Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/36—Hydroxylated esters of higher fatty acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3228—Polyamines acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/348—Hydroxycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/68—Unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/68—Unsaturated polyesters
  • C08G18/683—Unsaturated polyesters containing cyclic groups
  • C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/022—Emulsions, e.g. oil in water

Definitions

• the invention relates to a rosin-based polyurethane resin obtained from a rosin-modified hydroxyl-modified polyester, polyester of biobased origin and also relates to the aqueous dispersions of these resins and their uses in aqueous coatings.
• alkyds in organic solvent medium are resins well known to the skilled person for a long time, used, as a rule, in coatings and decorative and industrial paint formulations.
• organic solvent medium otherwise known as solvent
• specific alkyd emulsions have been developed and put on the market for about twenty years, with interesting levels of performance in terms of brilliance. , drying, appearance / color, stability, odor.
• a conventional technical implementation solution employed to form stable time-stable alkyd emulsions is to use a combination of a nonionic surfactant with anionic surfactant as described in WO 2008/076360.
• VOCs VOCs
• the resin of the invention allows the preparation of aqueous polyurethane dispersions based on fatty polyesters that meet these needs or overcome the disadvantages of known dispersions cited.
• the solution of the invention is first of all a friendly solution for man and his environment because of the absence of both organic solvents with low VOC content (volatile organic compounds) in the aqueous dispersion and the absence of drying agents, also called siccatives, in drying but also by the choice of the essential raw materials of the fatty polyester serving as a base for the polyurethane resin, insofar as a high rate of these raw materials is of renewable and sustainable origin and may lead to more easily biodegradable chemical structures.
• Said aqueous binders according to the present invention are prepared mainly from rosin and natural fats.
• This advantage is notable since, in some cases, the proportion of renewable raw materials in the polyester polyol fatty-based polyurethane resin reaches a level of 100% on the overall composition of this fatty polyester resin.
• the durability of said resin is related to the sustainable and seasonal availability of said raw materials. These same causes also make it possible to limit the environmental impact via a reduced carbon footprint and an improved life cycle. These two parameters reflect the impact of manufactured products on the environment and health.
• the use of so-called renewable or biobased resources makes it possible in particular to reduce greenhouse gas emissions such as carbon dioxide.
• the specific resin of the invention which makes these dispersions and technical performance possible, is based on a fatty polyester (non-oxidizable or oxidizable as an alkyd) urethanized (with formation of polyurethane based on this polyester).
• This base fatty polyester resin of biobased origin and, in particular alkyd and more particularly alkyd short or medium oil ⁇ 60%, uses a high rate of raw materials of renewable origin and allows specific performance, particularly with regard to Hardness development with time after application. Similarly, yellowing reduction can be achieved.
• the new polyurethane resin based on this polyester can be used as a binder in aqueous aqueous decorative or industrial coating compositions capable of curing in air with or without drying agent, preferably without drying agent.
• urethane moieties with said specific polyester provides particular additional advantages such as good substrate adhesion, good flexibility, abrasion resistance, excellent blocking resistance and good mechanical strength in general.
• the product of the invention has the specific ability to dry and harden very rapidly from the first hours of application as shown by the results and graph below (new urethanized polyester or
• An additional advantage in drying the resin dispersions, according to the present invention is the faster and more intense development over time of stable hardness and this without the need for addition of Co (cobalt) or other type of sicactivtion.
• the invention firstly covers a specific linear or branched polyurethane resin based on a specific fatty polyester, of biobased origin, more particularly based on a biosourced alkyd (oxidizable polyester).
• the invention relates to an organic binder composition based on said resin.
• the invention relates more particularly to an aqueous dispersion of said polyurethane resin.
• Another subject of the invention relates to a process for preparing said resin in the form of an aqueous dispersion.
• Another object relates to a coating composition which comprises said resin or resin dispersion.
• the invention relates to a substrate coating that results from said resin or resin dispersion.
• the first subject of the invention relates to a linear or branched polyurethane resin based on fatty polyester, in particular based on alkyd, obtained from at least one hydroxylated fatty polyester A), with:
• polyester A) being the product of the reaction of a) an alcohol component with b) an acid component, which acid component b) comprises b1) at least one fatty acid, said fatty acid being selected from b1 .1) at least one monoacid and / or an oxidizable fatty acid, having at least one oxidizable unsaturation or b1 .2) at least one monoacid and / or a non-oxidizable fatty polyacid or b1 .3) at least one mixture of fatty acids b1 .1) and b1 .2) and said component b) additionally comprising b2) rosin and / or rosin derivatives bearing at least one carboxylic acid function, said rosin and / or derivatives b2) representing from 30 to 85%, and preferably from 35 to 75%, more preferably from 40 to 75% and even more preferably from 45 to 75% by weight, relative to the total weight of A)
• said polyester A) having zero oil length (0%) or between 0 and 60%, preferably 0 to 50%, more preferably 0 to 40% optional, said polyester A) having a ratio of weight of fatty acids (monoacids) oxidizable b1 .1) relative to fatty acids b1 .1) + b1 .2) overall, from 0 or greater than 0 and up to 1 or overall from 0 to 1
• polyurethane resin being the reaction product of said polyester polyol A) with:
• said polyurethane resin is the polyaddition reaction product of an alcohol component, comprising the hydroxylated fatty polyester A) and diol B) with an isocyanate component consisting of at least one polyisocyanate C).
• an alcohol component comprising the hydroxylated fatty polyester A) and diol B) with an isocyanate component consisting of at least one polyisocyanate C).
• No crosslinked structure is present in said resin that can be used for the aqueous resin dispersion.
• a resin of linear structure is obtained for a linear and at most bifunctional fatty polyester A), with a polyisocyanate C) chosen from diisocyanates.
• the NCO / OH ratio is less than or equal to 1.
• said polyurethane resin carries reactive hydroxy residual functions that can be used for a crosslinking reaction in the separate step of application (end use) for crosslinkable coatings.
• the polyisocyanate C) may be chosen from any aliphatic, cycloaliphatic or aromatic polyisocyanate suitable for the preparation of polyurethanes by reaction with a polyol. They may be diisocyanates or triisocyanates or derivatives of these isocyanates, such as oligomers of diisocyanates or precondensates or prepolymers carrying isocyanate functional groups with a functionality ranging from 2 to 3. These polyisocyanates may optionally be in the form blocked by a blocking agent which is labile in the reaction conditions.
• diisocyanates include, but are not limited to, toluene diisocyanate-2,4 and -2,6 (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (TMDI), 4, 4'-diphenyl methane diisocyanate (MDI), 4,4'-dicyclohexyl methane diisocyanate (H12MDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 1,4-benzene diisocyanate, 1,5-naphthalene diisocyanate (NDI), cyclohexane-1,4 diisocyanate, dodecane diisocyanate, m-tetramethylene xylylene diisocyanate, 4,6-xylylene diisocyanate.
• suitable triisocyanates include
• trimer HDI (as Desmodur N of Bayer).
• said polyisocyanate is a diisocyanate and in particular cycloaliphatic such as NPDI, cyclohexane-1,4 diisocyanate, 4,4'-dicyclohexyl methane diisocyanate (H12MDI).
• cycloaliphatic such as NPDI, cyclohexane-1,4 diisocyanate, 4,4'-dicyclohexyl methane diisocyanate (H12MDI).
• Diol B is a diol carrying an acid function which can be in neutralized (salified) form in part or totally.
• the preferred acidic function is among carboxylic, sulfonic, phosphonic and more particularly carboxylic or sulfonic.
• this polyester preferably has an acid number of less than 10, preferably less than 6 and a hydroxyl number (IOH) of at least 25, of preferably from 50 to 150 and has a calculated number average molecular weight Mn ranging from 250 to 10,000 and preferably from 250 to 6000.
• the Mn calculated in the absence of other indications valid for the whole invention, corresponds to the Mn calculated from the OH and acid indices and the average functionality.
• the acid numbers are measured according to the ISO 21 14 titration method and the hydroxyl numbers are calculated according to the amounts of materials introduced (OH / COOH molar ratio).
• Said acid component b) of said polyester resin A) may comprise in addition to said fatty acid b1), in addition to said rosin and / or in addition to said rosin derivatives b2), at least one acid compound b3) having at least one function carboxylic acid, optionally additionally, a hydroxyl function and a global functionality (carboxy + optionally OH) of 2 to 3, with b3) being chosen from: b3.1) saturated polyacids and / or b3.2) polyacids ethylenically unsaturated or b3.3) hydroxy acids.
• Said acid compound b1) may be in a more particular case, a non-oxidizable fatty acid b1 .2) and preferably it comprises at least one C36 dimer and / or at least one C 54 fatty acid trimer.
• fatty acid as defined herein means a carboxylic acid C 12 -C 54.
• oil length means% by weight based on the total weight of the fatty polyester resin, the weight of "fatty mono-fatty acids” or the stand-alone oils or derivatives thereof. oils (standole is a product resulting from the reaction at high temperature, 250-300 ° C of a mixture of oil and fatty acid), this% by weight being expressed by weight equivalent of triglyceride derivatives (oils) which correspond to fatty acids b1 .1), said fatty acids being "oxidizable". Any calculation and mention of this feature in the present invention is based on this definition.
• oxygenizable fatty acids for b1 .1 means, according to the present invention, fatty acids or derivatives (oils or standolies) having an iodine number greater than or equal to 80 mg of iodine per g of product.
• Said fatty monoacids or triglycerides (oils) can be mixtures of natural origin and can comprise up to 30% by weight of saturated or non-oxidizable fatty acids b1 .2).
• the hydroxylated fatty polyester resin A) according to the present invention is in particular characterized by the presence in the acid component b) of the important component b2) bearing at least one carboxylic function and which is chosen from rosin and its derivatives, including maleinised or acrylated derivatives of rosin which can carry from 3 to 4 carboxylic functions.
• the polyester resin A) of the invention comprises less than 5%, preferably less than 3% by weight, and more preferably no (0% of) aromatic compound such as phthalic type (anhydride or acid phthalic, isophthalic, trimellitic or even terephthalic), apart from any rosin derivatives used.
• aromatic compound such as phthalic type (anhydride or acid phthalic, isophthalic, trimellitic or even terephthalic), apart from any rosin derivatives used.
• rosin derivatives is meant natural derivatives such as dehydroabietic acid.
• the saturated or non-oxidizable fatty acids b1.2 used have no reactive ethylenic unsaturation (i.e., if there is unsaturation, they are not oxidizable) and can also be derived from the hydrogenation of unsaturated fatty acids b1 .1), having at least one reactive unsaturation (oxidizable and hydrogenated). More particularly, said acid component b) may comprise b1 .3) a mixture of at least two of said acidic compounds b1 .1) and b1 .2).
• the polyester resin A) is based on an acid component comprising in addition to said fatty acid b1), in addition to b2) said rosin and / or said rosin derivatives, at least one acidic compound b3) having at least one carboxylic acid function and an overall functionality of 2 to 3, global functionality including the acid function and a possible other possible function, such as hydroxyl, said compound b3) being chosen from: b3.1) saturated polyacids or b3 .2) ethylenically unsaturated polyacids or b3.3) hydroxy acids.
• Suitable saturated polybasic acid (b3.1) can be chosen from the acid and / or anhydride corresponding to: succinic acid, adipic acid, sebacic acid, dodecanedioic acid, citric acid ( functionality 3), C36 fatty acid dimer (of functionality 2 to 2.2) or C 54 fatty acid trimer (of functionality 2.5 to 3).
• Suitable unsaturated polybasic acid (b3.2) can be chosen from the existing acid and / or anhydride corresponding to: itaconic acid of functionality 2, maleic or fumaric acid of functionality 2 or tetrahydrophthalic acid (THP )
• itaconic acid of functionality 2 maleic or fumaric acid of functionality 2
• tetrahydrophthalic acid THP
• Preferred hydroxy acids b3.3) include glycolic acid or lactic acid.
• a combination of several polyacids and monoacids is often used to optimize the physicochemical properties of the polyurethane resin that results from the polyester A) especially alkyd, more particularly to obtain the desired compromise of hardness / flexibility or flexibility.
• the incorporation into A) according to the invention, in particular in alkyds, of aromatic acid derivatives such as phthalic (diacid / anhydride) or benzoic (monoacid) is possible but preferably with a level of less than 5% by weight, and more preferably with less than 3% by weight. Even more preferably, there is no aromatic derivative (0% aromatics) apart from any natural derivatives of rosin.
• a mono-acid component such as abietic or facultic acids, in particular rosin and / or its derivatives, and more particularly at such a high level, constitutes the essential element of the structure of the polyester, in particular alkyd.
• A) as defined according to the invention, to allow the particular properties observed.
• the rosin content in A) is high and varies from 30 to 85%, preferably from 35 to 75%, more preferably from 40 to 75% and even more preferably from 45 to 75%.
• the fatty acids used, given their natural origin, are mixtures as defined according to b1.3) comprising saturated or non-oxidizable fatty acids b1.1) and unsaturated fatty acids b1.2) with non-conjugated unsaturations and conjugated unsaturations . These fatty acids, as well as dimeric and / or trimeric fatty acids synthesized from these same natural fatty acids, provide the necessary flexibility and flexibility to the binder and the resulting coating that results.
• the polyurethane resin of the invention is based on a fatty polyester A) wherein said oxidizable fatty acid b1 .1) is selected from mono fatty acids of vegetable or animal origin, preferably in IC6 C2 to 4, with an average iodine value of from 100 to 200 mg I 2 / g.
• polyester polyol fatty resin resin A may preferably comprise at least one polyol of functionality ranging from 2 to 10 and more preferably from 2 to 6.
• Suitable polyols a) according to the invention may be selected from: ethylene glycol, polyethylene glycol, preferably having a number average molecular weight Mn (calculated from the OH number) ranging from 250 to 3000, propylene glycol (propane diol -1, 2), 1,3-propanediol, dipropylene glycol, triethylene glycol, glycerol, diglycerol, trimethylol propane or trimethylol ethane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, methyl glucoside, polyglycerol, in particular oligomers of glycerol, such as polyglycerol -3 (glycerol trimer) and decaglycerol and preferably, glycerol oligomers and mixtures thereof, such as Polyglycerol-3, which Polyglycerol-3 is a mixture of oligomers of gly
• said polyol a) may be selected from: ethylene glycol, polyethylene glycol, preferably Mn from 250 to 3000, propylene glycol, 1,3-propanediol, dipropylene glycol, triethylene glycol, glycerol, diglycerol, trimethylol propane (or ethane), pentaerythritol, dipentaerythritol, sorbitol, mannitol, methyl glucoside, polyglycerol, in particular glycerol.
• said polyurethane resin and bound aqueous dispersion is based on a fatty polyester resin A), wherein said polybasic acid b1 .2) comprises at least one C36 fatty acid dimer and / or a C 54 fatty acid trimer and said polyol a) comprises glycerol or at least one glycerol oligomer and / or pentaerythritol and / or dipentaerythritol and preferably glycerol and / or pentaerythritol.
• said acid function of said diol B) may be in neutralized (salified) form with a neutralizing agent which is a weak base, preferably selected from tertiary amines, in particular trialkyl amines or phosphines and more preferably it is neutralized (salified) with tertiary amines.
• the neutralizing agent is a weak base, which means a lower basicity than soda or potash (pK a ⁇ 14).
• said polyurethane resin of the invention carries hydroxyl reactive groups, preferably with an OH number of at least 20, more preferably at least 40. It is in fact residual OH groups remaining after the reaction between the alcohol component comprising the polyol fatty polyester and the diol B) and the polyisocyanate C).
• an excess of at least 5% of OH functions relative to the NCO isocyanate functional groups is used for the polyurethane resin.
• the excess of the OH functions with respect to the isocyanate functional groups is adjusted as a function of this index.
• the presence of these residual OH functions allows the additional modification of the resin of the invention but especially its crosslinking at a later stage when used in a final coating application.
• the crosslinking can be carried out with a suitable crosslinking agent (reactive with respect to the hydroxyl functional groups and multifunctional), for example melamine or blocked or unblocked polyisocyanates.
• the second subject of the invention relates to an organic binder composition which comprises at least one resin as defined according to the invention described above.
• This binder composition may comprise in addition to the resin of the invention, at least a second resin different from the first, this second resin being selected from polyesters based on fatty acids, preferably from modified alkyd resins.
• Suitable modified alkyds for this composition include acrylic modified alkyds, modified amide modified styrene modified alkyds, and silicone modified ones.
• aqueous resin dispersion which comprises at least one polyurethane resin or at least one binder composition of the invention, preferably with said acid function of said diol B) being neutralized partially or totally by a base low, preferably selected from amines, in particular tertiary amines or phosphine, preferably tertiary amines and in particular trialkyl amines such as triethylamine (TEA).
• a base low preferably selected from amines, in particular tertiary amines or phosphine, preferably tertiary amines and in particular trialkyl amines such as triethylamine (TEA).
• said dispersion has a solids content ranging from 20 to 60%, and preferably from 30 to 50% and an average particle size ranging from 30 to 200 nm.
• it may be free of any organic solvent with a corresponding level of VOC of less than 5000 ppm, preferably less than 1000 ppm and more preferably less than 500 ppm.
• This aqueous resin dispersion according to the invention may comprise a mixture of dispersions, with at least a first aqueous resin dispersion according to the invention and with at least a second resin dispersion different from the first, this second resin dispersion being selected.
• this second resin dispersion may be selected among the dispersions of alkyds, optionally modified, acrylic dispersions (or emulsions) (including styrene-acrylic) or dispersions of other polymers and in particular dispersions of polyurethanes, saturated or unsaturated polyesters.
• the weight ratio of said first dispersion may vary from 50 to 99.5% relative to said mixture.
• a more particular case of aqueous dispersion according to the invention is that in which said dispersion comprises a polyurethane resin bearing OH groups with an OH number being at least 20 and more preferably at least 40.
• a dispersion can be used in particularly for aqueous compositions of crosslinkable coatings in the presence of a multifunctional crosslinking agent carrying functional groups reactive with OH groups.
• a crosslinking agent is melamine, whether polyisocyanates are blocked or not.
• the invention then relates to a process for preparing said polyurethane resin and more particularly in the form of an aqueous dispersion.
• this also relates to a process for preparing said aqueous dispersion.
• This method for preparing a resin of the invention, in the aqueous dispersion state comprises at least the following successive stages:
• a polyester polyol A) (fatty) as defined above, by reaction of the melt-forming polycondensation of said alcohol components a) and acid b), until an index of acid less than 10, ii) dissolving and diluting said polyester in a volatile solvent (having a boiling point of less than 150 ° C., preferably less than 100 ° C.), iii) polyaddition reaction in a solvent medium of said polyester A ) as obtained in step ii) by addition of said diol B) and said polyisocyanate, preferably diisocyanate C), with partial or complete neutralization of said acid function of B) with a weak base chosen from amines or phosphines , preferably amines, in particular tertiary amines, said neutralization being able to take place before or after said polyaddition,
• step iv) at the end of the reaction of step iii), dispersion in water with stirring, of the polyurethane solution, as obtained in step iii), before
• the invention relates more particularly to an aqueous coating composition which comprises as binder at least one resin or at least one binder composition or at least one aqueous dispersion as defined above according to the invention.
• aqueous coating composition which comprises as binder at least one resin or at least one binder composition or at least one aqueous dispersion as defined above according to the invention.
• These compositions are distinguished from the state of the art in terms of application performance, particularly with regard to faster development of hardness and rapid physical drying, and Yellowing development reduced and controlled over time.
• the resulting coatings have additional performance among: abrasion resistance, good flexibility, blocking resistance, adhesion and mechanical strength. Given the particular adhesion of the polyurethane resins on a metallic substrate and the barrier effect characterized by the high hydrophobicity / hardness of the rosin-based binder, this type of binder gives the final coating particularly effective anticorrosive properties. It is an intended application in particular for aqueous coatings based on the polyurethane resin of the
• said coating composition of the invention is crosslinkable and comprises at least one aqueous polyurethane resin dispersion according to the present invention comprising hydroxyl groups (residual of the reaction with said polyisocyanate), preferably with an OH number. at least 20, more preferably at least 40 and said dispersion further comprises at least one crosslinking agent capable of reacting with said hydroxyl functions, preferably said crosslinking agent being selected from: melamine, blocked or non-blocked polyisocyanate, epoxy and silane.
• the coating composition of the invention is more particularly used for aqueous coatings such as adhesives, paints, stains, primers and varnishes.
• these compositions contain a reduced level of drying agents and more preferably they are free from driers such as heavy-metal salts such as cobalt or tin salts and more particularly they contain no drying agent.
• the invention relates to a substrate coating as obtained from at least one resin or a binder composition or an aqueous dispersion as defined above according to the invention.
• Said polyester A is formed by "one pot” condensation (at a stage) at 230-250 ° C. of a mixture composed of glycerol, fatty acid dimer (Pripol® 1017 marketed by CRODA) and rosin in the proportions following weights (see Table 1):
• the condensation is stopped so as to obtain a final viscosity of 70 Pa.s (measured at 110.degree. C. using a CAP 1000 viscometer) with an acid number of less than 10 mg KOH / g (between 6 and 8).
• Polyester A as described in Example 1 above, is diluted in acetone to be modified in polyurethane in the presence of isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA) and triethylamine (TEA), then the product is finally dispersed in water after almost complete reaction of the isocyanate functions.
• IPDI isophorone diisocyanate
• DMPA dimethylolpropionic acid
• TAA triethylamine
• the hardness evaluation is carried out on films obtained by application on a glass plate of an aqueous resin dispersion layer of Example 2 with a wet thickness of 100 ⁇ .
• the hardness test is according to the ISO 1522 method. It is a pendular hardness (Persoz) carried out at 23 ° C. and at 50% relative humidity. The varnishes are applied at 100 m wet thickness and then dried on a perfectly horizontal surface at 23 ° C and 50% relative humidity for 24 hours before the first measurement.
• Persoz pendular hardness
• Example 2 are compared with those of a commercial dispersion WorleeSol E 150 W marketed by Worlee representing the state of the art (siccativée and non siccativée).
• Figure 1 shows the strictly comparative drying, obtained under the same test conditions, without addition of siccative (such as cobalt derivatives).
• siccative such as cobalt derivatives
• Resin dispersion according to Example 2 of the invention compared to Worlee Sol E 150 W dries and hardens much faster and above all more intensely than the reference product representing the state of the art.
• the product according to the invention reaches more than 85% of its hardness potential only after 1 hour of application and without adding a drying agent.
• FIG. 2 shows dramatically that the resin dispersion according to the invention of Example 2, even when not siccativée, remains again superior to the commercial resin resin of reference siccativée by cobalt (Additol® VXW 6206 marketed by Cytec, added to 1.5% by weight on dry resin).

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• 2012
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