• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a polyester resin of linear or branched structure and free of unsaturated fatty acids, which is hydroxylated or carboxylated and characterized in that it is based on: a) an acid component comprising: a1) at least one polyacid or C4-C6 carboxylic anhydride, a2) at least one optional C8-C54 polycarboxylic acid or anhydride, a3), at least one C2-C22 saturated monoacid, b) an alcohol component comprising: b1) at least one polyol biosourced with functionality of at least 2, and at least one of the following two polyols b2) or b3): b2) at least one polyol different from b1) of functionality of at least 2, b3) at least one polyol other than b1 ) and b2) of functionality of at least 3. Said resin is more particularly 100% biosourced. The invention also relates to a resin solution and a coating composition comprising said resin and its use in coatings having a high durability and based on renewable raw materials.
    公开号:FR3025797A1
    申请号:FR1458597
    申请日:2014-09-12
    公开日:2016-03-18
    发明作者:Gregory Delmas；Alain Riondel；Frank Cogordan；Herve Ozeray
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to a polyester resin of linear or branched structure and free of unsaturated fatty acids, which is hydroxylated or carboxylated based on renewable raw materials, in particular at least based on specific biosourced polyol, a coating composition. comprising said resin and its use in coatings having high durability and based on renewable raw materials, in particular for coatings of metal foils. Oil-free functionalized polyester resins are well known for coils applications known as coils.
    [0002] Polyester resins polyols based on renewable origin components also known as "biobased" for application in metal foil coatings are already described in WO 2012/042153 and in particular resins without oil. These polyester resins are based on rosin. However, as such, they need improvement in terms of durability and resistance to yellowing.
    [0003] BA Noordover et al describes in J. Biomacromolecules, 2006, 7, 3406-3416 co- and terpolyesters based on isosorbide and succinic acid and other monomers of renewable origin such as 2,3 butanediol or 1, 3 propanediol or citric acid. No presence of polyacids longer chain in at least Cg is mentioned or suggested.
    [0004] The present invention seeks to develop new hydroxylated or carboxylated polyester resins, without oil and free of any unsaturated fatty acid residue having improved durability and yellowing resistance and compromise toughness / flexibility while having a good chemical resistance, in particular to organic solvents and water, concerning the coating obtained, in particular for application on metal sheets. The first object of the present invention relates to said linear or branched polyester resin which is hydroxyl and / or carboxyl based on a specific composition with renewable raw materials and in particular based on a specific biosourced polyol.
    [0005] Also covered is the solution of said resin in an organic solvent. Another object of the invention relates to a coating composition comprising said resin and in particular a crosslinkable coating composition. Also part of the invention is the use of said resin in said coating compositions and finally the resulting coating. Therefore, the first subject of the invention relates to a polyester resin of linear or branched structure and free of unsaturated fatty acids, which is hydroxylated or carboxylated, optionally hydroxylated and carboxylated, which resin is based on: a component acid comprising: al) at least one C4 to C6 polycarboxylic acid or carboxylic anhydride, preferably having a functionality ranging from 2 to 4, more preferably equal to 2 to 2), at least one C 8 to C 64 carboxylic polyacid or anhydride, preferably of fat functionality ranging from 2 to 4, more preferably equal to 2 to 3) optionally at least one monoacid saturated with 02 to 022, optionally capable of carrying a hydroxyl group an alcohol component comprising: 131) at least one biosourced polyol of functional fbl at least 2, preferably 2, carrying a 1,4: 3,6 dianhydrohexitol unit and at least one of the following two polyols b2) or b3): b2) at least one different polyol 131) and of functionality fb2 of at least 2, preferably 2, more particularly a C3 to 036 b3 polyol) at least one polyol other than 131) and b2) of functionality fb3 of at least 3, preferably 3. According to one particular option, the two polyols b2) and b3) may be present.
    [0006] The term "unsaturated fatty acid-free resin" means, in accordance with the present invention, the absence of any unsaturated fatty acid or unsaturated fatty acid oil in chemically incorporated form in the structure of said resin or in free form. (not chemically incorporated). Said polyacid al) includes in its cover acids such as aconitic acid derived from sugarcane, C6 and functional fai = 3. The polyacid al) may also carry a hydroxyl group such as citric acid with = 3 and carrier in addition to a hydroxyl or malic function with fai = 2 and carrying a hydroxyl or glutamic acid with fai = 2 and carrying an amine group. More particularly, said unit carried by said polyol 131) is isosorbide (1,4: 3,6 dianhydro-D-sorbitol), isomannide (1,4: 3,6 dianhydro-D-mannitol) or isoidide (1,4: 3,6 dianhydro-L-iditol). According to a particular preference, a fraction of at least 50%, preferably at least 75% by weight of said resin is biosourced. A resin or biobased product means that it comprises a raw material of non-fossil origin that is renewable and of vegetable or animal origin. The "biobased" characteristic of a product or resin or raw material used as a component of said product, such as a polyacid, a polyol or a fatty acid can be determined by determining the carbon content of the product. which attests the renewable origin of the carbon of said component as such or incorporated into a final product after reaction (which in no way modifies this rate). Indeed, a biobased component is a component in which the carbon comes from carbon dioxide (002) fixed by photosynthesis from the Earth's atmosphere. The specific fixed content of carbon 14C is the signature of a biobased component which is different from that corresponding to a component of fossil origin. This content can be determined according to ASTM D 6866 (ASTM D 6866-06) or ASTM D 7026 (ASTM D 7026-04), in particular by mass spectrometry according to ASTM D6866-06. In a particular case, said component b) comprises b2) and b3) and at least 50% by weight, preferably at least 75% by weight of said component b) is bio-sourced. More particularly, components a) and b) can be 100% biobased.
    [0007] According to another particular option, said polyol b2) is bio-sourced and chosen from 1,3 propylene diol or 1,2 propylene diol, 1,4 butanediol or diols based (meaning derived) from saturated fatty acids. . Such diols may have a chain at 0-12 to 036. Still more particularly, said polyol b3) may be bio-sourced and selected from glycerol and its ether-polyol derivatives, such as polyglycerols (oligomeric derivatives of glycerol). In the case where the functionality of one of the components mentioned is greater than 2, preferably the number-average functionality of the mixture of components a) + b) does not exceed 2. Said polyester is therefore of linear or branched structure and by definition it can not include a crosslinked structure, which is thus excluded by definition. Those skilled in the art know in particular to choose the proportions and the functionalities of reactive components as well as the conversion rate of the reactive functions, in order to avoid any crosslinking or chemical gelling of the reactive system. This question can only arise when one of the reactive components (a) and (b) has an average functionality greater than 2 to obtain a branched structure. It is possible to control the structure without any possible crosslinking, by adjusting the proportions of the components a) and b) so that the number average functionality (per mole of reactant component) over all the reactive components (a + b ) does not exceed 2 or if it exceeds 2 to limit the conversion rate well before the gel point (gelling) predictable either by experimentation or by calculation according to the Macosko-Miller relationship and / or by progressive addition of component the least functionalized on the most functionalized component with efficient stirring (maintained in excess of reactive functions by the progressive addition of the second reactive component). The Macosko-Miller relationship cited above is as defined by Macromolecules, vol. 9, pp. 199-211 (1976) and is considered well known to those skilled in the art. For clarity, we recall below this relation which links the critical ratio I-, reactive functions for two reactive components A and B at the gel point, I-, = functions of A / functions B, with the functionality average of A which is fA, and that of B which is fB with the critical conversion rate at the following gelling point xg: rc * x92 = 1 / [(fB -1) * (fA-1) 1 Said polyacid al) may be in particular a biosourced aliphatic diacid selected from: succinic acid, tartaric acid, citric acid, malic acid or itaconic acid, glutaric acid, glutamic acid, fumaric acid, furan dicarboxylic acid, tetrahydrofuran 2,5 dicarboxylic acid and tetrahydrofuran acid 3 Dicarboxylic acid and preferably: succinic acid, itaconic acid, glutamic acid, fumaric acid, furan dicarboxylic acid, tetrahydrofuran 2,5 dicarboxylic acid and tetrahydrofuran 3,5 dicarboxylic acid. Said polyacid a2) may also be bio-sourced and chosen from: azelaic acid (Ce), sebacic acid (Cie), undecanedioic acid, dodecane dioic acid or dimers and trimers of fatty acids respectively in 036 and 054. The presence of this diacid a2) and its proportion with respect to al) are important factors for playing on the hardness / flexibility compromise of the final coating and adjusting the hardness / flexibility ratio, increasing the a2) ratio improves the flexibility. Conversely, the hardness of the coating increases with the rate of al). Preferably, the molar ratio a1) / a2) varies from 2 to 8 and more preferably from 3 to 7.
    [0008] According to a particular embodiment, said monoacid a3) is present in the composition of said resin and selected from: acetic acid, pyruvic acid, lactic acid or rosin (abietic acid and C20 isomers) or an acid saturated fat in 012 to 022. According to a particular and preferred embodiment of said resin, said polyol 131) represents at least 30% by weight of said resin, this weight of "said resin" meaning here "with respect to the total weight of the components a) + b) used for said resin ". More particularly, the level of polyol 131) in% mol / mol over the entire alcohol component b) ranges from 40 to 80 and preferably from 55 to 65. The level corresponding to polyol b2) can vary from 0 to 50 and preferably from 25 to 35.
    [0009] The molar ratio of the polyol b3) can vary from 0 to 20 and preferably from 5 to 15. With regard to the OH or carboxy, optionally OH and carboxy functionality of said resin, it can correspond to an OH number and / or acid ranging from 10 to 200 mg KOH / g. More particularly, said resin may have a carboxy functionality corresponding to an acid number of less than 20, preferably less than 10 and more preferably less than 5 and in particular 0 mg KOH / g and an OH functionality corresponding to an index. OH ranging from 10 to 200, preferably from 10 to 150 mg, more preferably from 10 to 100 KOH / g. The OH number is determined according to ISO 2554. The acid number is determined according to ISO 2114.
    [0010] The resin according to the invention can therefore be functionalized OH or carboxy or OH and carboxy, preferably in the latter case with a predominant OH functionality, that is to say more than 90% of functional groups being OH. As regards the number-average molecular mass Mn of said resin, it may vary from 500 to 20000 and preferably from 750 to 10000. This molecular weight Mn 15 is determined by calculation from the functional index (in mg KOH / g ) and the average functionality fr of said resin which represents the average number of OH and / or carboxylic acid functions, calculated from the material balance (molar proportions) and the known functionality of components a) and b) used. The Tg of said resin may vary from -10 ° C to 100 ° C and preferably from 10 to 50 ° C.
    [0011] Said Tg is determined by DSC measurement with 2 passes at 10 ° C / min. The second subject of the invention relates to a solution of resin in an organic solvent, which solution comprises at least one resin as defined above according to the invention. More particularly, said solvent may be selected from methyl esters or ethyl esters of C2-C4 monocarboxylic acids or esters of said monocarboxylic acids with methoxy or ethoxy monoethers of C2-C4 diols, in particular propyl methoxy acetate. or from methyl or ethyl diesters of C4 to C6 dicarboxylic diacids, terpenes, polyhydroxyalkanoates, methyl or ethyl esters of fatty acid oils or lactic acid esters with C1 to Cs alcohols.
    [0012] The resin of the invention may be prepared by reaction between the acid components a) and alcohol b) as defined above and in the following successive steps: i) reaction of the whole acid component a) with said component b1 ) of said alcohol component b) up to a conversion of at least 85%, preferably 100% of said component b1), followed by ii) reaction of the product from step i) with the remainder of said alcohol component b) , comprising at least one of polyols b2) or b3) as defined above, the reactions of said steps i) and ii) taking place in solution in at least one organic solvent which can form an azeotrope with water. The carboxy / OH ratio in the first step i) can vary from 1.1 to 2.1, preferably from 1.2 to 2.
    [0013] The functionality of said resin is regulated by the nature of component a) or b) being in stoichiometric overall excess. A third object of the invention relates to a coating composition, preferably a coating composition in organic solvent medium, which composition comprises at least one resin as defined above according to the invention or (comprises) a resin solution as defined above. Preferably, said composition is a crosslinkable composition comprising in addition to said resin at least one crosslinking agent bearing reactive groups with the hydroxyl groups and / or carboxyls carried by said resin. When said resin is hydroxylated, said crosslinking agent may be selected from: melamine or polyisocyanate, in particular blocked polyisocyanate or polyanhydride or polysilane, in particular alkoxy-blocked polysilane and when said resin is carboxylated, said crosslinking agent may be selected from polyepoxides or polyols. Suitable crosslinking polyols when said resin is carboxylated include all monomeric or oligomeric polyols of aliphatic or cycloaliphatic structure. Examples of aliphatic monomeric polyols that may be mentioned include trimethylol propane or glycerol or pentaerythritol or ditrimethylolpropane or dipentaerythritol, these polyols possibly being alkoxylated. Other suitable polyols are acrylic polyol oligomers, polyether polyols or polyester polyols. Polyester polyester oligomers which are suitable as crosslinking agents when said resin is carboxylated are also hydroxylated polyester resins as defined according to the present invention. More particularly, said coating composition is fully biosourced with said resin and said crosslinking agent being both biosourced, preferably 100% biobased. In the possible case where the resin carries both hydroxyl and carboxy functions, a mixture of crosslinking agents corresponding respectively to each functionality of said resin can be used and optionally with two addition steps to avoid possible coreaction between the two. crosslinking agents. Preferably, the OH or carboxy functionality is predominant or unique and said crosslinking agent is specific for OH functionality only or specific for carboxy functionality only. According to a particularly preferred option, said composition is a coating composition in an organic solvent medium and in particular a paint or varnish composition, more particularly for metal surfaces. More preferably, said metal surfaces are in the form of metal sheets (in English "coils"). Another subject of the invention relates to the use of a resin as defined above or the use of a solution of such a resin in coating compositions, in particular in coating compositions. crosslinkable. Such a use relates in particular to "one-component" behavior of coating compositions for metal and in particular for metal foil coating. A composition with a "one-component" behavior is characterized by the fact that it is stable in storage and can only be crosslinked by thermal activation, a characteristic which is indispensable for this purpose. According to one particular option, said use relates to a primary coating, a finish, a tape backing or a monolayer coating. The term "tape backing" here means a coating applied to the "back" or "hidden" side of the metal foil (tape).
    [0014] Another potential use of said resin is for powder coatings, in particular crosslinkable coatings. Said resin may be carboxylated and the crosslinking agent may be a polyepoxide or a polyol based on cyanurate, in particular trihydroxyethyl cyanurate. According to another option, said use relates to "two-component" coatings. The two-component coating compositions are crosslinkable at low temperature and without the need for thermal activation. In fact, in this case, said resin in the presence of said crosslinking agent reacts immediately mixed with said agent. Therefore, such a composition is prepared just prior to use and is therefore not storage stable, resulting after mixing and reaction of said resin with said crosslinking agent, with an irreversibly crosslinked structure. Finally, the invention relates to a finished product, in particular a coating, which results from the use of at least one resin as defined above or from a solution of such resin or a coating composition such as defined above according to the present invention.
    [0015] The following examples are presented by way of illustration of the invention and its performance and in no way limit its scope. Experimental part 1) Raw materials used (see Table 1 below) Table 1: Raw materials used Name Name Supplier Function Nature Commercial chemical technical component function and type according to invention functionality Polysorb® isosorbide Roquette Diol * OH / 2 131) P Oleris® Acid Arkema Diacid * Carboxy / 2 a2) Sebacic Sebacic Acid Bio SA Acid Bio Amber Diacid * Carboxy / 2 al) Succinic Glycerine® Glycerol Oleon Triol * OH / 3 b3) 4813 Fascat® Butyl Acid PMC Organo Catalyst - Catalyst 4100 Stannoic Metallix MIBK Methyl Arkema Solvent - Azeo Solvent Isobutyl Azeo Ketone MPA Methoxy BASF Solvent - Solvent Resin Resin Resin Acetate * Biobased 2) Resin Preparation (Procedure Example 1) 10 In a 3 liter reactor, electrically heated, equipped : - a distillation column of the Vigreux type surmounted by a Dean Stark separator, - a diving rod to introduce the nitrogen, - a probe e of the temperature, 15 - 582 g of isosorbide, 246.8 g of sebacic acid, 380.9 g of succinic acid, 0.13 g of Fascat® 4100 (acid) are added. Butyl stannic) Under nitrogen flow, it is heated to 150 ° C and 50.62 g of methyl isobutyl ketone (MIBK) is introduced as a (azeotropic) solvent. The mixture is then heated to 220 ° C. while removing the water from the heteroazeotrope reaction with MIBK until a constant acid number of 165 mg KOH / g corresponding to a conversion level is obtained. isosorbide 99.5%. The duration of this first step is 8 hours. It is cooled to 180 ° C. and 55.7 g of glycerol are introduced into the reactor. The reaction medium is brought to 220 ° C., still under nitrogen, until an acid number of 10 <10 mg KOH / g is obtained. The reactor is cooled to 150 ° C and 617.57 g of methoxy propyl acetate (MPA) is added as a solvent for diluting the resin. At 90 ° C., the reactor is drained and the dry extract is adjusted by adding 68.62 g of MPA. The final characteristics of the product are: Coloring: 3 Gardner (ISO 4630 method) 15 Dry extract: 60% (ISO 3251 method) Brookfield viscosity at 25 ° C (ISO 3219 method): 4350 mPa.s Acid value: 8 mg KOH / g (ISO 2114 method) OH number (essential functionality) (mg KOH / g): 70 (ISO 2554 method) Isosorbide measured by 13 C-NMR analysis: 0.1% in the solvent resin, which corresponds to a final conversion rate of isosorbide of 99.7%. 3) Application of resins in satin-finished foil paints 3.1) Formulation of satin paints (see Table 2) Table 2: Compositions and raw materials used Component Parts Ref Function Chemical Name Supplier by weight component over 1000 Resin example 209 (1) Resin binder - 1 hydroxylated according to (part 1) the invention PMA 25.5 (2) Solvent Methoxy propyl BASF (Part 1) acetate Disperbyk® -161 5.5 (3) Dispersant Block copolymer BYK TiO2-KRONOS 243 (4) Pigment KRONOS Titanium Oxide 2360 3025797 -10- Aerosil® R 2.5 Silica (5) EVONIK 972 Rheological Silicon Additive Resin Example 220 (1) Hydroxylated Resin Binder - 1 (Part 2) according to the invention PMA (Part 2) 31 (2 ) Solvent Methoxy propyl BASF Acetate SYLOID® Silica 30 (6) Agent Silice Grace ED 40 Mattress CYMEL® 303 46 (7) Agent Melamine Allnex LF Methylated Crosslinking Catalyst PTSA 7.5 (8) Catalyst p-toluene Aldrich sulfonic acid (12, 5% in butanol) PMA (part 3) 154 (2 ) solvent Methoxy propyl BASF acetate Solvarex® 9 24 (9) solvent Hydrocarbon Total aromatic Crayvallac® 2 (10) Polyester Arkema Flow 200 spreading agent Total 1000 3.2) Procedure for the preparation of satin paints In a 1-liter beaker thermostatic to ambient temperature, the following compounds (1) (part 1), (2) (part 1), (3), (4) and (5) are introduced in the order indicated. This mixture was stirred with a Dispermat-type stirrer and then dispersed for 30 minutes at 3500 rpm. The remainder (part 2) of the binder (1), the remainder (part 2) of the solvent (2) and the compound (6) are then added. The dispersion is continued for 15 minutes at 2500 rpm. Still stirring at 1000 rpm, the compounds (7) and (8) are added. The viscosity of the paint is adjusted by the addition of (2) (part 3) 10 and (9). Finally, the compound (10) is always added with stirring at 1000 rpm. The characteristics of the satin paint obtained are shown in Table 3 below.
    [0016] 3025797 Table 3: characteristics of the satin finish Characteristic Measuring method Value Density (g / cm3) NF EN ISO 2811-1 1.27 Solid by weight (%) ES ISO 3251 58.3 Solid volume (%) ratio dry volume / total volume 44.2 VOC (g / I) * Calculated: solvent grams per 530 liter CPV paint (%) ** Calculated vs dry matter: ratio 22.8 by volume of pigments on sum pigments + binder Viscosity Cone plan to 25 ° C (m.Pas) ISO 2884-1 520 * VOC: Volatile Organic Compounds 5 ** CPV: Pigment Concentration Volume 3.3) Metal foil used, application conditions of satin paint and conditioning before evaluation tests Sheet metal used for testing is a 0.5 millimeter thick galvanized steel sheet pretreated with a chromate solution. The paint is applied using a Bar Coater type applicator. Two types of application are made: - top coating - direct coating on the sheet metal ("direct to metal") The thickness of the finishing coating and the direct coating on the sheet metal is 20 pm. In the case of the top coat, the paint is applied to a metal sheet already coated with a compatible primary coating 5 μm thick. The total thickness of the coating is 25 μm including the primary coating (20 μm top coat). The sheet thus coated is introduced into an oven at 385 ° C. Crosslinking with melamine occurs at a metal temperature peak (called PMT) of 232 ° C for 35 seconds. The paint, as a direct coating on the metal and applied to a primer as a finishing coat, is then evaluated according to various performance tests, after conditioning of the test panels (painted sheet) in a room. conditioned at 23 ° C ± 2 with humidity controlled at 50% ± 5%. 4) Paint performance evaluation tests (see Table 4 below) Table 4: Tests used Tests Description or reference to standardized method Resistance to methyl ethyl ketone (s) Linear 1Kg / TABER charge with round-trip 60 cycles / minute cotton soaked with solvent on coating until wear / destruction Stamping test (mm) NF EN ISO 1520 Test of adhesion NF EN ISO 2409 (rating from 0 = good to 5 = bad) Gloss to 60 ° (GU) NF EN ISO 2813 EN 13523-7 T-bend test (rating from 0.5 to 5 T with a pitch of 0.5 unit at each bend until last no degradation of the coating) Hardness PERSOZ (s) NF EN ISO 1522 5 10 3025797 -13- 5) Results and conclusion 5.1) Direct coating on the metal (DTM application): see table 5 Table 5: results obtained in direct coating on metal Resistance to methyl ethyl ketone ( s) 100 s ± 10 Stamping test (mm) 4.5 Adhesion test 0 Pliag test e 5 T Hardness PERSOZ (s) 207 5.2) Finishing coat on topcoat: see table 6 Table 6: finishing results obtained Resistance to methyl ethyl ketone (s) 170 s ± 15 Test d stamping (mm) 6.2 Adhesion test 0 Gloss at 60 ° (GU) 28 Folding test 3.5 T Hardness PERSOZ (s) 220 Polyester polyol based on raw materials of bio-based origin, object of The invention makes it possible to prepare metal sheet coatings with interesting application properties, in particular with a good compromise between solvent resistance and hardness. 5 10
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Polyester resin of linear or branched structure and free of unsaturated fatty acids, which is hydroxylated or carboxylated, optionally hydroxylated and carboxylated, characterized in that it is based on: a) an acid component comprising: a1) at least one polyacid or C4 to C6 carboxylic anhydride, preferably having a fat functionality ranging from 2 to 4 and more preferably equal to 2 a2) at least one C5 to C54 polycarboxylic acid or anhydride, preferably having a fat functionality ranging from 2 to 4 and more preferably at least 2 a3) optionally at least one saturated C2 to C22 monoacid, optionally capable of carrying a hydroxyl group, b) an alcohol component comprising: 131) at least one biosourced polyol with a functionality fbl of at least 2, preferably 2, carrying a 1,4: 3,6 dianhydrohexitol unit and at least one of the following two polyols b2) or b3): b2) at least one polyol other than 131) and of fb2 functionality of at least 2, preferably 2, more preferably a C3-C36 polyol b3) at least one polyol other than 131) and b2 of functionality fb3 of at least 3, preferably 3.
    [0002]
    2. A resin according to claim 1, characterized in that said polyol unit 131) is isosorbide (1,4: 3,6 dianhydro-D-sorbitol), isomannide (1,4: 3,6 dianhydro- D-mannitol) or isoidide (1,4: 3,6 dianhydro-L-iditol).
    [0003]
    3. Resin according to one of claims 1 to 2, characterized in that a fraction of at least 50%, preferably at least 75% by weight of said resin is biosourced.
    [0004]
    4. Resin according to one of claims 1 to 3, characterized in that said component b) comprises b2) and b3) and at least 50% by weight, preferably at least 75% by weight of said component b) is biobased.
    [0005]
    5. Resin according to one of claims 1 to 4, characterized in that components a) and b) are 100% biobased.
    [0006]
    6. Resin according to one of claims 1 to 5, characterized in that said polyol b2) is bio-sourced and selected from 1,3 propylene diol or 1,2 propylene diol, 1,4 butanediol or diols. saturated fatty acid base.
    [0007]
    7. Resin according to one of claims 1 to 6, characterized in that said polyol b3) is biosourced and selected from glycerol and its ether-polyol derivatives, such as polyglycerols. 3025797 -15-
    [0008]
    8. Resin according to one of claims 1 to 7, characterized in that said poly acid al) is a biosourced aliphatic diacid chosen from: succinic acid, tartaric acid, citric acid, malic acid, itaconic acid, glutaric acid, glutamic acid, fumaric acid, furan dicarboxylic acid, tetrahydrofuran 2,5 dicarboxylic acid and tetrahydrofuran 3,5 dicarboxylic acid, preferably succinic acid, itaconic acid, glutamic acid, fumaric acid, furan dicarboxylic acid, tetrahydrofuran 2,5 dicarboxylic acid and tetrahydrofuran acid 3 Dicarboxylic acid.
    [0009]
    9. Resin according to one of claims 1 to 8, characterized in that said polyacid a2) is biosourced and selected from: azelaic acid (Ce), sebacic acid (C10), undecanedioic acid, dodecanedioic acid or dimers and trimers of fatty acids respectively in 036 and 054.
    [0010]
    10. Resin according to one of claims 1 to 9, characterized in that said monoacid a3) is present in the composition of said resin and selected from: acetic acid, pyruvic acid, lactic acid or rosin (abietic acid and isomers) at 020) or a saturated fatty acid at 0-122. Resin according to one of claims 1 to 10, characterized in that said polyol 131) represents at least 30% by weight of said resin. 12. Resin according to one of claims 1 to 11, characterized in that it has an OH and / or carboxylic acid functionality corresponding to an OH and / or acid number ranging from 10 to 200 mg KOH / g. . 13. Resin according to one of claims 1 to 11, characterized in that it has a carboxyl functionality corresponding to an acid number of less than 20, preferably less than 10 and more preferably less than 5 and in particular 0 mg KOH / g and a functionality in OH corresponding to an OH number ranging from 10 to 200, preferably from 10 to 150 mg KOH / g, more preferably from 10 to 100 mg KOH / g. 14. Resin according to one of claims 1 to 13, characterized in that its number average molecular weight Mn varies from 500 to 20000, preferably from 750 to 10000. 15. Resin according to one of claims 1 to 14, characterized in that the Tg of said resin varies from -10 ° C to 100 ° C, preferably from 10 to 50 ° C. 16. Resin solution in an organic solvent, characterized in that it comprises at least one resin as defined according to one of claims 1 to 15. 17. Solution according to claim 16, characterized in that said solvent is selected from methyl esters or ethyl esters of C2-C4 monocarboxylic acids or esters of said monocarboxylic acids with methoxy or ethoxy monoethers of C2-C4 diols, especially methoxy propyl acetate or of methyl or ethyl diesters of C 4 -C 6 carboxylic diacids, terpene, polyhydroxyalkanoates, methyl or ethyl esters of fatty acid oils or lactic acid esters with C1 to C4 alcohols. 18. A coating composition, preferably in an organic solvent medium, comprising at least one resin as defined according to one of claims 1 to 5 or a resin solution as defined according to claim 16 or 17. 19. Composition according to claim 18, characterized in that it is a crosslinkable composition comprising in addition to said resin at least one crosslinking agent bearing reactive groups with hydroxyl groups and / or carboxyls carried by said resin. 20. Composition according to claim 18 or 19, characterized in that said crosslinking agent is selected from melamine or a polyisocyanate, in particular blocked polyisocyanate or a polyanhydride or a polysilane, in particular alkoxy-blocked polysilane when said resin is hydroxylated or said crosslinking agent is selected from polyepoxides or polyols when said resin is carboxylated. 21. Composition according to one of claims 17 to 20, characterized in that it is a coating composition in an organic solvent medium, in particular a paint or varnish composition, more particularly for surfaces metal. 22. Use of a resin as defined in one of claims 1 to 15 or a resin solution as defined in claim 16 or 17 in coating compositions, particularly in crosslinkable coating compositions. . 23. Use according to claim 22, characterized in that it is a "monocomponent" behavior of coating compositions for metal, in particular for coating metal sheet ("coil"). 24. Use according to claim 22 or 23, characterized in that it is a primary coating, a finish, a tape backing or a monolayer coating. 25. Use according to claim 22 or 23, characterized in that it is powder coatings. 26. Use according to claim 22, characterized in that it is "two-component" coatings. 27. A coating characterized in that it results from the use of at least one resin as defined in one of claims 1 to 15 or a resin solution as defined according to claim 16 or 17 or a coating composition as defined in any one of claims 18 to 21.
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    WO2007074333A2|2007-07-05|Coating compositions and reactive diluents therefor
    US10189783B2|2019-01-29|Polyfunctional compounds
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    同族专利:
    公开号 | 公开日
    WO2016038302A1|2016-03-17|
    EP3191539B1|2019-12-25|
    DK3191539T3|2020-02-24|
    US20170291989A1|2017-10-12|
    CN106715525A|2017-05-24|
    MX2017002355A|2017-05-17|
    EP3191539A1|2017-07-19|
    PL3191539T3|2020-06-01|
    CA2958773A1|2016-03-17|
    US10457771B2|2019-10-29|
    CN106715525B|2019-05-07|
    ES2773458T3|2020-07-13|
    FR3025797B1|2018-03-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20020115817A1|2000-12-19|2002-08-22|Hayes Richard A.|Aliphatic-aromatic copolyesters|
    EP2325229A1|2009-11-13|2011-05-25|Cytec Surface Specialties, S.A.|Polyesters for coatings|
    US20130197152A1|2010-09-27|2013-08-01|Arkema France|Polyester resins based on fatty acids that have a short oil length, aqueous dispersions and associated coatings|
    EP2623538A1|2012-02-02|2013-08-07|A Et A Mader|Biosourced alkyd resin and method for manufacturing such an alkyd resin|
    US20140371419A1|2013-06-18|2014-12-18|Xerox Corporation|Carmine Colorants|
    DE1269989B|1961-05-26|1968-06-12|Atlas Chem Ind|Solidified fiber fleece as reinforcement for composite materials|
    US3391083A|1966-06-29|1968-07-02|Monsanto Co|Surface active agents|
    US7663004B2|2002-04-22|2010-02-16|The Curators Of The University Of Missouri|Method of producing lower alcohols from glycerol|
    WO2008031592A1|2006-09-15|2008-03-20|Stichting Dutch Polymer Institute|Process for the production of a dianhydrohexitol based polyester|
    US20080091039A1|2006-10-13|2008-04-17|Archer-Daniels-Midland Company|Hydrogenation Process and High Monoene Compositions Obtained Therefrom|
    US20090018300A1|2007-07-11|2009-01-15|Archer-Daniels-Midland Company|Monomers and polymers from bioderived carbon|
    CN102459381A|2009-04-30|2012-05-16|阿姆斯特郎世界工业公司|Uvv curable coating compositions and method for coating flooring and other substrates with same|
    US8163459B2|2010-03-01|2012-04-24|Xerox Corporation|Bio-based amorphous polyester resins for emulsion aggregation toners|
    WO2012005645A1|2010-07-07|2012-01-12|Perstorp Ab|Alkyd resin|
    FR3009304B1|2013-08-05|2016-09-30|A Et A Mader|BIOSOURCEE ALKYDE RESIN AND METHOD FOR MANUFACTURING SUCH ALKYDE RESIN|
    FR3025798B1|2014-09-12|2016-09-16|Arkema France|SPECIFIC PROCESS FOR PREPARING BIOSOURCES POLYESTERS.|CN107163234A|2017-05-31|2017-09-15|广东猛特新材料有限公司|A kind of powdery paints bio-based polyester resin and preparation method thereof|
    CN108610476A|2018-03-16|2018-10-02|哈尔滨工业大学无锡新材料研究院|A kind of biology base biodegradable thermoplastic polyester and preparation method thereof|
    US10544158B1|2019-03-14|2020-01-28|Covestro Llc|Process for producing polycyclic polyether polyols|
    FR3102988A1|2019-11-08|2021-05-14|Roquette Freres|Bio-based resin for a cosmetic composition and its manufacturing process|
    法律状态:
    2015-08-11| PLFP| Fee payment|Year of fee payment: 2 |
    2016-03-18| PLSC| Publication of the preliminary search report|Effective date: 20160318 |
    2016-08-16| PLFP| Fee payment|Year of fee payment: 3 |
    2017-08-10| PLFP| Fee payment|Year of fee payment: 4 |
    2018-08-13| PLFP| Fee payment|Year of fee payment: 5 |
    2019-08-15| PLFP| Fee payment|Year of fee payment: 6 |
    2020-08-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-08-12| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1458597|2014-09-12|
    FR1458597A|FR3025797B1|2014-09-12|2014-09-12|POLYESTER RESINS HYDROXYL OR CARBOXYL BIOSOURCEES.|FR1458597A| FR3025797B1|2014-09-12|2014-09-12|POLYESTER RESINS HYDROXYL OR CARBOXYL BIOSOURCEES.|
    CN201580049265.3A| CN106715525B|2014-09-12|2015-09-10|The hydroxy or carboxy polyester resin of biology base|
    PCT/FR2015/052407| WO2016038302A1|2014-09-12|2015-09-10|Biobased hydroxyl or carboxyl polyester resins|
    DK15770568.2T| DK3191539T3|2014-09-12|2015-09-10|BIOBASED HYDROXYL OR CARBOXYL POLYESTER RESIN|
    ES15770568T| ES2773458T3|2014-09-12|2015-09-10|Biofuels hydroxylated or carboxylated polyester resins|
    PL15770568T| PL3191539T3|2014-09-12|2015-09-10|Biobased hydroxyl or carboxyl polyester resins|
    CA2958773A| CA2958773A1|2014-09-12|2015-09-10|Biobased hydroxyl or carboxyl polyester resins|
    US15/509,497| US10457771B2|2014-09-12|2015-09-10|Biobased hydroxyl or carboxyl polyester resins|
    MX2017002355A| MX2017002355A|2014-09-12|2015-09-10|Biobased hydroxyl or carboxyl polyester resins.|
    EP15770568.2A| EP3191539B1|2014-09-12|2015-09-10|Biobased hydroxyl or carboxyl polyester resins|
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