Air drying waterborne resin composition
Abstract
An air-dried water resin composition comprising at least one dendritic amphiphilic air-drying polymer, at least one non-amphiphilic air-drying resin, at least one dryer that initiates and / or promotes self-oxidation, water and optionally at least one anionic and / or non-ionic surfactant, and / or at least one coalescing agent, characterized in that said at least one amphiphilic air drying dendritic polymer is composed of a polyhydric dendritic core polymer having at least 4 terminal hydroxyl groups and, accordingly, a hydroxyl (f) functionality of at least 4, such as 8, 16 or 32, and at least one unsaturated carboxylic acid bonded to at least one and at most f-1 of said terminal hydroxyl group and at least one adduct, obtainable by adding at least one monoalkylated polyethylene glycol to at least one dicarboxylic acid or at least one corresponding anhydride and / or at least one diisocyanate, bound to at least one and at most f-1 of said hydroxy terminal terminal group, and because said At least one non-amphiphilic air drying resin is an air drying alkyne of short, medium or long chain oil.
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Projected expiry passed 16 October 2023, 2.9 years ago.
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16 claims: 13 independent, 3 dependent
- 1ES 2 283 807 T3 REIVINDICACIONES 1. Una composición de resina al agua de secado al aire que comprende al menos un polímero dendrítico de secado al aire anfifílico, al menos una resina de secado al aire no anfifílica, al menos un secador que inicia y/o promueve la autooxidación, agua y opcionalmente al menos un tensioactivo aniónico y/o no iónico, y/o al menos un agente coalescente, caracterizada porque dicho al menos un polímero dendrítico de secado al aire anfifílico está compuesto a partir de un polímero de núcleo dendrítico polihídrico que tiene al menos 4 grupos hidroxilo terminales y, de acuerdo con ello, una funcionalidad (f) hidroxilo de al menos 4, tal como 8,16 ó 32, y al menos un ácido carboxílico insaturado unido al menos a uno y como mucho a f-1 de dicho grupo hidroxilo terminal y al menos un aducto, obtenible mediante adición de al menos un polietileno glicol monoalquilado a al menos un ácido dicarboxílico o al menos un anhídrido correspondiente y/o al menos un diisocianato, unido al menos a uno y como mucho a f-1 de dicho grupo hidroxilo terminal, y porque dicha al menos una resina de secado al aire no anfifílica es un alquido de secado al aire de aceite de cadena corta, media o larga.
- 2Una composición de resina al agua de secado al aire de acuerdo con la Reivindicación 1, caracterizada porque dicho polímero de núcleo dendrítico polihídrico se puede obtiener mediante la adición de al menos un ácido monocarboxílico di, tri o polihídrico a una molécula de núcleo di, tri o polihídrica en una relación molar que proporciona un polímero dendrítico polihídrico que comprende una molécula de núcleo y al menos una generación de ramificación unida a dicha molécula de núcleo di, tri o polihídrica.
- 3Una composición de resina al agua de secado al aire de acuerdo con la Reivindicación 1, caracterizada porque dicho polímero de núcleo dendrítico polihídrico se puede obtiener mediante la adición por apertura de anillos de al menos un oxoetano de un compuesto di, tri o polihídrico a una molécula de núcleo di, tri o polihídrica en una relación molar que proporciona un polímero dendrítico polihídrico que comprende una molécula de núcleo y al menos una generación de ramificación unida a dicha molécula de núcleo di, tri o polihídrica.
- 4Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-3, caracterizada porque dicho al menos un polietileno glicol monoalquilado tiene un peso molecular de al menos 500, tal como 500-2500 ó 700-1500.
- 5Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-4, caracterizada porque dicho al menos un polietileno glicol monoalquilado es un polietileno glicol monometilado.
- 6Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-5, caracterizada porque dicho al menos un ácido o anhídrido dicarboxílico es al menos un ácido o anhídrido dicarboxílico alifático, cicloalifático o aromático, lineal o ramificado, tal como ácido adípico, ácido azeláico, ácido fumárico, anhídrido maléico, ácido o anhídrido ftálico, ácido isoftálico, anhídrido tetrahidroftálico, anhídrido hexahidroftálico, ácido o anhídrido succínico y/o ácido sebácico.
- 7Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-6, caracterizada porque dicho al menos un ácido carboxílico insaturado es un ácido graso alifático lineal o ramificado que tiene 8-24 átomos de carbono en la cadena de carbono principal.
- 8Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-7, caracterizada porque dicho al menos un ácido carboxílico insaturado es un ácido graso sebo, ácido graso de soja, ácido graso de cártamo, ácido graso de girasol, ácido graso de semilla de algodón, ácido graso de ricino, acido oleico, ácido linoleico y/o ácido linolénico.
- 9Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-8, caracterizada por una relación en peso de dicho polímero dendrítico de secado al aire a dicho alquido de secado al aire de entre 1:99 y 99:1, tal como 50:50, 10:90, 20:80, 70:30, 90:10, 80:20 ó 70:30.
- 10Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-9, caracterizada porque dicho al menos un secador es al menos un secador de metal, tal como un secador de Pb, Zr, Co, Li, K, Mn o Mg o una combinación de los mismos o con los mismos.
- 11Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-10, caracterizada porque dicho al menos un secador de metal está presente en una cantidad de 0,01-0,3%, preferiblemente 0,05-0,1%, calculada como metal sobre resinas sólidas.
- 12Una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-11, caracterizada porque dicho al menos un tensioactivo opcional está presente en una cantidad de 1-15%, tal como 210%, en peso calculado sobre resinas sólidas.
- 13Un procedimiento para la producción de una composición de resina al agua de secado al aire de acuerdo con cualquiera de las Reivindicaciones 1-12, caracterizado porque dicho procedimiento comprende ES 2 283 807 T3 i) mezclado de dicho al menos un polímero dendrítico de secado al aire, dicho al menos un alquido de secado al aire y opcionalmente al menos un agente coalescente a 40-80°C, tal como 50-70°C ó 50-60°C, hasta que se obtiene una mezcla homogénea, ii) adición y mezclado de dicho al menos un secador y opcionalmente dicho al menos un tensioactivo y/o otros aditivos, iii) mezclado de dichos ingredientes a 40-80°C, tal como 50-70°C ó 50-60°C, durante 10-60 minutos, tal como 2040 ó 20-30 minutos, y iv) adición, lentamente bajo agitación vigorosa, de agua caliente, tal como 40-80°C, 50-70°C o 50-60°C, hasta el contenido en sólidos y/o viscosidad finales requeridos.
- 14Un procedimiento de acuerdo con la Reivindicación 13, caracterizado porque dicho un agente neutralizante, tal como una amina o amoníaco, se agrega para neutralizar grupos ácidos residuales en dicho alquido de secado al aire y/o dicho polímero dendrítico de secado al aire.
- 15Uso de un polímero dendrítico de secado al aire anfifílico de acuerdo con cualquiera de las Reivindicaciones 1-9 como resina dispersante del agua para una resina de secado al aire no anfifílica, tal como un alquido de aceite de cadena larga, media o corta.
- 16Uso de un polímero dendrítico de secado al aire anfifílico de acuerdo con cualquiera de las Reivindicaciones 1-9 como resina dispersante para pigmentos y/o cargas.
Independent claims16
124 paragraphs in 8 sections, as filed
ES 2 283 807 T3
DESCRIPTION
Air-drying water-based resin composition.
The present invention relates to a water-based resin composition, such as a resin emulsion, dispersion or solution, comprising at least one amphiphilic air-drying dendritic polymer and at least one non-amphiphilic air-drying resin, such as a short, medium or long chain oil alkyd. In further aspects, the present invention relates to a process for the production of said resin composition and to the use of said amphiphilic dendritic polymer as a dispersant resin.
A waterborne coating or resin is one that is diluted with water before use. Even considering that the dominant volatile is water, most waterborne coatings contain some solvent. Latex coatings dominate the construction market, both interior and exterior, with matt, semi-gloss and gloss coatings. Water-based systems are also used in industrial maintenance coatings based on dispersible or water-soluble resin systems. An additional class includes waterborne alkyds and polyesters. Although no longer the main class of resins used in coatings, alkyds are still very important and a wide range of types of alkyds are manufactured. While some of the non-drying alkyds are used as plasticizers in lacquers or cross-linked with melamine-formaldehyde resins in kiln-dried enamels, most are auto-oxidative drying alkyds for use in coatings for room air drying and force drying applications. . The main advantages of alkyds are low cost and relatively foolproof application characteristics.
Waterborne alkyd and polyester resins typically have terminal hydroxyl and carboxyl groups and an acid number of 40-60 mg KOH / g. In order to make such a resin reproducible with minimal risk of gelation, the reactivity of the different carboxyl groups must vary significantly. The use of trimellitic anhydride near the end of the reaction at a lower temperature takes advantage of the greater reactivity of the anhydride group. Another process uses, for example, dimethylolpropionic acid, as part of the diol in obtaining a polyester. Highly hindered carboxylic acid esterifies more slowly than carboxyl groups derived, for example, from isophthalic and adipic acids. After carrying out the reaction to the appropriate acid number, the alkyd or polyester is dissolved, for example, in a glycol ether. To neutralize the acid groups an amine or ammonia is used, the pigment is dispersed in the resin solution, additives such as surfactants and driers are added, and the coating is reduced to application viscosity with water. The resin in the diluted coating is not in solution but forms solvent and water swollen aggregates. The shelf life of such systems is limited by their relatively easy hydrolysis. Improved storage stability is often achieved by the addition of large amounts of surfactants, which, however, increase the moisture sensitivity of dry coatings.
Water alkyds as discussed above provide drying characteristics comparable to conventional and traditional solvent based alkyds. However, they are not very widely used since film properties tend to be poorer than solvent based alkyds, especially in air drying systems. Typically, water alkyds, as discussed above, have high acid numbers and are neutralized in order to be water-dilutable, whereas conventional alkyds have low acid numbers that do not provide water-dilutable if they are water-soluble. or when they are neutralized. Film formation takes place by evaporation of volatiles followed by crosslinking by ambient autooxidative reactions or reactions at elevated temperatures. Solvents are used, for example, as coalescers, that is, to promote film formation and improve film quality. Relative humidity can have a significant impact on drying behavior and film quality. Waterborne formulations that perform well when applied under dry conditions may be poor under high humidity conditions. The evaporation rate of water is much slower at high humidity, but solvent evaporation continues. This results in solvent exhaustion during critical stages of film formation and consequent poor film development. The slow loss of amine or ammonia, used to neutralize the high acid value, leads to high short-term sensitivity to water. Even in completely dry films, the presence of unreacted carboxyl groups leads to films that have comparatively poor water resistance which limits their usefulness. Water-based and solvent-based alkyds are widely described and discussed in Surface Coatings Technology, Vol. VI, Waterborne and Solvent Based Alkyds and their End User Applications, by N. Tuck, John Wiley and Sons 2000 © SITA Techno-logy Ltd.
Latex and water-soluble polymers dry by different mechanisms than alkyd resins. A latex is composed of polymeric particles dispersed in water, film formation occurs when the particles coalesce to establish a continuous film. The particles must have a glass transition temperature (Tg) low enough to flow and adhere to each other at the application temperature. The coalescers act as temporary plasticizers during the film-forming process, promoting reduction in Tg and flow, and then evaporating after film-formation has occurred. The most common coalescers are slowly evaporating glycol ethers and glycol ether esters. Glycols such as ethylene glycol or propylene glycol are commonly added for storage stability and resistance to freezing.
The present invention describes a novel water-based resin composition, such as an air-drying resin emulsion, dispersion or solution, comprising an amphiphilic air-drying dendritic polymer as a dispersant resin for a non-amphiphilic air-drying alkyd resin. , such as a conventional alkyd normally
ES 2 283 807 T3 used in solvent-based systems, whereby the disadvantages, described above, with alkyds to water are eliminated or substantially reduced.
The waterborne resin composition of the present invention comprises at least one amphiphilic air-drying dendritic polymer, at least one non-amphiphilic air-drying resin, at least one auto-oxidation initiating and / or promoting dryer, and water. Additionally, said resin composition may comprise as optional components at least one anionic and / or non-ionic surfactant, and / or at least one coalescent agent.
The amphiphilic air-drying dendritic polymer is non-ionic and self-emulsifying and is composed of a dendritic core polymer, which has terminal hydroxyl groups, the chain extending through a combination of hydrophobic chains comprising an unsaturated carboxylic acid that provides the air drying properties and hydrophilic polyethylene glycol chains. The amphiphilic dendritic polymer is present in the resin composition used as a drying dispersant resin and stabilizer for emulsification of, for example, conventional alkyd resins typically used in solvent-based systems.
The amphiphilic air-drying dendritic polymer is nonionic and self-emulsifying and is composed of a polyhydric dendritic core polymer having at least 4 terminal hydroxyl groups and, accordingly, a hydroxyl (f) functionality of al minus 4, such as 8, 16, 32 or 64, at least one carboxylic acid bound to at least one and at most f-1 of said terminal hydroxyl groups and at least one adduct, obtainable by adding a monoalkylated polyethylene glycol to an anhydride of a dicarboxylic acid, a dicarboxylic acid or a diisocyanate, also bound to at least one and at most to f-1 of said terminal hydroxyl groups.
The dendritic core polymer of said amphiphilic dendritic polymer is in various embodiments a polyhydric dendritic polymer as described, for example, in WO 93/17060, WO 93/18079, WO 96/07688, WO 96/12754, WO 99/00439, WO / 00440, WO 00/56802 and WO 02/40572. Said polyhydric dendritic core polymer is in said embodiments most preferably obtainable by adding at least one di, tri or polyhydric monocarboxylic acid to a di, tri or polyhydric core molecule in a molar ratio that provides a polyhydric dendritic polymer comprising a core molecule and at least one branch generation attached to said core molecule di, tri or polyhydric that is obtainable by ring-opening addition of at least one oxoethane of a di, tri or polyhydric compound to a di, tri or polyhydric core molecule in a molar ratio that provides a polyhydric dendritic polymer comprising one molecule core and at least one branch generation attached to said di, tri or polyhydric core molecule.
Said di, tri or polyhydric core molecule is most preferably a 1, m-diol, a 5,5- (di (hydroxyalkyl) -1,3 dioxane, a 2-alkyl-1,3-propanediol, a 2,2 -dialkyl-1,3-propanediol, a 2-hydroxy-1,3-propanediol, a 2-hydroxy-2-alkyl-1,3-propanediol, a 2-hydroxyalkyl-2-alkyl-1,3-propanediol, a 2 , 2-di (hydroxyalkyl) -1,3-propanediol, a dimer, trimer or polymer of one of said di-tri or polyhydric alcohol, or a reaction product between at least one alkylene oxide and one of said di, tri or polyhydric alcohol or one of said dimer, trimer or polymer.
Said di, tri or polyhydric monocarboxylic acid is most preferably 2,2-dimethylolpropionic acid, a, a-bis (hydroxymethyl) butyric acid, a, a, a-tris- (hydroxymethyl) acetic acid, a, a-bis acid (hydroxymethyl) valeric, α, αbis (hydroxymethyl) propionic acid, α, β-dihydroxypropionic acid and / or 3,5-dihydroxybenzoic acid.
Said oxetane is most preferably a 3-alkyl-3- (hydroxyalkyl) -oxetane, a 3,3-di (hydroxyalkyl) oxetane, a 3-alkyl-3- (hydroxyalkoxy) oxetane, a 3-alkyl-3- ( hydroxyalkoxyalkyl) oxetane, or a dimer, trimer or polymer of a 3-alkyl-3- (hydroxyalkyl) oxetane, a 3,3-di (hydroxyalkyl) oxetane, a 3-alkyl-3- (hydroxyalkoxy) oxetane or a 3-alkyl-3- (hydroxyalkoxyalkyl) oxetane.
Said unsaturated carboxylic acid, added by reaction to said polyhydric dendritic core polymer, is in various embodiments of the amphiphilic dendritic polymer a linear or branched aliphatic fatty acid having, for example, 8-24 carbon atoms in its main carbon chain, such as tallow fatty acid, soybean fatty acid, safflower fatty acid, sunflower fatty acid, cottonseed fatty acid, castor fatty acid, oleic acid, linoleic acid and / or linolenic acid. Other suitable unsaturated carboxylic acids are among vinyl acids, such as acrylic, methacrylic and / or crotonic acid used, for example, in combination with one or more of said fatty acids.
Said adduct, added by reaction to said polyhydric dendritic polymer is preferably and advantageously composed from at least one monoalkylated polyethylene glycol having a molecular weight of at least 500, such as 500-2500 or 700-1500, and at least one linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acid, or the corresponding anhydride, such as adipic acid, azelaic acid, fumaric acid, maleic anhydride, phthalic acid or anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid or anhydride, and / or sebacic acid. Said monoalkylated polyethylene glycol is most preferably a monomethylated polyethylene glycol.
Said at least one non-amphiphilic alkyd resin included in the resin composition of the present invention is a short, medium and / or long chain oil air drying alkyd, such as a conventional alkyd resin typically used in resin compositions. solvent-based.
ES 2 283 807 T3
The preferred weight ratio of amphiphilic dendritic polymer to non-amphiphilic resin is between 1:99 and 99: 1, such as 50:50, 10:90, 20:80, 70:30, 90:10, 80:20, or 7030 The most preferred weight ratio is typically 20-30% by weight of the amphiphilic dendritic polymer and 70-80% by weight of the non-amphiphilic resin. The amphiphilic dendritic polymer can further and advantageously be used as a dispersing resin in pigment pastes.
Said at least one drier included in the resin composition of the present invention is in embodiments, preferably, a metal drier, such as a Pb, Zr, Co, Li, K, Mn or Mg drier or combinations thereof. and with them, for example as octoate and / or naphthenate, mixed in an amount of, for example, 0.010.3%, such as 0.05-0.1% calculated as metal on solid resins, i.e. Solid amphiphilic air-drying dendritic polymer and solid non-amphiphilic air-drying resin.
Said optional surfactant, when present, is suitably mixed in an amount of 1-15%, such as 2-10%, by weight calculated on said at least one amphiphilic air-drying dendritic polymer and said at least one resin. non-amphiphilic air drying.
In a further aspect, the present invention relates to a process for the production of a waterborne air drying resin composition as described above. This procedure includes:
i) mixing said air drying dendritic polymer, said air drying resin and optionally said coalescing agent (s) at 40-80 ° C, such as 50-70 ° C or 50-60 ° C, until obtains a homogeneous mixture, ii) addition and mixing of said dryer and optionally said surfactant and / or other additives, such as neutralizing, flow and leveling agents, iii) mixing of the ingredients at 40-80 ° C, such as 50- 70 ° C or 50-60 ° C, for, for example 10-60 minutes, such as 20-40 or 20-30 minutes, and iv) addition, slowly under vigorous stirring, of hot water, such as 40-80 ° C, 50-70 ° C, 50-60 ° C, to the solids content , such as 40-50%, and / or final viscosity required, while maintaining the temperature at 4080 ° C, such as 50-70 ° C or 50-60 ° C.
To neutralize residual acid groups mainly in said air drying alkyd and / or said air drying dendritic polymer, a neutralizing agent, such as an amine or ammonia, can be added.
In a still further aspect, the present invention relates to the use of said amphiphilic air-drying dendritic polymer, as described herein, as a water-dispersing resin for non-amphiphilic air-drying resins, such as said conventional alkyds, and or as a dispersing resin for pigments and / or fillers.
The amphiphilic air-drying dendritic polymer can be used as a dispersant resin to prepare waterborne alkyd coatings from such conventional alkyd resins. Surfactant-free or solvent-free water-based systems based on long, medium or short chain oil alkyds can be obtained.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, use the present invention to its fullest extent. Accordingly, the following preferred specific embodiments are to be construed as merely illustrative and not limiting of the remainder of the description in any way whatsoever. The following Examples 1-19 illustrate the preparation of components included in the present invention, embodiments of the present invention, and comparative tests.
Example 1: Synthesis of a polyalkoxylated adduct used in Example 2.
Example 2: Synthesis of an amphiphilic dendritic polymer, according to an embodiment of the invention, composed from a polyhydric dendritic core polymer, a fatty acid and the adduct obtained in Example 1.
Example 3: Synthesis of a conventional medium long chain oil alkyd.
Example 4: Synthesis of a conventional short chain oil alkyd.
Example 5: Preparation of a surfactant-free water-based resin composition, according to an embodiment of the invention, comprising the product obtained in Example 2 and a commercially available long-chain oil alkyd.
Example 6: Preparation of a water-based resin composition, according to an embodiment of the invention, comprising the products obtained in Examples 2 and 3.
Example 7: Preparation of a coalescing agent-free water-based resin composition, according to an embodiment of the invention, comprising the products obtained in Examples 2 and 3.
ES 2 283 807 T3
Example 8: Preparation of a water-based resin composition, according to an embodiment of the invention, comprising the products obtained in Examples 2 and 4.
Example 9: Preparation of a coalescing agent-free water-based resin composition, according to an embodiment of the invention, comprising the products obtained in Examples 2 and 4.
Example 10: Preparation of a pigment paste comprising the product obtained in Example 2.
Example 11: Preparation of a white paint using the resin composition of Example 5 and the pigment paste of Example 10.
Example 12: Preparation of a white paint using the resin composition of Example 6 and the pigment paste of Example 10.
Example 13: Preparation of a white paint using the resin composition of Example 7 and the pigment paste of Example 10.
Example 14: Preparation of a white paint using the resin composition of Example 8 and the pigment paste of Example 10.
Example 15: Preparation of a white paint using the resin composition of Example 9 and the pigment paste of Example 10.
Example 16: Evaluation of the drying characteristics and film properties of resin compositions obtained in Examples 5-7 compared to solvent-based alkyds according to Examples 3 and 4.
Example 17: Evaluation of the drying characteristics and film properties of the white paints obtained in Examples 12-16.
Example 18: Preparation of a water-based resin composition free of coalescing agent and surfactant, according to an embodiment of the invention, comprising the products obtained in Example 2 and the commercially available long-chain oil used in Example 5 .
Example 19: Comparative example outside the scope of the invention. Emulsification of the medium chain oil alkyd obtained in Example 3 without using the amphiphilic dendritic polymer of Example 2, but using the same additive package used in Example 6.
Example 1
618 g of a monomethylated polyethylene glycol (molecular weight 750 / mol) was charged into a 1 liter reaction flask, equipped with a stirrer, and heated to 100 ° C. Next, vacuum was applied and the temperature was increased to 120 ° C and 18.2 g of succinic anhydride were added. The reaction was stopped after about 30 minutes, when an acid number of 66 mg KOH / g was reached, by cooling to room temperature. The final product was a semi-crystalline solid at room temperature.
Example 2
Step 1: 246 g of Boltorn® H20 (hydroxyfunctional dendritic polyester, from Perstorp Specialty Chemicals AB, Sweden) and 440 g of sunflower fatty acid were charged into a 1 liter reaction flask, equipped with stirrer and Dean water trap Stark, and heated to 125 ° C. Next, 0.68 g of benzoic acid, 0.07 g of Fascat® 4100 (esterification catalyst) and xylene were added and the temperature was increased to 190 ° C and held for about 5 hours. The acid number after the aforementioned 5 hours was 2.5 mg KOH / g and the xylene was removed under vacuum. The reaction was quenched by cooling to room temperature.
The product obtained had a hydroxyl number of 62 mg KOH / g and a viscosity of 1.84 Pas at 23 ° C.
Stage 2: 340 g of the product obtained in Stage 1 and 200 g of the adduct obtained in Example 1 were charged into a 1 liter reaction flask, equipped with a stirrer and a Dean Stark water trap. The reaction mixture was heated to 180 ° C and xylene and 0.05 g of Fascat® 4100 (esterification catalyst) were added to the reaction mixture. The reaction was stopped when an acid number of 8.5 mg KOH / g was reached. The xylene was removed under vacuum, the product was cooled to 90 ° C and 25 g distilled water were added.
The amphiphilic air-drying dendritic polymer obtained was a room temperature liquid having a viscosity of 12 Pas and a final acid number of 5.7 mg KOH / g. The average molecular weight was 10032 g / mol.
ES 2 283 807 T3
Example 3
942 g of soybean fatty acid was charged into a 2 liter reaction flask, equipped with stirrer, Dean Stark water trap and nitrogen purge, and the temperature was increased to 160 ° C. Under nitrogen atmosphere, 207 g of pentaerythritol, 394 g of phthalic anhydride and xylene (azeotropic solvent) were charged to the reactor and the temperature was increased to 240 ° C. The reaction was allowed to continue until an acid number below 15 mg KOH / g was reached. The product was cooled to room temperature.
The alkyd obtained had a final acid number of 7 mg KOH / g, a hydroxyl number of 134 mg KOH / g and an oil chain length of 62.9% (as triglyceride).
Example 4
574 g of soybean fatty acid was charged into a 2-liter reaction flask, equipped with a stirrer, a Dean Stark water trap, and nitrogen purge, and the temperature was increased to 160 ° C. Under nitrogen atmosphere, 45 g of pentaerythritol, 462 g of trimethylolpropane, 508 g of phthalic anhydride and xylene (azeotropic solvent) were charged to the reactor and the temperature was increased to 240 ° C. The reaction was allowed to continue until an acid number below 15 mg KOH / g was reached. The product was cooled to room temperature.
The alkyd obtained had a final acid number of 15 mg KOH / g, a hydroxyl number of 120 mg KOH / g and an oil chain length of 40% (as triglyceride).
Example 5
40 g of the amphiphilic dendritic polymer obtained in Example 2.160 g of a commercially available tallow long chain oil alkyd resin (Duramac® 301-2007, from McWorther Inc.) with an oil chain length of 82% ( as triglyceride), 10 g of dipropylene glycol methyl ether and 11 g of dipropylene glycol n-butyl ether, in a 1 liter laboratory flask, equipped with a stirrer. The mixture was heated to 60 ° C and kept at this temperature. The mixture was stirred until homogeneous and then adjusted to pH 7.5 by the addition of dimethylethylamine. Next, 4 g of a Co / Li / Zr drier (Additol® VXW 6206, from Solutia Inc.) was added and stirring was allowed to continue for another 10 minutes. Next, 319 g of demineralized hot (50 ° C) water was added slowly over a 15 minute period and stirring was allowed to continue for another 20 minutes. Finally, the emulsion obtained was cooled to room temperature with stirring.
The obtained emulsion (air-drying water-based resin composition) had a solids content of 38% and a viscosity of 150 mPas at 23 ° C. The emulsion was stable for at least 1 week at 50 ° C and at least 6 months at room temperature.
Example 6
60 g of the amphiphilic dendritic polymer obtained in Example 2, 180 g of the medium chain oil alkyd obtained in Example 3, 7.5 g of dipropylene glycol methyl ether and 10 g of dipropylene glycol n-butyl ether were charged, into a 1-liter laboratory flask equipped with a stirrer. The mixture was heated to 60 ° C and kept at this temperature. The mixture was stirred until homogeneous and then adjusted to pH 7.5 by adding dimethylethylamine and 6 g of a nonionic surfactant (Triton X100) was added and mixed. Then 4 g of a Co / Li / Zr drier (Additol<sup>®</sup> VXW 6206, ex Solutia Inc.) and stirring was allowed to continue for another 10 minutes. Next, 236 g of demineralized hot (50 ° C) water was added slowly over a 15 minute period and stirring was allowed to continue for another 20 minutes. Finally, the emulsion obtained was cooled to room temperature with stirring.
The obtained emulsion (air-drying water-based resin composition) had a solids content of 38% and a viscosity of 100 mPas at 23 ° C. The emulsion was stable for at least 2 weeks at 50 ° C.
Example 7
60 g of the amphiphilic dendritic polymer obtained in Example 2 and 180 g of the medium chain oil alkyd obtained in Example 3 were charged into a 1 liter laboratory flask equipped with a stirrer. The mixture was heated to 60 ° C and kept at this temperature. The mixture was stirred until homogeneous and then adjusted to pH 7.5 by the addition of dimethylethylamine and 12.5 g of a nonionic surfactant (Triton X100) was added and mixed. Next, 4 g of a Co / Li / Zr drier (Additol® VXW 6206, from Solutia Inc.) was added and stirring was allowed to continue for another 10 minutes. Next, 243 g of demineralized hot (50 ° C) water was added slowly over a 15 minute period and stirring was allowed to continue for another 20 minutes. Finally, the emulsion obtained was cooled to room temperature with stirring.
The obtained emulsion (air-drying water-based resin composition) had a solids content of 50% and a viscosity of 200 mPas at 23 ° C. The emulsion was stable for at least 2 weeks at 50 ° C.
ES 2 283 807 T3
Example 8
60 g of the amphiphilic dendritic polymer obtained in Example 2, 180 g of the short chain oil alkyd obtained in Example 4, 7.5 g of dipropylene glycol methyl ether and 10 g of dipropylene glycol n-butyl ether were charged, in a 1-liter laboratory flask equipped with a stirrer. The mixture was heated to 60 ° C and kept at this temperature. The mixture was stirred until homogeneous and then adjusted to pH 7.5 by adding dimethylethylamine and 6 g of a nonionic surfactant (Triton X100) was added and mixed. Next, 4 g of a Co / Li / Zr drier (Additol® VXW 6206, from Solutia Inc.) was added and stirring was allowed to continue for another 10 minutes. Next, 239 g of demineralized hot (50 ° C) water was added slowly over a 15 minute period and stirring was allowed to continue for another 20 minutes. Finally, the emulsion obtained was cooled to room temperature with stirring.
The obtained emulsion (air-drying water-based resin composition) had a solids content of 48% and a viscosity of 100 mPas at 23 ° C. The emulsion was stable for at least 1 week at 50 ° C.
Example 9
60 g of the amphiphilic dendritic polymer obtained in Example 2 and 180 g of the short chain oil alkyd obtained in Example 4 were charged into a 1 liter laboratory flask equipped with a stirrer. The mixture was heated to 60 ° C and kept at this temperature. The mixture was stirred until homogeneous and then adjusted to pH 7.5 by adding dimethylethylamine and 12.5 g of a nonionic surfactant (Triton X100) was added and mixed. Next, 4 g of a Co / Li / Zr drier (Additol® VXW 6206, from Solutia Inc.) was added and stirring was allowed to continue for another 10 minutes. Next, 243 g of demineralized hot (50 ° C) water was added slowly over a 15 minute period and stirring was allowed to continue for another 20 minutes. Finally, the emulsion obtained was cooled to room temperature with stirring.
The obtained emulsion (air-drying water-based resin composition) had a solids content of 50% and a viscosity of 150 mPas at 23 ° C. The emulsion was stable for at least 1 week at 50 ° C.
Example 10
48 g of the amphiphilic dendritic polymer obtained in Example 2 were charged into a 1 liter laboratory flask equipped with a stirrer. 5 g of dipropylene glycol n-butyl ether and 15 g of a partially neutralized alkylammonium salt of a polycarboxylic acid polymer and a polydimethylsiloxane (Lactimon® WS, from Dow Inc) were added with stirring. 210 g of hot water (50 ° C) were added over a 15 minute period. 25 g of the emulsion obtained were loaded into a high speed dissolver and 75 g of TiO were added<sub>2</sub> (Kronos® 2310, from Kronos GMBH) for 5 minutes. Dissolution was allowed to continue for another 30 minutes.
The obtained pigment paste had a viscosity of 15 Pas and a solid content of 78%.
Example 11
45 g of the emulsion obtained in Example 5 were charged into a 1 liter laboratory flask, equipped with a stirrer, and mixed with 55 g of the pigment paste obtained in Example 10. The mixture was stirred for 30 minutes at room temperature. The obtained white paint was stored for 24 hours before evaluation of drying and other properties.
The obtained white paint, comprising an air-drying water-based resin composition, had a solids content of 60%, a ratio of pigment to resin of 1.9: 1 and a viscosity of 150 mPas at 23 ° C. Example 12
45 g of the emulsion obtained in Example 6 were charged into a 1 liter laboratory flask, equipped with a stirrer, and mixed with 55 g of the pigment paste obtained in Example 10. The mixture was stirred for 30 minutes at room temperature. The obtained white paint was stored for 24 hours before evaluation of drying and other properties.
The obtained white paint, comprising an air-drying water-based resin composition, had a solids content of 65%, a ratio of pigment to resin of 1.6: 1 and a viscosity of 150 mPas at 23 ° C. Example 13
45 g of the emulsion obtained in Example 7 were charged into a 1 liter laboratory flask, equipped with a stirrer, and mixed with 55 g of the pigment paste obtained in Example 10. The mixture was stirred for 30 minutes at room temperature. The obtained white paint was stored for 24 hours before evaluation of drying and other properties.
ES 2 283 807 T3
The obtained white paint, comprising an air-drying water-based resin composition, had a solids content of 65%, a ratio of pigment to resin of 1.6: 1 and a viscosity of 150 mPas at 23 ° C. Example 14
45 g of the emulsion obtained in Example 8 were charged into a 1 liter laboratory flask, equipped with a stirrer, and mixed with 55 g of the pigment paste obtained in Example 10. The mixture was stirred for 30 minutes at room temperature. The obtained white paint was stored for 24 hours before evaluation of drying and other properties.
The white paint obtained, which comprises an air-drying water-based resin composition, had a solid content of 65%, a ratio of pigment to resin of 1.6: 1 and a viscosity of 200 mPas at 23 ° C. Example 15
45 g of the emulsion obtained in Example 6 were charged into a 1 liter laboratory flask, equipped with a stirrer, and mixed with 55 g of the pigment paste obtained in Example 10. The mixture was stirred for 30 minutes at room temperature. The obtained white paint was stored for 24 hours before evaluation of drying and other properties.
The white paint obtained, comprising an air-drying water-based resin composition, had a solids content of 65%, a ratio of pigment to resin of 1.6: 1 and a viscosity of 150 mPas at 23 ° C. Example 16
The drying properties of the emulsions, air-drying water-based resin compositions, obtained in Examples 5-9 were determined on a Beck Koller ™ test kit (Sheen Instrument, UK). Hardness was measured as pendulum hardness and expressed as Konig seconds.
The alkyd resins obtained in Examples 3 and 4 (Ref. 1 and 2) were dissolved in xylene and used as references. The same dryer and amount of dryer were used as in the water-based resin compositions and the same evaluations were performed.
Drying time
<td></td><td>Ref. 1</td><td>Ref. 2</td><td>Ex. 5</td><td>Ex. 6</td><td>Ex. 7</td><td>Ex 8</td><td>Ex. 9</td>
<td>Dry film, pm</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td>
<td>No stickiness, hrs</td><td> 12,5</td><td> 4,5</td><td> 5,5</td><td> 2</td><td> 1,5</td><td> 5</td><td> 4</td>
<td>Complete drying, hrs</td><td> >24</td><td> 14</td><td> 20,5</td><td> 6</td><td> 5,5</td><td> 22</td><td> 21</td>
Pendulum hardness
<td></td><td>Ref. 1</td><td>Ref. 2</td><td>Ex. 5</td><td>Ex. 6</td><td>Ex-7</td><td>Ex 8</td><td>Ex-9</td>
<td>Dry film, pm</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td><td> 50-60</td>
<td>2 days, seconds Konig</td><td> 14</td><td> 21</td><td> 25</td><td> 16</td><td> 16</td><td> 7</td><td> 7</td>
<td>4 days,</td><td> 14</td><td> 32</td><td> 25</td><td> 15</td><td> 15</td><td> 8</td><td> 9</td>
<td>7 days,</td><td> 14</td><td> 36</td><td> 25</td><td> 15</td><td> 15</td><td> 9</td><td> 9</td>
<td>10 days,</td><td> 16</td><td> 42</td><td> 24</td><td> 14</td><td> 14</td><td> 8</td><td> 8</td>
<td>14 days</td><td> 18</td><td> 46</td><td> 24</td><td> 14</td><td> 14</td><td> 8</td><td> 8</td>
Example 17
The drying properties of the white paints obtained in Examples 11-15 were determined on a Beck Koller ™ tester (Sheen Instrument, UK). The gloss, at 20 ° and 60 °, was determined after 48 drying and the hardness was measured as pendulum hardness and expressed as Konig seconds. All paints were coated to a wet film thickness of 120 μιη.
ES 2 283 807 T3
Drying time and shine
<td></td><td>Ex. 11</td><td>Ex. 12</td><td>Ex. 13</td><td>Ex. 14</td><td>Ex. 15</td>
<td>No stickiness, hrs</td><td> 3,5</td><td> 0,4</td><td> 0,4</td><td> 2,5</td><td> 2,4</td>
<td>Complete drying, hrs</td><td> 18</td><td> 4</td><td> 4</td><td> 16</td><td> 16</td>
<td></td><td></td><td></td><td></td><td></td><td></td>
<td>Brightness at 20 °</td><td> 40</td><td> 54</td><td> 61</td><td> 22</td><td> 48</td>
<td>Brightness at 60 °</td><td> 75</td><td> 88</td><td> 89</td><td> 66</td><td> 75</td>
Pendulum hardness
<td></td><td>Ex. 11</td><td>Ex. 12</td><td>Ex 13</td><td>Ex. 14</td><td>Ex. 15</td>
<td>2 days, seconds Konig</td><td> 25</td><td> 16</td><td> 16</td><td> 7</td><td> 7</td>
<td>4 days,</td><td> 25</td><td> 15</td><td> 15</td><td> 8</td><td> 9</td>
<td>7 days,</td><td> 25</td><td> 15</td><td> 15</td><td> 9</td><td> 9</td>
<td>10 days,</td><td> 24</td><td> 14</td><td> 14</td><td> 8</td><td> 8</td>
<td>14 days</td><td> 24</td><td> 14</td><td> 14</td><td> 8</td><td> 8</td>
Example 18
40 g of the amphiphilic dendritic polymer obtained in Example 2 and 160 g of commercially available tallow long chain oil alkyd resin (Duramac® 301-2007, from McWorther, Inc.) with an oil chain length of the 82% (as triglyceride), in a 1-liter laboratory flask equipped with a stirrer. The mixture was heated to 60 ° C and kept at this temperature. The mixture was stirred until homogeneous and then adjusted to pH 7.5 by the addition of dimethylethylamine. Next, 4 g of a Co / Li / Zr drier (Additol® VXW 6206, from Solutia Inc.) was added and stirring was allowed to continue for another 10 minutes. Next, 450 g of demineralized hot (50 ° C) water was added slowly over a 15 minute period and stirring was allowed to continue for another 20 minutes. Finally, the emulsion obtained was cooled to room temperature with stirring.
The obtained emulsion (air-drying water-based resin composition) had a solids content of 30% and a viscosity of 300 mPas at 23 ° C. The emulsion was stable for at least 6 months at room temperature. Example 19
240 g of the medium chain oil alkyd obtained in Example 3, 7.5 g of dipropylene glycol methyl ether and 10 g of dipropylene glycol n-bthyl ether were charged into a 1 liter laboratory flask equipped with a stirrer. The mixture was heated to 60 ° C and kept at this temperature. The mixture was stirred until homogeneous and then adjusted to pH 7.5 by the addition of dimethylethylamine and 6 g of a nonionic surfactant (Triton X100) was added and mixed. Then 4 g of a Co / Li / Zr drier (Additol® VXW 6206, from Solutia Inc.) was added and stirring was allowed to continue for another 10 minutes. Next, 236 g of demineralized hot (50 ° C) water was added slowly over a 15 minute period and stirring was allowed to continue for another 20 minutes. Finally, the emulsion obtained was cooled to room temperature with stirring.
The obtained emulsion separated within 15 minutes at room temperature.
Contents8
30 members in 18 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 0203156 | Sweden | A | |
| 0203156 | Sweden | A | |
| 20020003156 | Sweden | – | |
| 037517060203156 | – | – | – |
| SE20020003156 | – | – | – |
Members30
| Document | Office | Kind | |
|---|---|---|---|
| SE0203156D0 | Sweden | D0 | |
| SE0203156L | Sweden | L | |
| CA2502662A1 | Canada | A1 | |
| WO2004037928A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2003269776A1 | Australia | A1 | |
| SE524568C2 | Sweden | C2 | |
| KR20050072116A | Republic of Korea | A | |
| EP1554349A1 | European Patent Office (EPO) | A1 | |
| BR0315525A | Brazil | A | |
| MXPA05004298A | Mexico | A | |
| CN1708558A | China | A | |
| JP2006503955A | Japan | A | |
| US2006052510A1 | United States of America | A1 | |
| HK1080883A1 | Hong Kong, China | A1 | |
| ZA200503027B | South Africa | B | |
| NZ539471A | New Zealand | A | |
| US7186771B2 | United States of America | B2 | |
| EP1554349B1 | European Patent Office (EPO) | B1 | |
| AU2003269776B2 | Australia | B2 | |
| AT358164T | Austria | T | |
| ATE358164T1 | Austria | T1 | |
| DK1554349T3 | Denmark | T3 | |
| DE60312880D1 | Germany | D1 | |
| ES2283807T3This record | Spain | T3 | |
| DE60312880T2 | Germany | T2 | |
| CN100480335C | China | C | |
| JP4447462B2 | Japan | B2 | |
| KR100996170B1 | Republic of Korea | B1 | |
| CA2502662C | Canada | C | |
| BR0315525B1 | Brazil | B1 |
Numbers
- Publication
- 2283807
- Publication, DOCDB
- 2283807
- Publication, EPODOC
- ES2283807T
- Application
- 3751706
- Application, DOCDB
- 03751706
- Application, EPODOC
- ES20030751706T
Titles2
- Spanish
- COMPOSICION DE RESINA AL AGUA DE SECADO AL AIRE.
- English
- COMPOSITION OF RESIN TO AIR DRYING WATER.
Classification
- CPC, 10
- C08L101/005
- C09D201/005
- C08L101/00
- C08L71/02
- C08K5/092
- C08K5/09
- C08K5/01
- C08J3/20
- C08L2666/14
- C08L2205/02
- IPC, 4
- C08L101 00
- C08L
- C08L101 06
- C09D201 00