature of the binder according to the invention is preferably less than 40 ° C to allow the formation of film at room temperature during drying.
  • the hydrazide and acetoacetate functions for fixing the formaldehyde of the air tend to increase this glass transition temperature or to cause excessive crosslinking characterized by macroscopic defects of the formed film such as cracks or detachments. It was therefore not obvious to provide a polymeric binder that contains sufficient formaldehyde-fixing functions of air to be effective while allowing for the formation of satisfactory coating film.
  • One or more alkyd emulsions bearing one or more formaldehyde-fixing functional groups may be mixed with one or more aqueous dispersions of acrylic polymers carrying one or more formaldehyde-fixing functional groups in order to obtain a binder having the desired properties according to the application .
  • the combination can be a simple mixture of the two binders.
  • the combination can also be reactive, forming a hybrid.
  • a formaldehyde-fixing acrylic binder bearing carboxyl groups with the hydroxyl groups of an alkyd binding binder (or not) of formaldehyde.
  • Acrylic acid being used as a comonomer.
  • the coating binder according to the invention covalently binds formaldehyde. This fixation is permanent, there is no subsequent rejection of formaldehyde and this especially because the binder is stable. Indeed, the binder comprises a polymer and therefore with a high molecular weight limiting its migration or its modification over time.
  • the binder according to the invention is easily integrable with different coating formulations.
  • the binder is stable in dispersion in water.
  • the binder according to the invention is a film-forming binder.
  • film-forming agent means a polymer capable, in less than 6 hours and at a temperature of between 5 and 30 ° C., of passing from the liquid state to the solid state, forming a film that is dry to the touch, homogeneous, taut, continuous and adherent. and this by any physical and / or chemical drying mechanism, in the presence or absence of a catalyst.
  • the coatings that can incorporate the binder according to the invention are various such as for example: Primary paint and finishing paint for walls, ceilings, floors, woodwork, furniture regardless of the material including kitchen furniture type closets and worktops. Indeed, the cooking stages in the kitchen are an additional source of formaldehyde emission.
  • Nail polish in particular to limit the exposure of smokers to formaldehyde
  • Textiles curtains, fabrics used in the automobile, nonwoven
  • the coatings incorporating the binder according to the invention are intended to be used on preferentially non-porous, non-fibrous substrates such as for example cement, a cinder block, a melamine panel, an old paint, plaster, wood, a metal , a plastic.
  • These supports are said closed. That is to say, a flow of air can not, or hardly, cross them.
  • This type of support differs from media such as filters that are said to be open because a flow of air can easily pass through them.
  • the coating has a sanitizing effect as soon as it is applied, more specifically as soon as it is dry, ie at least 1 hour, preferably 6 hours, after application.
  • the invention relates to a process for purifying air, characterized in that a coating comprising a binder as described above is applied, and that the formaldehyde-fixing function reacts with formaldehyde present in the air. and fixes it covalently
  • the coating requires a single coat of paint to clean the air. However, it is possible to apply several layers, in particular for support coverage issues without effect on the cleaning power of the coating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to a binder for coatings, including a polymer having at least one function for binding formaldehyde, which is used to react with the formaldehyde present in air in order to bind same covalently. Said binder is useful for decorative or industrial coatings that can be applied to various media in order to sanitize the quality of the internal air of a room by binding the free formaldehyde.

Description

"Liant pour revêtement comprenant une fonction fixatrice de formaldéhyde de l'air "  "Binder for coating comprising a fixing function of formaldehyde of air"
La présente invention concerne un liant pour revêtement comprenant une fonction fixatrice de formaldéhyde de l'air. The present invention relates to a coating binder comprising a formaldehyde-fixing function of air.
Elle trouvera son application pour les revêtements décoratifs ou industriels pouvant être appliqués sur divers supports pour assainir la qualité de l'air intérieur d'une pièce en fixant le formaldéhyde libre.  It will find its application for decorative or industrial coatings that can be applied on various substrates to clean up the indoor air quality of a room by fixing the free formaldehyde.
En effet, l'air intérieur est un enjeu majeur de santé publique. Il est 5 à 10 fois plus pollué que l'air extérieur. Plusieurs composés organiques volatils sont cités notamment le benzène et le formaldéhyde.  In fact, indoor air is a major public health issue. It is 5 to 10 times more polluted than outside air. Several volatile organic compounds are mentioned including benzene and formaldehyde.
Le formaldéhyde est un polluant très répandu dans l'air intérieur. Il provient de différentes sources comme les meubles, les tapis, les cuissons ménagères, les textiles d'ameublement, les fumées de cigarette, le contre-plaqué, les panneaux mélaminés, etc.... Depuis 2004, il est classé comme cancérogène par le CIRC (Centre International de Recherche contre le Cancer). Le formaldéhyde provoque des irritations et des inflammations des yeux, des voies respiratoires et de la peau. Il peut également avoir des conséquences neurologiques qui se traduisent par une fatigue accrue, des migraines, des nausées et des vertiges. La principale solution proposée à ce jour sont des filtres placés dans les pièces à assainir et au travers desquels l'air qui circule est débarrassé du formaldéhyde présent. Formaldehyde is a pollutant that is very common in indoor air. It comes from different sources such as furniture, carpets, household cooking, upholstery, cigarette smoke, plywood, melamine panels, etc. Since 2004, it has been classified as a carcinogen by IARC (International Agency for Research Against Cancer). Formaldehyde causes irritation and inflammation of the eyes, respiratory tract and skin. It can also have neurological consequences that result in increased fatigue, migraines, nausea and vertigo. The main solution proposed to date are filters placed in rooms to be cleaned and through which the circulating air is cleared of formaldehyde present.
L'efficacité de ces filtres est limitée par le flux d'air les traversant. Ce flux est le plus souvent amélioré par une pompe, ce qui entraîne une consommation d'énergie et une pollution sonore plus importante. De plus, ces filtres sont particulièrement inesthétiques. Selon la concentration du formaldéhyde présent, les filtres sont rapidement saturés et il faut alors les changer pour maintenir l'assainissement.  The efficiency of these filters is limited by the flow of air passing through them. This flow is most often improved by a pump, resulting in higher energy consumption and noise pollution. In addition, these filters are particularly unsightly. Depending on the concentration of formaldehyde present, the filters are quickly saturated and need to be changed to maintain sanitation.
Une autre solution est représentée par les revêtements à base de nanoparticules qui décomposent des composés organiques volatils dont le formaldéhyde par photocatalyse. Cette technique nécessite une exposition à la lumière, ce qui la rend plus qu'aléatoire en termes d'efficacité. De plus la désorption des COV captés est élevée dans le temps et les nanoparticules sont elles-mêmes aisément désolidarisées de leur support et sont donc relarguées dans l'environnement. Les risques liés à la manipulation et à l'exposition de nanoparticules restent insuffisamment connus. La fabrication de peintures contenant des nanoparticules implique donc un risque pour les opérateurs. De plus, le grand public n'est pas prêt à utiliser des produits à base de nanoparticules (risque pour les enfants qui pourraient ingérer des écailles de ce type de peinture).  Another solution is represented by nanoparticle-based coatings which break down volatile organic compounds including formaldehyde by photocatalysis. This technique requires exposure to light, which makes it more than random in terms of efficiency. In addition, the desorption of captured VOCs is high in time and the nanoparticles themselves are easily separated from their support and are released into the environment. The risks associated with the manipulation and exposure of nanoparticles remain insufficiently known. The manufacture of paints containing nanoparticles therefore involves a risk for the operators. In addition, the general public is not ready to use products based on nanoparticles (risk for children who could ingest scales of this type of paint).
Il existe donc le besoin de proposer une solution pour assainir l'air intérieur qui résolve tout ou partie de ces inconvénients. There is therefore the need to propose a solution for cleaning the indoor air that solves all or part of these disadvantages.
A cet effet, la présente invention concerne un liant pour revêtement comprenant un polymère portant au moins une fonction fixatrice de formaldéhyde destinée à réagir avec du formaldéhyde présent dans l'air pour le fixer de manière covalente.  To this end, the present invention relates to a coating binder comprising a polymer carrying at least one formaldehyde-fixing function for reacting with formaldehyde present in the air to covalently fix it.
Le liant présente l'avantage de fixer de manière permanente et irréversible le formaldéhyde de l'air. La fixation se fait de manière covalente. Il n'y a pas de rejet ultérieur de formaldéhyde et ce notamment du fait que le liant est stable. En effet, le liant comprend un polymère de poids moléculaire élevé limitant sa migration ou sa modification au cours du temps. Le liant est un composé non volatil.  The binder has the advantage of permanently and irreversibly fixing the formaldehyde of the air. Fixation is covalent. There is no subsequent rejection of formaldehyde, particularly because the binder is stable. Indeed, the binder comprises a high molecular weight polymer limiting its migration or its modification over time. The binder is a non-volatile compound.
Le liant selon l'invention est facilement intégrable à différentes formulations de revêtement. Un revêtement tel que par exemple de la peinture est un élément particulièrement présent dans l'habitat ce qui permet d'avoir des surfaces de peinture et donc des surfaces actives importantes tout en étant non invasives. D'autres buts et avantages apparaîtront au cours de la description qui suit de l'invention.  The binder according to the invention is easily integrable with different coating formulations. A coating such as for example paint is a particularly present in the habitat which allows to have paint surfaces and therefore important active surfaces while being non-invasive. Other objects and advantages will become apparent from the following description of the invention.
On rappelle que l'invention concerne un liant pour revêtement comprenant un polymère portant au moins une fonction fixatrice de formaldéhyde destinée à réagir avec du formaldéhyde présent dans l'air pour le fixer de manière covalente. It is recalled that the invention relates to a binder for coating comprising a polymer carrying at least one formaldehyde scavenger function for reacting with formaldehyde present in the air to covalently fix it.
Suivant des variantes préférées mais non limitatives pouvant être alternatives ou cumulatives, le liant est tel que :  According to preferred but nonlimiting variants that may be alternative or cumulative, the binder is such that:
- la fonction fixatrice est une fonction acétoacétate greffée par transestérification sur au moins une fonction hydroxyle d'un polymère,  the fixing function is a function acetoacetate grafted by transesterification on at least one hydroxyl function of a polymer,
- la fonction acétoacétate est greffée à hauteur de 1 % à 50% massique, préférentiellement 7% à 25% par rapport à la masse du polymère,  the acetoacetate function is grafted at a level of 1% to 50% by weight, preferably 7% to 25% relative to the weight of the polymer,
- la fonction fixatrice est une fonction hydrazide greffée par condensation de l'hydrazine sur au moins une fonction carboxylique d'un polymère,  the fixing function is a hydrazide function grafted by condensation of hydrazine on at least one carboxylic function of a polymer,
- la fonction fixatrice est une fonction hydrazide greffée par réaction d'un polyhydrazide avec au moins une fonction carbonyle (cétone ou aldéhyde) d'un polymère,  the fixing function is a hydrazide function grafted by reaction of a polyhydrazide with at least one carbonyl (ketone or aldehyde) function of a polymer,
- la fonction fixatrice est un comonomère fixateur de formaldéhyde portant au moins une fonction acétoacétate tel que l'AAEM ajouté à des monomères acryliques, the fixing function is a formaldehyde-fixing comonomer carrying at least one acetoacetate function such as AAEM added to acrylic monomers,
- le ou les comonomère(s) portant la fonctionnalité acétoacétate sont introduits à hauteur de 1 % à 50% massique, de préférence de 7% à 25% massique, de la masse totale du polymère, the comonomer (s) bearing the acetoacetate functionality are introduced at a level of from 1% to 50% by weight, preferably from 7% to 25% by weight, of the total weight of the polymer;
- le polymère est choisi parmi les polymères obtenus par polycondensation tels que les polyesters, alkydes, polyuréthanes, polyamides ou les polymères obtenus par polyaddition tels que les polyacrylates, polyvinylalcools ou les résines époxy,  the polymer is chosen from polymers obtained by polycondensation such as polyesters, alkyds, polyurethanes, polyamides or polymers obtained by polyaddition such as polyacrylates, polyvinylalcohols or epoxy resins,
- le polymère alkyde comprend au moins un acide gras, insaturé ou non, introduit en quantité massique strictement supérieure à 0% en masse et inférieure ou égale à 70 % en masse, de préférence entre 10 et 50 % en masse,  the alkyd polymer comprises at least one unsaturated fatty acid or not, introduced in a mass quantity strictly greater than 0% by weight and less than or equal to 70% by weight, preferably between 10 and 50% by weight,
- le polymère alkyde a une masse moléculaire en poids allant de 10000 à the alkyd polymer has a molecular weight in weight ranging from 10,000 to
250000, préférentiellement de 20000 à 90000, 250000, preferably from 20000 to 90000,
- le polymère alkyde a un indice d'acide compris entre 1 et 140 préférentiellement de 10 à 40,  the alkyd polymer has an acid number of between 1 and 140, preferably from 10 to 40,
- le polymère alkyde a un indice d'OH compris entre 1 et 170, préférentiellement de 25 à 80,  the alkyd polymer has an OH number of between 1 and 170, preferably of 25 to 80,
- le polymère acrylique a une masse moléculaire en poids allant de 50000 à 1000000, préférablement entre 100000 et 300000,  the acrylic polymer has a molecular weight in weight ranging from 50,000 to 1,000,000, preferably between 100,000 and 300,000,
- le polymère acrylique a une température de transition vitreuse comprise entre - 10°C et 60°C, préférablement entre 0°C et 40°C,  the acrylic polymer has a glass transition temperature of between -10 ° C. and 60 ° C., preferably between 0 ° C. and 40 ° C.,
- le revêtement est une peinture ou un vernis ou une lasure ou un vitrificateur. - The coating is a paint or varnish or a stain or a glazer.
Un autre objet de l'invention concerne un revêtement comprenant un liant tel que décrit ci-dessus. Another subject of the invention relates to a coating comprising a binder such as described above.
Un autre objet de l'invention concerne un procédé pour assainir de l'air caractérisé en ce qu'on applique un revêtement comprenant un liant tel que décrit ci- dessus et que la fonction fixatrice de formaldéhyde réagit avec du formaldéhyde présent dans l'air et le fixe de manière covalente.  Another subject of the invention relates to a process for purifying air, characterized in that a coating comprising a binder as described above is applied and the formaldehyde-fixing function reacts with formaldehyde present in the air. and covalently fixes it.
Le liant pour revêtement selon l'invention est destiné à fixer le formaldéhyde de l'air. On entend par formaldéhyde de l'air, le formaldéhyde à l'état gazeux libre. L'air est préférentiellement de l'air intérieur d'une habitation ou d'un bâtiment.  The binder for coating according to the invention is intended to fix the formaldehyde of the air. By formaldehyde is meant air, formaldehyde in the free gaseous state. The air is preferentially air inside a house or a building.
Le liant comprend un polymère choisi parmi les polymères obtenus par polycondensation tels que les polyesters, alkydes, polyuréthanes, polyamides ou les polymères obtenus par polyaddition tels que les polyacrylates, polyvinylalcools ou les résines époxy. Des combinaisons de ces types de liants peuvent être envisagées.  The binder comprises a polymer chosen from polymers obtained by polycondensation such as polyesters, alkyds, polyurethanes, polyamides or polyaddition-based polymers such as polyacrylates, polyvinylalcohols or epoxy resins. Combinations of these types of binders can be envisaged.
Selon un mode de réalisation la fonction fixatrice de formaldéhyde est un alkyl acétoacétate (formule 1 ). Le polymère est préférentiellement un polymère obtenu par polycondensation de préférence un polyester ou alkyde. Cette fonction fixatrice est préférentiellement greffée au polymère par transestérification sur un groupement hydroxyle du polymère.  According to one embodiment, the formaldehyde fixing function is an alkyl acetoacetate (formula 1). The polymer is preferably a polymer obtained by polycondensation, preferably a polyester or alkyd. This fixing function is preferably grafted to the polymer by transesterification on a hydroxyl group of the polymer.
Figure imgf000005_0001
Figure imgf000005_0001
Formule 1 : alkyl acétoacétate  Formula 1: alkyl acetoacetate
Selon un autre mode de réalisation, la fonction fixatrice de formaldéhyde est une fonction hydrazide (Formule 2). Le polymère est préférentiellement un polymère obtenu par polycondensation de préférence un polyester ou un alkyde. Préférentiellement, le groupement hydrazide est ajouté en faisant réagir de l'hydrazine sur les groupements carboxyles du polymère.
Figure imgf000005_0002
In another embodiment, the formaldehyde scavenger function is a hydrazide function (Formula 2). The polymer is preferably a polymer obtained by polycondensation, preferably a polyester or an alkyd. Preferably, the hydrazide group is added by reacting hydrazine on the carboxyl groups of the polymer.
Figure imgf000005_0002
Formule 2 : alkyl hydrazide  Formula 2: alkyl hydrazide
Selon un autre mode de réalisation, la fonction fixatrice de formaldéhyde est une fonction dihydrazide. Le polymère est préférentiellement un polymère obtenu par polycondensation de préférence un alkyde. Préférentiellement un excès de dihydrazide tel que l'acide adipique dihydrazide réagit avec les groupements carbonyles d'un polymère contenant un groupement cétone. Selon un autre mode de réalisation, la fonction fixatrice de formaldéhyde de l'air est un comonomère portant au moins une fonction acétoacétate tel que par exemple de l'acétoacétoxyéthyl méthacrylate (AAEM) (formule 3). Le polymère est préférentiellement un polymère obtenu par polyaddition, de préférence un acrylique. Le comonomère est préférentiellement ajouté à une composition de monomères acryliques couramment utilisés dans les liants pour revêtements.
Figure imgf000006_0001
According to another embodiment, the formaldehyde fixing function is a dihydrazide function. The polymer is preferably a polymer obtained by polycondensation, preferably an alkyd. Preferably an excess of dihydrazide such as adipic acid dihydrazide reacts with the carbonyl groups of a polymer containing a ketone group. According to another embodiment, the formaldehyde fixing function of the air is a comonomer bearing at least one acetoacetate function such as, for example, acetoacetoxyethyl methacrylate (AAEM) (formula 3). The polymer is preferably a polymer obtained by polyaddition, preferably an acrylic. The comonomer is preferentially added to a composition of acrylic monomers commonly used in coating binders.
Figure imgf000006_0001
Formule 3 : acétoacétoxyéthyl méthacrylate (AAEM) Suivant un mode de réalisation, le polymère est un polyester obtenu par polycondensation entre au moins un polyol, préférentiellement de fonctionnalité supérieure ou égale à 2, préférentiellement supérieure à 3, et au moins un polyacide, préférentiellement de fonctionnalité supérieure ou égale à 2, et modifié par des huiles ou acides gras dans le cas des alkydes et d'éventuels monoacides.  Formula 3: Acetoacetoxyethyl Methacrylate (AAEM) According to one embodiment, the polymer is a polyester obtained by polycondensation between at least one polyol, preferably of greater than or equal to 2, preferably greater than 3, and at least one polyacid, preferably of functionality greater than or equal to 2, and modified by oils or fatty acids in the case of alkyds and possible monoacids.
Le polymère polyester peut être obtenu par tout procédé conventionnel de fabrication de polymères polyesters, soit par procédé « fusion » soit par procédé «solvant».  The polyester polymer can be obtained by any conventional method of manufacturing polyester polymers, either by "melting" or "solvent" process.
Avantageusement, une des caractéristiques de ces polymères alkydes est la présence dans ceux-ci d'au moins un acide gras insaturé ou non, introduit en quantité massique strictement supérieure à 0% massique et inférieure ou égale à 70% massique, de préférence entre 10 et 50 % en masse.  Advantageously, one of the characteristics of these alkyd polymers is the presence in them of at least one unsaturated fatty acid or not, introduced in a mass quantity strictly greater than 0% by weight and less than or equal to 70% by mass, preferably between 10% and 10% by weight. and 50% by weight.
Le polymère alkyde selon l'invention possède les caractéristiques supplémentaires suivantes : une masse moléculaire en poids allant de 10000 à 250000, préférentiellement de 20000 à 90000 et un indice d'acide compris entre 1 et 140 préférentiellement de 10 à 20 et un indice d'OH compris entre 1 et 170, préférentiellement de 25 à 80.  The alkyd polymer according to the invention has the following additional characteristics: a weight-average molecular weight ranging from 10,000 to 250000, preferably from 20000 to 90000 and an acid number of between 1 and 140, preferably from 10 to 20, and an index of OH between 1 and 170, preferably from 25 to 80.
Selon un mode de réalisation préféré, le polyol utilisé pour synthétiser des alkydes est choisi parmi les polyols à fonctionnalité hydroxyle supérieure ou égale à 2, préférentiellement supérieure à 3, tel que, par exemple et à titre non-limitatif, le butylène diol, le diéthylène glycol, le dipropylène glycol, le dipentaérythritol, l'éthylène glycol, le glycoltriéthylène, le glycol, le glycérol, l'hexane diol, le néopentyl glycol, le méthyle glucoside, le pentaérythritol, le pentane diol, le polyéthylène glycol de masse moléculaire comprise entre 300 et 6000 g. mol"1, le propylène glycol, le propane-1 ,3- diol, le butane-1 ,4-diol, le sorbitol, l'isosorbide, le xylitol, le xylose, le benzène-1 ,2-diol, le benzène-1 ,4-diol, le benzène-1 ,3-diol, le triéthylène glycol, le triméthylolpropane, le triméthyloléthane, un sucre et les dérivés cellulosiques. Des mélanges de ces polyols peuvent aussi être envisagés. According to a preferred embodiment, the polyol used to synthesize alkyds is chosen from hydroxyl-functional polyols greater than or equal to 2, preferably greater than 3, such as, for example and without limitation, butylene diol, diethylene glycol, dipropylene glycol, dipentaerythritol, ethylene glycol, glycoltriethylene, glycol, glycerol, hexane diol, neopentyl glycol, methyl glucoside, pentaerythritol, pentane diol, polyethylene glycol of molecular weight between 300 and 6000 g. mol "1 , propylene glycol, propane-1,3-diol, butane-1,4-diol, sorbitol, isosorbide, xylitol, xylose, benzene-1,2-diol, benzene -1,4-diol, benzene-1,3-diol, triethylene glycol, trimethylolpropane, trimethylolethane, a sugar and cellulose derivatives. Mixtures of these polyols can also be envisaged.
Selon un mode de réalisation préféré, le polyacide utilisé pour synthétiser des alkydes est choisi parmi les polyacides carboxyliques à fonctionnalité carboxyle supérieure ou égale à 2, tel que, par exemple et à titre non-limitatif, l'acide adipique, l'acide azélaïque, l'acide citrique, l'acide diglycolique, l'acide fumarique, l'acide isophtalique, l'acide phtalique, l'acide tétrahydrophtalique, l'acide maléique, l'acide succinique, l'acide tartrique, l'acide sébacique, l'acide triméllitique, l'acide téréphtalique, l'anhydride pyroméllitique, les acides gras dimères, l'acide 2,5- furandicarboxylique, l'acide 3,4-furandicarboxylique et le diacide abiétique. Des mélanges de ces polyacides peuvent aussi être envisagés.  According to a preferred embodiment, the polyacid used to synthesize alkyds is chosen from carboxyl-functional polyacrylic acids of greater than or equal to 2, such as, for example and without limitation, adipic acid or azelaic acid. citric acid, diglycolic acid, fumaric acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, maleic acid, succinic acid, tartaric acid, sebacic acid , trimellitic acid, terephthalic acid, pyromellitic anhydride, dimer fatty acids, 2,5-furandicarboxylic acid, 3,4-furandicarboxylic acid and abietic diacid. Mixtures of these polyacids can also be envisaged.
Les anhydrides équivalents aux polyacides précédemment décrits peuvent aussi être utilisés, seuls ou en mélange.  The anhydrides equivalent to the previously described polyacids may also be used, alone or as a mixture.
Les huiles et acides gras sont choisis parmi des huiles et acides gras comprenant une chaîne carbonée de C8 à C32, préférentiellement C14 à C22.  The oils and fatty acids are chosen from oils and fatty acids comprising a carbon chain of C8 to C32, preferentially C14 to C22.
Préférentiellement, l'acide gras utilisé pour synthétiser des alkydes est choisi parmi les acides gras insaturés conjugués ou non, tel que, par exemple et à titre non- limitatif, l'acide éthyl-2-hexanoïque, l'acide linoléique, l'acide linolénique, l'acide pinoléique, l'acide oléique, l'acide pélargonique, l'acide alpha-éléostéarique, l'acide alpha-licanique, l'acide ricinoléique, l'acide ricinoléique déshydraté, l'acide vernolique. L'acide gras peut aussi être choisi parmi les acides gras saturés, tel que, par exemple et à titre non-limitatif, l'acide stéarique. Des mélanges de ces acides gras peuvent aussi être envisagés.  Preferably, the fatty acid used to synthesize alkyds is chosen from conjugated or unsaturated unsaturated fatty acids, such as, for example and without limitation, 2-ethylhexanoic acid, linoleic acid, linolenic acid, pinoleic acid, oleic acid, pelargonic acid, alpha-eleostearic acid, alpha-licanic acid, ricinoleic acid, dehydrated ricinoleic acid, vernolic acid. The fatty acid may also be chosen from saturated fatty acids, such as, for example and without limitation, stearic acid. Mixtures of these fatty acids may also be contemplated.
Préférentiellement, l'huile utilisée pour synthétiser des alkydes est choisie parmi les huiles insaturées conjuguées ou non, tel que, par exemple et à titre non-limitatif, huile de tournesol, de lin, de soya, de ricin déshydratée ou non, de coco, de coton, de tall oil, de tung, d'oïticica, de soja, de tournesol, de carthame des teinturiers, de pépins de raisin, d'olive, de palme, de lin, de perilla, de noix, d'œillette. L'huile peut aussi être choisie parmi les huiles saturées, tel que, par exemple et à titre non-limitatif, l'huile de palme, de ricin hydrogénée, de colza, de tallow, de maïs. Des mélanges de ces huiles peuvent aussi être envisagés.  Preferably, the oil used to synthesize alkyds is chosen from conjugated or unsaturated unsaturated oils, such as, for example and without limitation, sunflower oil, linseed, soybean oil, dehydrated castor oil or not, coconut oil. , cotton, tall oil, tung, oitica, soya, sunflower, safflower safflower, grapeseed, olive, palm, flax, perilla, walnuts, carnation . The oil may also be chosen from saturated oils, such as, for example and without limitation, palm oil, hydrogenated castor oil, rapeseed oil, tallow oil, corn oil. Mixtures of these oils can also be considered.
Préférentiellement, le monoacide utilisé pour synthétiser des alkydes est choisi parmi les mono acides carboxyliques non gras, tel que, par exemple et à titre non- limitatif, les acides benzoïque, butanoïque, para tertiobutylbenzoïque, propanoïque, pentanoïque, abiétique, colophane, furoïque, hexanoïque, octanoïque, décanoïque, trans-2-buténoïque, 2-oxopropanoïque et 4-oxopentanoïque. Des mélanges de ces monoacides peuvent aussi être envisagés. Preferably, the monoacid used to synthesize alkyds is chosen from non-fatty carboxylic mono acids, such as, for example and without limitation, benzoic, butanoic, para-tert-butylbenzoic, propanoic, pentanoic, abietic, rosin, furoic acids, hexanoic, octanoic, decanoic, trans-2-butenoic, 2-oxopropanoic and 4-oxopentanoic. Mixtures of these monoacids can also be envisaged.
Une fonctionnalité cétone ou aldéhyde peut être ajoutée au polymère par estérification entre un acide et un alcool.  A ketone or aldehyde functionality may be added to the polymer by esterification between an acid and an alcohol.
L'acide utilisé pour greffer la fonctionnalité aldéhyde ou cétone sur le polymère alkyde peut être choisi parmi les acides oxocarboxyliques, tels que, par exemple et à titre non-limitatif, l'acide acétoacétique, l'acide 4-oxopentanoïque, l'acide 2- oxopropanoïque, l'acide 4-oxo-octadéca-9,1 1 ,13-trienoïque, l'acide diméthyl-keto- caproïque, méthylène acétoacétique, éthylidene acétoacétique. L'alcool utilisé pour greffer la fonctionnalité aldéhyde ou cétone sur le polymère alkyde peut être choisi parmi les hydroxycétones ou hydroxyaldéhydes, tels que, par exemple et à titre non- limitatif, l'hydroxyacétone, hydroxybenzaldéhyde, le 3-hydroxybutanone) et le 2- hydroxy-1 ,2-di(phényl)éthanone). The acid used to graft the aldehyde or ketone functionality on the alkyd polymer may be chosen from oxocarboxylic acids, such as, for example and without limitation, acetoacetic acid, 4-oxopentanoic acid, 2-oxopropanoic acid, 4-oxo-octadeca-9,1 1, 13-trienoic acid, dimethyl-keto-caproic acid, methylene acetoacetic acid, ethylidene acetoacetic acid. The alcohol used to graft the aldehyde or ketone functionality on the alkyd polymer can be selected from hydroxyketones or hydroxyaldehydes, such as, for example and as non- limiting example, the hydroxyacetone, hydroxybenzaldehyde, 3-hydroxybutanone) and 2 - hydroxy-1, 2-di (phenyl) ethanone).
Selon une possibilité, la fonctionnalité hydrazide permettant de fixer le formaldéhyde est greffée par réaction entre la fonction cétone ou aldéhyde décrite précédemment et un polyhydrazide pouvant être obtenu à partir des polyacides carboxyliques à fonctionnalité carboxyle supérieure ou égale à 2, tel que, par exemple et à titre non-limitatif, l'acide adipique, l'acide azélaïque, l'acide citrique, l'acide diglycolique, l'acide fumarique, l'acide isophtalique, l'acide phtalique, l'acide tétrahydrophtalique, l'acide maléique, l'acide succinique, l'acide tartrique, l'acide sébacique, l'acide triméllitique, l'acide téréphtalique, l'anhydride pyroméllitique, les acides gras dimères, l'acide 2,5-furandicarboxylique, l'acide 3,4-furandicarboxylique et le diacide abiétique. Le polyhydrazide est introduit à hauteur de 1 % à 50% massique de la masse totale de polymère, préférablement entre 7% et 25% massique, en veillant à ce que le ratio molaire de polyhydrazide/fonction cétone ou aldéhyde soit strictement supérieur à 0,5 et inférieur ou égal à 1.  According to one possibility, the hydrazide functionality for fixing the formaldehyde is grafted by reaction between the ketone or aldehyde function described above and a polyhydrazide obtainable from carboxyl-functional polyacrylic acids greater than or equal to 2, such as, for example, and non-limiting, adipic acid, azelaic acid, citric acid, diglycolic acid, fumaric acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, maleic acid succinic acid, tartaric acid, sebacic acid, trimellitic acid, terephthalic acid, pyromellitic anhydride, dimer fatty acids, 2,5-furandicarboxylic acid, acid 3, 4-furandicarboxylic and abietic diacid. The polyhydrazide is introduced at a level of 1% to 50% by weight of the total mass of polymer, preferably between 7% and 25% by mass, ensuring that the molar ratio of polyhydrazide / ketone or aldehyde function is strictly greater than 0, 5 and less than or equal to 1.
Selon une autre possibilité, la fonctionnalité hydrazide permettant de fixer le formaldéhyde est greffée par condensation entre les fonctions carboxyliques de l'alkyde et l'hydrazine.  According to another possibility, the hydrazide functionality for fixing the formaldehyde is grafted by condensation between the carboxylic functions of the alkyd and hydrazine.
Selon un mode de réalisation, la fonctionnalité acétoacétate permettant de fixer le formaldéhyde est greffée par transestérification des fonctions hydroxyles libres de l'alkyde avec des alkylacétoacétates tels que t-butyl acétoacétate, éthyl acétoacétate, méthyl acétoacétate, isobutyl acétoacétate, isopropyl acétoacétate, n-propyl acétoacétate ou n-butyl acétoacétate. Préférentiellement, la fonction acétoacétate est greffée à hauteur de 1 % à 50% massique, préférentiellement 7% à 25% par rapport à la masse de l'alkyde. Avantageusement, le polymère alkyde greffé par les fonctionnalités permettant de fixer le formaldéhyde subit une dernière étape de dilution en solvant ou de dispersion en milieu aqueux ou mise en émulsion afin de devenir le liant selon l'invention. According to one embodiment, the acetoacetate functionality for fixing the formaldehyde is grafted by transesterification of the free hydroxyl functions of the alkyd with alkylacetoacetates such as t-butyl acetoacetate, ethyl acetoacetate, methyl acetoacetate, isobutyl acetoacetate, isopropyl acetoacetate, n- propyl acetoacetate or n-butyl acetoacetate. Preferably, the acetoacetate function is grafted at a level of 1% to 50% by weight, preferably 7% to 25% relative to the mass of the alkyd. Advantageously, the alkyd polymer grafted with the functionalities for fixing the formaldehyde undergoes a final stage of dilution into a solvent or dispersion in an aqueous medium or emulsification in order to become the binder according to the invention.
La dilution en solvant se fait à une température inférieure à la température d'évaporation du solvant. Le solvant peut être choisi parmi les solvants tels que, par exemple et à titre non-limitatif le white-spirit, le Dowanol, l'isobutanol ou les solvants d'origine naturelle. L'émulsification est préférentiellement réalisée en présence de tensioactifs non ioniques et/ou anioniques. Les méthodes d'émulsification sont connues de l'homme de l'art et ne sont, par conséquent, pas décrites ici.  The solvent dilution is at a temperature below the evaporation temperature of the solvent. The solvent may be chosen from solvents such as, for example and without limitation, white spirit, Dowanol, isobutanol or solvents of natural origin. The emulsification is preferably carried out in the presence of nonionic and / or anionic surfactants. Emulsification methods are known to those skilled in the art and are therefore not described here.
Les polymères acryliques sont obtenus par polymérisation radicalaire de monomères acryliques, par exemple et à titre non limitatif : le méthyl acrylate, méthyl méthacrylate, éthyl acrylate, éthyl méthacrylate, butyl acrylate, butyl méthacrylate, isobutyle acrylate, isobutyle méthacrylate, éthyl hexyl acrylate, 2-ethyl hexyl acrylate, 2-éthyl hexyl méthacrylate, isoprène, octyl acrylate, octyl méthacrylate, iso octyl acrylate, iso octyl méthacrylate, glycidyl méthacrylate. Des comonomères contenant une insaturation peuvent être introduits comme par exemple et à titre non limitatif : le styrène, l'acide acrylique, l'acide méthacrylique, l'acide itaconique, l'acide crotonique, l'acide fumarique, l'acide maléique, les esters vinyliques.  The acrylic polymers are obtained by radical polymerization of acrylic monomers, for example and without limitation: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethyl hexyl acrylate, 2 ethyl hexyl acrylate, 2-ethyl hexyl methacrylate, isoprene, octyl acrylate, octyl methacrylate, iso octyl acrylate, iso octyl methacrylate, glycidyl methacrylate. Comonomers containing unsaturation may be introduced, for example and without limitation: styrene, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, vinyl esters.
La fonctionnalité permettant de fixer le formaldéhyde est greffée sur le polymère par ajout de comonomères possédant la fonction acétoacétate. Le comonomère peut être par exemple et à titre non limitatif : le 2-(acétoacétoxy)éthyl méthacrylate (AAEM), 2-(acétoacétoxy)éthyl acrylate (AAEA), 2-(acétoacétoxy)propyl méthacrylate, 2- (acétoacétoxy) propylacrylate. Ces comonomères portant la fonctionnalité acétoacétate sont introduits à hauteur de 1 % à 50% massique, de préférence de 7% à 25% massique, de la masse totale du polymère.  The functionality for fixing the formaldehyde is grafted onto the polymer by addition of comonomers having the acetoacetate function. The comonomer can be for example and without limitation: 2- (acetoacetoxy) ethyl methacrylate (AAEM), 2- (acetoacetoxy) ethyl acrylate (AAEA), 2- (acetoacetoxy) propyl methacrylate, 2- (acetoacetoxy) propylacrylate. These comonomers carrying the acetoacetate functionality are introduced at a level of from 1% to 50% by weight, preferably from 7% to 25% by weight, of the total weight of the polymer.
Le polymère acrylique contenant des fonctions acétoacétates est synthétisé en émulsion via un latex. Un initiateur radicalaire, un catalyseur et des tensioactifs sont nécessaires. L'initiateur peut être choisi parmi le péroxyde d'hydrogène, persulfate d'ammonium, péroxyde de dibenzoyl, 2,24-azobisisobuteronitrile, dérivés azonitriles, etc .. Le catalyseur est un dérivé de métal capable de décomposer l'initiateur. Le polymère acrylique selon l'invention possède les caractéristiques supplémentaires suivantes : une masse moléculaire en poids allant de 50000 à 1000000, préférablement entre 100000 et 300000, et/ou une température de transition vitreuse comprise entre -10°C et 60°C, préférablement entre 0°C et 40°C. La température de transition vitreuse du liant selon l'invention est préférentiellement inférieure à 40°C afin de permettre la formation de feuil à température ambiante lors du séchage. Or, les fonctions hydrazides et acétoacétates destinées à fixer le formaldéhyde de l'air ont tendance à augmenter cette température de transition vitreuse ou à provoquer une réticulation excessive se caractérisant par des défauts macroscopiques du feuil formé tels que des craquelures ou décollements. Il n'était donc pas évident de proposer un liant polymérique qui contient suffisamment de fonctions fixatrices de formaldéhyde de l'air pour être efficace tout en permettant la formation de feuil de revêtement satisfaisant. The acrylic polymer containing acetoacetate functions is synthesized in emulsion via a latex. A radical initiator, a catalyst and surfactants are needed. The initiator may be chosen from hydrogen peroxide, ammonium persulfate, dibenzoyl peroxide, 2,24-azobisisobutonitrile, azonitrile derivatives, etc. The catalyst is a metal derivative capable of decomposing the initiator. The acrylic polymer according to the invention has the following additional characteristics: a weight-average molecular weight ranging from 50,000 to 1,000,000, preferably between 100,000 and 300,000, and / or a glass transition temperature of between -10 ° C. and 60 ° C., preferably between 0 ° C and 40 ° C. The glass transition temperature of the binder according to the invention is preferably less than 40 ° C to allow the formation of film at room temperature during drying. However, the hydrazide and acetoacetate functions for fixing the formaldehyde of the air tend to increase this glass transition temperature or to cause excessive crosslinking characterized by macroscopic defects of the formed film such as cracks or detachments. It was therefore not obvious to provide a polymeric binder that contains sufficient formaldehyde-fixing functions of air to be effective while allowing for the formation of satisfactory coating film.
Une ou plusieurs émulsions d'alkyde portant une ou plusieurs fonctions fixatrices de formaldéhyde pourront être mélangées à une ou plusieurs dispersions aqueuses de polymères acryliques portant une ou plusieurs fonctions fixatrices de formaldéhyde en vue d'obtenir un liant possédant les propriétés souhaitées selon l'application.  One or more alkyd emulsions bearing one or more formaldehyde-fixing functional groups may be mixed with one or more aqueous dispersions of acrylic polymers carrying one or more formaldehyde-fixing functional groups in order to obtain a binder having the desired properties according to the application .
Selon un autre mode de réalisation, des combinaisons des deux types de liants, alkydes et acryliques, peuvent être envisagées.  According to another embodiment, combinations of the two types of binders, alkyd and acrylic, can be envisaged.
La combinaison peut être un simple mélange des deux liants.  The combination can be a simple mixture of the two binders.
La combinaison peut aussi se faire de manière réactive, en formant un hybride. Par exemple en faisant réagir un liant acrylique fixateur de formaldéhyde et portant des groupements carboxyles avec les groupements hydroxyles d'un liant alkyde fixateur (ou non) de formaldéhyde. L'acide acrylique étant utilisé en tant que comonomère.  The combination can also be reactive, forming a hybrid. For example, by reacting a formaldehyde-fixing acrylic binder bearing carboxyl groups with the hydroxyl groups of an alkyd binding binder (or not) of formaldehyde. Acrylic acid being used as a comonomer.
Le liant pour revêtement selon l'invention fixe de manière covalente le formaldéhyde. Cette fixation est permanente, il n'y a pas de rejet ultérieur de formaldéhyde et ce notamment du fait que le liant est stable. En effet, le liant comprend un polymère donc avec un poids moléculaire élevé limitant sa migration ou sa modification au cours du temps.  The coating binder according to the invention covalently binds formaldehyde. This fixation is permanent, there is no subsequent rejection of formaldehyde and this especially because the binder is stable. Indeed, the binder comprises a polymer and therefore with a high molecular weight limiting its migration or its modification over time.
Le liant selon l'invention est facilement intégrable à différentes formulations de revêtement.  The binder according to the invention is easily integrable with different coating formulations.
Préférentiellement, le liant est stable en dispersion dans l'eau.  Preferably, the binder is stable in dispersion in water.
Le liant selon l'invention est un liant filmogène. On entend par filmogène un polymère apte, en moins de 6h et à une température comprise entre 5 et 30°C de passer de l'état liquide à l'état solide en formant un feuil sec au toucher, homogène, tendu, continu et adhérent et ce par un quelconque mécanisme de séchage physique et/ou chimique, en présence ou non d'un catalyseur.  The binder according to the invention is a film-forming binder. The term "film-forming agent" means a polymer capable, in less than 6 hours and at a temperature of between 5 and 30 ° C., of passing from the liquid state to the solid state, forming a film that is dry to the touch, homogeneous, taut, continuous and adherent. and this by any physical and / or chemical drying mechanism, in the presence or absence of a catalyst.
Les revêtements pouvant intégrer le liant selon l'invention sont divers tels que par exemple : Peinture primaire et peinture de finition pour les murs, les plafonds, les sols, les boiseries, le mobilier quel qu'en soit le matériau notamment le mobilier de cuisine type placards et plans de travail. En effet, les étapes de cuisson en cuisine sont une source additionnelle d'émission de formaldéhyde. The coatings that can incorporate the binder according to the invention are various such as for example: Primary paint and finishing paint for walls, ceilings, floors, woodwork, furniture regardless of the material including kitchen furniture type closets and worktops. Indeed, the cooking stages in the kitchen are an additional source of formaldehyde emission.
Vernis primaire et finition pour boiseries telles que les charpentes, le parquet, le mobilier quel qu'en soit le matériau  Primary varnish and finish for woodwork such as carpentry, parquet, furniture whatever the material
Lasure transparente de finition pour murs et plafonds Transparent finish stain for walls and ceilings
Vernis à ongles notamment pour limiter l'exposition des fumeurs au formaldéhyde Nail polish, in particular to limit the exposure of smokers to formaldehyde
Textiles : rideaux, tissus utilisés dans l'automobile, non tissé  Textiles: curtains, fabrics used in the automobile, nonwoven
Papiers utilisant des polymères liants  Papers using binder polymers
Les revêtements intégrant le liant selon l'invention sont destinés à être utilisés sur des supports préférentiellement non poreux, non fibreux tels que par exemple du ciment, un parpaing, un panneau de mélaminé, une ancienne peinture, du plâtre, du bois, un métal, un plastique. Ces supports sont dit fermés. C'est-à-dire qu'un flux d'air ne peut pas, ou difficilement, les traverser. Ce type de support se distingue des supports tels que des filtres qui sont dits ouverts car un flux d'air peut aisément les traverser.  The coatings incorporating the binder according to the invention are intended to be used on preferentially non-porous, non-fibrous substrates such as for example cement, a cinder block, a melamine panel, an old paint, plaster, wood, a metal , a plastic. These supports are said closed. That is to say, a flow of air can not, or hardly, cross them. This type of support differs from media such as filters that are said to be open because a flow of air can easily pass through them.
Selon l'invention, le revêtement présente un pouvoir assainissant dès son application, plus précisément dès qu'il est sec soit au moins 1 h, préférablement 6h, après application.  According to the invention, the coating has a sanitizing effect as soon as it is applied, more specifically as soon as it is dry, ie at least 1 hour, preferably 6 hours, after application.
Suivant un autre aspect, l'invention concerne un procédé pour assainir de l'air caractérisé en ce qu'on applique un revêtement comprenant un liant tel que décrit précédemment, et que la fonction fixatrice de formaldéhyde réagit avec du formaldéhyde présent dans l'air et le fixe de manière covalente  According to another aspect, the invention relates to a process for purifying air, characterized in that a coating comprising a binder as described above is applied, and that the formaldehyde-fixing function reacts with formaldehyde present in the air. and fixes it covalently
Le revêtement nécessite une seule couche de peinture pour assainir l'air. Toutefois, il est possible d'appliquer plusieurs couches notamment pour des questions de couvrance de support sans effet sur le pouvoir d'assainissement du revêtement.  The coating requires a single coat of paint to clean the air. However, it is possible to apply several layers, in particular for support coverage issues without effect on the cleaning power of the coating.
Exemple 1 : Préparation d'un polymère alkvde contenant 14% massique de fonction fixatrice Example 1 Preparation of an Alkyd Polymer Containing 14% by Mass of Fixative Function
Dans un réacteur tricol surmonté d'un dean stark et d'un réfrigérant, introduire 32g d'acide benzoïque, 52g d'anhydride phtalique, 48g de pentaérythritol, 67g d'acide linoléique et 8g de xylène. Agiter à 250°C pendant 10 heures jusqu'à obtenir un condensât de 20 mL d'eau environ. Extraire le xylène. Abaisser la température à 150°C puis ajouter 28g de méthylacétoacétate. Agiter pendant environ 1 heure en recueillant le méthanol formé dans le dean stark. In a tricolor reactor surmounted by a stark dean and a condenser, introduce 32 g of benzoic acid, 52 g of phthalic anhydride, 48 g of pentaerythritol, 67 g of linoleic acid and 8 g of xylene. Stir at 250 ° C for 10 hours until a condensate of 20 ml of water is obtained. Extract the xylene. Lower the temperature to 150 ° C then add 28g of methylacetoacetate. Stir for about 1 hour by collecting the methanol formed in the stark dean.
Exemple 2 : Préparation d'un polymère acrylique contenant 10% massique de monomères AAEM Example 2 Preparation of an Acrylic Polymer Containing 10% by Mass of AAEM Monomers
Dans un réacteur double enveloppe chauffé à 60°C, purgé à l'azote et agité mécaniquement, introduire 45 mL d'eau distillée contenant 60mg de carbonate de sodium, et 160mg de sodium lauryl sulfate. Préparer un mélange de comonomères (16,95g méthacrylate de méthyle, 8,25g acrylate de butyle, 3,98g 2-(acétoacétoxy) éthyl méthacrylate, 10,60g 2-éthyl hexyl acrylate). Préparer une solution d'initiateur : 40g de persulfate d'ammonium dans 15 mL d'eau distillée. Introduire 4g du mélange de monomère puis 5,5g de solution de persulfate d'ammonium. Mettre sous agitation pour former une émulsion et introduire ensuite simultanément les solutions de monomères et de persulfate d'ammonium sur un intervalle de 180 minutes en contrôlant la température à 60°C. Poursuivre la réaction 40 minutes après la fin de l'introduction puis laisser refroidir et filtrer.  In a jacketed reactor heated to 60 ° C, purged with nitrogen and stirred mechanically, introduce 45 mL of distilled water containing 60 mg of sodium carbonate, and 160 mg of sodium lauryl sulfate. Prepare a mixture of comonomers (16.95 g methyl methacrylate, 8.25 g butyl acrylate, 3.98 g 2- (acetoacetoxy) ethyl methacrylate, 10.60 g 2-ethyl hexyl acrylate). Prepare an initiator solution: 40g of ammonium persulfate in 15mL of distilled water. Introduce 4 g of the monomer mixture and then 5.5 g of ammonium persulfate solution. Agitate to form an emulsion and then simultaneously introduce the monomer and ammonium persulfate solutions over an interval of 180 minutes by controlling the temperature to 60 ° C. Continue the reaction 40 minutes after the end of the introduction then allow to cool and filter.

Claims

REVENDICATIONS
Liant pour revêtement comprenant un polymère portant au moins une fonction fixatrice de formaldéhyde destinée à réagir avec du formaldéhyde présent dans l'air pour le fixer de manière covalente. A coating binder comprising a polymer having at least one formaldehyde scavenger function for reacting with formaldehyde present in the air to covalently fix it.
Liant selon la revendication 1 dans lequel le polymère est choisi parmi les polymères obtenus par polycondensation tels que les polyesters, alkydes, polyuréthanes, polyamides ou les polymères obtenus par polyaddition tels que les polyacrylates, polyvinylalcools ou les résines époxy.  A binder according to claim 1 wherein the polymer is selected from polycondensation polymers such as polyesters, alkyds, polyurethanes, polyamides or polyaddition polymers such as polyacrylates, polyvinylalcohols or epoxy resins.
Liant selon la revendication précédente dans lequel le polymère alkyde comprend au moins un acide gras insaturé, introduit en quantité massique strictement supérieure à 0 et inférieure ou égale à 70 % en masse, de préférence entre 10 et 50 % en masse.  Binder according to the preceding claim wherein the alkyd polymer comprises at least one unsaturated fatty acid, introduced in a mass quantity strictly greater than 0 and less than or equal to 70% by weight, preferably between 10 and 50% by weight.
Liant selon l'une quelconque des deux revendications précédentes dans lequel le polymère alkyde a une masse moléculaire en poids allant de 10000 à 250000, préférentiellement de 20000 à 90000.  Binder according to any one of the two preceding claims, in which the alkyd polymer has a weight-average molecular mass ranging from 10,000 to 250000, preferably from 20000 to 90000.
Liant selon l'une quelconque des trois revendications précédentes dans lequel le polymère alkyde a un indice d'acide compris entre 1 et 140 préférentiellement de 10 à 20.  Binder according to any one of the three preceding claims, in which the alkyd polymer has an acid number of between 1 and 140, preferably from 10 to 20.
Liant selon l'une quelconque des quatre revendications précédentes dans lequel le polymère alkyde a un indice d'OH compris entre 20 et 170, préférentiellement de 25 à 80.  Binder according to any of the four preceding claims wherein the alkyd polymer has an OH value of between 20 and 170, preferably 25 to 80.
Liant selon la revendication 2 dans lequel le polymère acrylique a une masse moléculaire en poids allant de 50000 à 1000000, préférablement entre 100000 et 300000.  A binder according to claim 2 wherein the acrylic polymer has a weight average molecular weight of from 50000 to 1000000, preferably from 100000 to 300000.
Liant selon la revendication 2 ou 7 dans lequel le polymère acrylique a une température de transition vitreuse comprise entre -10°C et 60°C, préférablement entre 0°C et 40°C.  The binder of claim 2 or 7 wherein the acrylic polymer has a glass transition temperature of from -10 ° C to 60 ° C, preferably from 0 ° C to 40 ° C.
Liant selon l'une quelconque des revendications précédentes dans lequel la fonction fixatrice est une fonction acétoacétate greffée par transestérification sur au moins une fonction hydroxyle d'un polymère. Liant selon la revendication précédente dans lequel la fonction acétoacétate est greffée à hauteur de 1 % à 50% massique, préférentiellement 7% à 25% par rapport à la masse du polymère.  Binder according to any one of the preceding claims wherein the fixing function is a function acetoacetate grafted by transesterification on at least one hydroxyl function of a polymer. Binder according to the preceding claim wherein the acetoacetate function is grafted at 1% to 50% by weight, preferably 7% to 25% relative to the weight of the polymer.
Liant selon l'une quelconque des revendications 1 à 8 dans lequel la fonction fixatrice est une fonction hydrazide greffée par condensation de l'hydrazine sur au moins une fonction carboxylique d'un polymère. Binder according to any one of claims 1 to 8 wherein the fixer function is a hydrazide function grafted by condensation of hydrazine on at least one carboxylic function of a polymer.
12. Liant selon l'une quelconque des revendications 1 à 8 dans lequel la fonction fixatrice est une fonction hydrazide greffée par réaction d'un polyhydrazide avec au moins une fonction carbonyle d'un polymère.  12. Binder according to any one of claims 1 to 8 wherein the fixing function is a hydrazide function grafted by reaction of a polyhydrazide with at least one carbonyl function of a polymer.
13. Liant selon l'une quelconque des revendications 1 à 8 dans lequel la fonction fixatrice est un comonomère fixateur de formaldéhyde portant au moins une fonction acétoacétate tel que l'AAEM ajouté à des monomères acryliques.  13. Binder according to any one of claims 1 to 8 wherein the fixing function is a formaldehyde fixing comonomer carrying at least one acetoacetate function such as AAEM added to acrylic monomers.
14. Liant selon la revendication précédente dans lequel le ou les comonomères portant la fonctionnalité acétoacétate sont introduits à hauteur de 1 % à 50% massique, de préférence de 7% à 25% massique, de la masse totale du polymère. 14. Binder according to the preceding claim wherein the comonomer or comonomers carrying the acetoacetate functionality are introduced at a level of 1% to 50% by weight, preferably 7% to 25% by weight, of the total weight of the polymer.
15. Liant selon l'une quelconque des revendications précédentes dans lequel le revêtement est une peinture ou un vernis ou une lasure ou un vitrificateur.  15. Binder according to any one of the preceding claims wherein the coating is a paint or varnish or a glaze or a glazer.
16. Revêtement comprenant un liant selon l'une quelconque des revendications précédentes.  16. A coating comprising a binder according to any one of the preceding claims.
17. Procédé pour assainir de l'air caractérisé en ce qu'on applique un revêtement comprenant un liant selon l'une quelconque des revendications 17. Process for cleaning air characterized in that a coating comprising a binder according to any one of the claims is applied.
1 à 15, et que la fonction fixatrice de formaldéhyde réagit avec du formaldéhyde présent dans l'air et le fixe de manière covalente. 1-15, and that the formaldehyde scavenger function reacts with formaldehyde present in the air and covalently fixes it.
PCT/EP2014/061355 2013-05-31 2014-06-02 Binder for coatings including a function for binding formaldehyde in air WO2014191573A1 (en)

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