• 专利附录
  • 专利说明
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    • 专利摘要:
    CROSSOVER COMPOSITION, KIT OF PARTS, USES OF A COMPONENT, OF A MIXTURE OF COATING ADDITIVES, AND OF A HANDLING COMPOSITION, MIXING OF RMA COATING ADDITIVES, AND, COATING COMPOSITION. The invention relates to a crosslinkable composition, comprising a component A with at least 2 CH acid protons in activated methylene or methyl groups (the RMA donor group) and a component B with at least 2 activated unsaturated groups (the acceptor group of RMA) and a catalyst C system that contains or is capable of generating a basic catalyst capable of activating the RMA reaction between components A and B, characterized by the fact that the crosslinkable composition additionally comprises an XH group containing component D, which is also an addition donor Michael reactable with component B under the action of catalyst C, where X is N, P, O, S or where X is C, as part of an acid methyl group (CH3). The invention also relates to the use of component D and mixtures of catalyst additives, for the manufacture of crosslinkable composition of RMA, having improved surface appearance.
    公开号:BR112014008233B1
    申请号:R112014008233-2
    申请日:2012-10-08
    公开日:2020-11-10
    发明作者:Richard Hendrikus Gerrit Brinkhuis；Antonius Johannes Wilhelmus Buser；Petrus Johannes Maria David Elfrink；Ferry Ludovicus Thys；Elwin Aloysius Cornelius Adrianus De Wolf
    申请人:Allnex Netherlands B.V；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a crosslinkable composition, crosslinkable by Michael Real Addition reaction (RMA), in which at least 2 activated unsaturated groups (hereinafter also referred to as the RMA acceptor) and a component with at least 2 CH acid protons in activated methylene or methyl groups (hereinafter also referred to as the RMA donor), react and cross-link with each other in the presence of a strong base catalyst.
    [0002] RMA chemistry can be tuned to provide fast curing compositions (also at lower curing temperatures) in coating compositions, acceptable or good pot lives and good material properties, which make this chemistry very attractive, as a base for coating compositions. Details of the crosslinkable RMA compositions, employing a latent based crosslinkable catalyst, are described in WO2011 / 055463, which is hereby incorporated by reference.
    [0003] The addition of real Michael is activated by strong bases, but also inhibited by the presence of acidic species that will consume these basic catalysts. In tuning the reactivity of the coating systems, in order to obtain a desirable drying profile, there are several requirements for balance. The drying profile (also referred to as the reaction profile or as the cure profile) is the progress of the crosslinkable reaction, as a function of time. It is necessary that the drying profile allows the formation of mechanical properties as quickly as possible, to help the productivity of the coater. It is therefore also necessary to have a drying profile that is robust, that is, that the reactivity (and, consequently, the resulting drying profile) is not strongly influenced by low accidental levels of acid contaminants being present.
    [0004] On the other hand, it is required to have a good appearance of the resulting coating. This implies the need for sufficient leveling during the immediate period after application, when the curing coating composition is present as a liquid and capable of such leveling. This also implies the need for the absence of artifacts such as solvent inclusions or gas inclusions or other surface irregularities that may occur if the cure is very fast, especially if it is faster on the surface than in deeper layers, which is with often the case if curing occurs on the solvent evaporation time scale or activation of a catalyst surface. Also, the formation of surface hardness will be affected under conditions in which solvent entrapment occurs.
    [0005] The requirements described are, to some extent, opposite. For a fast curing profile, but also for high strength against accidental acid contaminants, reasonably high levels of catalyst are preferred, while at the same time, such high levels of catalysts can negatively influence the appearance of the surface and the development of hardness as described above. The aim of the invention is to provide a crosslinkable RMA composition, which provides a better balance of these seemingly contradictory requirements, in particular crosslinkable compositions having a high solids content.
    [0006] There is also a desire for crosslinkable compositions, which can be simply cured under ambient conditions, as opposed to, for example, compositions comprising photo-latent amine catalysts, known as T. Jung et al Farbe und Lacke Oct 2003. Such photo-latent amine catalysts, which really generate a strong base in UV radiation, are not suitable for coating more complex irregular substrates, where parts of the surfaces are not reachable with UV or visible light, or for highly pigmented systems.
    [0007] According to the invention, at least one of the problems mentioned above has been overcome by a crosslinkable composition, comprising: a. a component A with at least 2 C-H acid protons in methylene or activated methyl groups (the RMA donor group), and b. a component B with at least 2 unsaturated groups activated (the RMA acceptor group), and c. a catalyst system C that contains, or is capable of generating, a basic catalyst capable of activating the RMA reaction between components A and B, d. characterized by the fact that the crosslinkable composition additionally comprises an XH group containing component D, which is also a Michael addition donor, reactable with component B under the action of catalyst C, where X is N, P, O, S or where X is C, as part of an acid methyl group (CH3).
    [0008] In a preferred crosslinkable composition according to the invention, the acceptor groups B are acryloyl groups and preferably the RMA A donor groups are predominantly malonate groups. Typically, at least one of the A and B components are in the form of a polymer, for example, a polyester containing malonate groups. Preferably, catalyst C is a carbonate salt according to formula X + ROCO2, where X + is a non-acidic cation, preferably ammonium or quaternary phosphonium, and R is hydrogen or a substituted or unsubstituted alkyl, aryl or aralkyl group .
    [0009] It has been found that by using component D containing group XH as described, preferably those in which X is N, P or C, as part of an acid methyl (CH3) group, it is possible to create a reactivity profile comprising an initial induction time of decreased reaction rate, directly after application and activation of the system, followed by a relative increase in reactivity in later stages. This induction time can be adjusted, to allow an “open time”, a period allowing solvent flow and trapped air bubbles to escape, to be prolonged. The induction time allows for a significantly higher amount of flow and leveling of the system, avoiding surface defects, which can result from very fast curing without these additives, and better hardness formation due to solvent trapping, while still benefiting from the full potential of the catalysts, in addition to this induction time, thus creating an acceleration of the reaction in later stages, to complete the crosslinking at higher rates than would be found if simply using lower levels of catalyst. Also the high sensitivity of lower levels of catalyst, in relation to acid contamination accidentally present, is avoided.
    [00010] The effect obtained according to the present invention is illustrated in Fig. 1, which describes the conversion of acryloyl (when followed by FTIR at 80 cm-1) in the preferred acryloyl / malonate system, using succinimide as a component D. The crosslinkable composition without component D has a very fast hardness formation (open diamonds). The profile of the same composition with component D (closed diamonds) shows that the modifier component D of open time D creates an induction time in the reactivity profile in which the conversion is taken slowly and, after which, the conversion accelerates, to provide completion of complete cure. This effect cannot simply be achieved by choosing a smaller amount of catalyst C.
    [00011] The components of the crosslinkable composition form an acid-base balance system. The reactivity profile of the crosslinkable composition is the result of choosing the relative pKa values of the acidic components A and D in the composition, which contribute to the acid-base balance system and the relative reactivity of the deprotonated forms of the components in relation to component B A list of Pka values of suitable components D or A2: succinimide 9,5 ethosuximide 9,3 5,5-dimethylidantoin 10,2 1,2,4-triazole 10,2 1,2,3-triazole 9,4 benzotriazole 8.2 bezene s sulfonamide 10.1 nitromethane 10.2 isatin 10.3 uracil 9.9 4-nitro-2-methylimidazole 9.6 phenol 10.0 ethylacetoacetate 10.7 acetylacetone 9.0 diethylmalonate 13.0
    [00012] The XH group of component D has a higher acidity than the CH groups of component A, preferably being characterized by the fact that component D has a pKa (defined in the aqueous environment) of at least one unit, preferably two units, less than that of component A. Preferably, the pKa of the XH group of component D is less than 13, preferably less than 12, more preferably less than 11, more preferably less than 10. Excessive acidity may create problems with the components in the catalyst system; therefore, in consequence, the pKa is preferably higher than 7, more preferably 8. The difference in acidity ensures that, in the application of the coating, component D is activated (deprotonated) preferably on component A.
    [00013] It is preferred that component D has a reactivity in a Michael addition to component B, so that when present in a mixture side by side with CH functional groups of component A and a base catalyst, it is converted if relatively faster, compared to the CH of component A. This preference of D converting faster than A helps to create an induction time. Such a preference can be established by formulating both components A and D (or model compounds with similar functional groups) in similar amounts, with a limited amount of a component with similar functional groups as component B (eg, butylacrylate, de so that the number of RMA donor groups for RMA acceptor groups is 2 to 1), and completing the Michael addition in the presence of a base and analyzing the results with an appropriate technique, e.g. eg with LC or NMR. The conditions (eg, temperature) are then best chosen close to the conditions used in curing. As a first for RMA, this can be done under ambient temperature conditions. In this context, we observed that the addition-Michael procedures, through the reaction of the X-H component and not through some other independent component in another part of the molecule. However, in some examples, such as phenol, the proton abstraction of the X-H component can be followed by an electronic rearrangement resulting in the fact that component D is attached to a different part of the molecule.
    [00014] It is further preferred that component D has a reactivity towards the Michael addition, when activated with a base, which is less by at least a factor 3, preferably at least 10, more preferably at least 30, compared to that of the CH groups of component A, when it is also tested under comparable conditions in a formulation at room temperature with an excess of RMA B accepting groups and in the presence of a base at least capable of deprotonating 1 mol% of the RMA donor. The lower reactivity of D anions towards B, compared to that of A anions, helps to create an induction time. When considering its application for other curing temperatures, this relative reactivity is best determined at set temperatures.
    [00015] Catalyst C is mixed with components A and B just before use. Components A and B are usually stored together and must have a long shelf life. Component D can be mixed and stored with catalyst C or with components A and B. In particular in the latter case, in order to maintain acceptable pot life and shelf life, it is preferred that the XH group of component D is not too highly reactive towards Component B (eg acryloyl), in the absence of base catalyst C; that is, without activation by a base. Therefore, it is preferred that component D has a reactivity in a Michael addition to component B, so that, without activating the base, it has a half-life at room temperature, when dissolved in butylacrylate, of more than 30 minutes, preferably more than 1 hour, preferably more than 2 hours, preferably more than 4 hours, more preferably more than 8 hours, even more preferably more than 24 hours, most preferably more than 72 hours.
    [00016] In the crosslinkable composition, the XH groups of component C are preferably present in an amount corresponding to at least 50 mol%, preferably at least 100 mol%, most preferably at least 150 mol%, based on the amount of base to be generated by catalyst C. In addition, the XH groups of component D are preferably not more than 20 mol% compared to the CH donor groups of component A.
    [00017] Suitable components are the group X-H containing component D, where X is C as part of an acid methyl group (CH3), preferably nitromethane. Another group X-H containing component D or components where X is O, preferably a hydroxyl aromatic compound.
    [00018] Preferred components D are acid-aza compounds (X is N) preferably comprising a molecule containing NH as part of an Ar-NH- (C = O) -, - (C = O) -NH- (C = O) -, or a group -NH- (O = S = O) - or a heterocycle in which the nitrogen of the NH group is contained in a heterocyclic ring, more preferably component D is an imide derivative, preferably cyclic, preferably a succinimide or glutarimide (optionally substituted). A suitable example of substituted succinimide is ethosuximide.
    [00019] Other suitable components D, where X is N, are derivatives of hydantoin, for example, 5,5-dimethylidantoin, sufonamides such as benzene or toluenesulfonamide or components D being an N-H group containing heterocycle, preferably one substituted or not substituted triazole, pyrazole or imidazole, preferably 1,2,4-triazole, benzotriazole or 2-methyl-4-nitroimidazole or a derivative of uracil.
    [00020] In the crosslinkable composition, the XH groups of component D are present in an amount corresponding to at least 50 mol%, preferably at least 100 mol%, most preferably at least 150 mol% relative to the amount of base a be generated by catalyst C. The appropriate amount is highly determined by the acid-base characteristics of component D, relative to component A, and the reactivity of the corresponding anions relative to B, so that it can vary for different systems. We observed that the effect of improving open time can, in some cases, be obtained in very small amounts of component D, which is very advantageous because such small amounts do not or do not significantly affect the properties of the resulting cured composition; for example, the chemical and mechanical properties of a coating. Typically, the X-H groups of component D are present in an amount corresponding to no more than 30 mol%, preferably not more than 20, relative to the CN donor groups of component A.
    [00021] It should be noted that component D may be present in its deprotonated form (in acid-base equilibrium with other components). The amounts for component D referred to include both neutral as well as deprotonated form. This implies that, if present in quantities of more than 100% relative to a C-based catalyst, components C and D may be in equilibrium, so that effectively the deprotonated form of D is present as the dominant species to initiate additional RMA cure (then coexist as basic (C) and acidic (D) species in the formulation). Preferably, the X-H (number of groups per molecule) functionality of component D is low, preferably less than 4, more preferably less than 2, most preferably it is 1.
    [00022] The crosslinkable composition may comprise close to one or more different components D an A2 component comprising acid protons (CH) in methylene or methyl groups, having a higher acidity than component A and which are also reactive with respect to the component B. Such an A2 component can also contribute to the open time improvement effect, however, in order to have a significant A2 effect, it must typically be present in an amount between 10 - 40% by weight, which is a significantly higher amount than for component D. In the crosslinkable composition, the CH groups of component A2 are present in an amount between 1 and 50 mol%, preferably 5 - 50% by weight (for total CH in the RMA donor A).
    [00023] The A2 components preferably have a structure according to formula 2:
    wherein R is hydrogen or an alkyl, aralkyl or aryl substituent and Y and Y 'are the same or different substituent groups, preferably alkyl, aralkyl or aryl (R *), alkoxy (-OR *) or a polymeric backbone or in that -C (= O) -Y and / or -C (= O) -Y 'is replaced by CN or phenyl.
    [00024] The difference in acidity of the two acidic components CH A and A2 is chosen preferably by the fact that the pKa of component A2 is between 0.5 and 6, preferably between 1 and 5 and, more preferably, between 1.5 and 4 units smaller than the pKa of component A. Preferably, component A is a malonate containing component and component A2 is an acetoacetate or acetylacetone containing component, preferably of low CH functionality (preferably less than 10, more preferably less than 5, most preferably it is not more than 2).
    [00025] In a preferred embodiment, the crosslinkable composition comprises a mixture of RMA additives comprising: a. one or more components selected from the group of substituted or unsubstituted triazoles and A2 components, preferably a benzotriazole, acetoactate or acetylacetone and, additionally b. one or more components selected from the group of non-triazole D components, preferably N-H acid compounds, most preferably a succinimide.
    [00026] In another embodiment, the crosslinkable composition comprises a mixture of RMA additives comprising three different additives: a. one or more components selected from the group of substituted or unsubstituted triazoles (including benzotriazole) and b. one or more A2 components and, in addition, c. one or more components selected from the non-triazole D group.
    [00027] It was found that the additives listed in types a. - ç. above mentioned have a somewhat different effect on the crosslinking reaction kinetics and can be used in combination to optimize the curing crosslinking reaction, for example, in view of specific applications (paint formulations) or specific process conditions of application or coating requirements. We found that, especially, type a and b components greatly improve appearance at higher film thicknesses, while type c components have a more pronounced effect on hardness formation.
    [00028] The invention therefore also relates to a mixture of RMA coating additives comprising at least 2 different additives a. one or more components selected from the group of components A2, comprising C-H acid protons in activated methylene or methyl groups, preferably acetoacetate or acetylacetone, and substituted or unsubstituted triazole components, preferably triazole or benzotriazole and, in addition, b. one or more components selected from the group XH not triazole, containing components D, where X is N, P, O or S or where X is C, as part of an acid methyl group (CH3), preferably D components containing NH, most preferably a succinimide.
    [00029] In another embodiment the invention relates to such a mixture of RMA coating additives comprising at least 3 different additives; The. one or more A2 components, preferably acetoacetate or actilacetone and, in addition, b. one or more components selected from the group of substituted or unsubstituted triazoles, preferably benzotriazoles or triazoles, and c. one or more existing components, selected from the group of non-triazole D components.
    [00030] In said mixture of RMA coating additives, the pKa of group X-H of component D is preferably between 7 and 13, preferably less than 12, more preferably less than 11, most preferably less than 10; and preferably greater than 7, more preferably 8.
    [00031] The invention also relates to the use of component D or the above described mixtures of RMA coating additives for improving the appearance and hardness of a cured coating made of a crosslinkable RMA composition, comprising a component A with at least minus 2 two CH acid protons in activated methylene or methyl groups (the RMA donor group) and a B component with at least 2 activated unsaturated groups (the RMA acceptor group) and a crosslinking catalyst C, preferably a basic carbonate salt latent, as described herein, wherein said additive components are also Michael donor donor groups reactable with a component B and wherein the XH group of component D preferably has a pKa (defined in aqueous environment) of at least one unit, preferably two units, less than that of the CH groups of component A. Component A
    [00032] Suitable examples of components A containing activated methylene or methyl groups are well known in the art. Preferred are components containing oligomeric and / or polymeric group A, such as, for example, polyesters, polyurethanes, polyacrylates, epoxy resins, polyamides and polyvinyl resins containing groups A in the main chain, pendant or both.
    [00033] Component A is preferably malonate or acetoacetate. Components containing both malonate and acetoacetate groups on the same molecule are also suitable. In addition, physical mixtures of components containing malonate and acetoacetate group are suitable.
    [00034] In a more preferred embodiment of the crosslinkable composition, compound A is a compound containing malonate. It is preferred that in the crosslinkable composition most of the activated CH groups are malonate, that is, more than 50%, preferably more than 60%, more preferably more than 70%, most preferably more than 80% of all activated CH groups of the crosslinkable composition are malonate and, preferably, more than 50%, 60, 70 and, more preferably, more than 80% of the components A in a polymer are malonate groups.
    [00035] In another embodiment, the crosslinkable composition comprises a component A, for example, a polymer, in which more than 50%, preferably more than 70% more preferably more than 80% and, most preferably, more than 90% of the activated CH groups are malonate and a separate component, for example, another polymer, oligomer or monomer comprising non-malonate activated CH groups, for example, acetoacetate.
    [00036] Especially preferred components containing malonate group for use with the present invention are esters, and oligomeric or polymeric, containing malonate group, ethers, urethanes and epoxy esters containing 1 - 50, more preferably 2-10 malonate groups per molecule. In practice, polyethers and polyurethanes are preferred. It is also preferred that such components containing malonate group have a numerical average molecular weight (Mn) in the range of about 100 to about 5000, more preferably, 250-2500, and an acid number of about 2 or preferably less. Monomalonates can also be used when they have 2 reactive C-H per molecule. Numerical malonates can, in addition, be used as reactive diluents. Component B
    [00037] Components B can generally be ethylenically saturated components, in which the carbon-carbon double bond is activated by an electron withdrawing group, e.g. eg, a carbonyl group in the alpha position. Suitable components B are known in the art, for example, (met-) acryloyl esters, (met-) acrylamides, alternatively polyesters based on maleic, fumaric and / or itaconic acid (and maleic and itaconic anhydride and polyesters, polyurethanes, polyethers and / or alkyd resins containing pendent activated unsaturated groups Acrylates, fumarates and maleates are preferred.Most preferably, component B is an unsaturated acryloyl functional component.
    [00038] It is also especially preferred that the acid value of the components containing activated unsaturated group (as of any other component used in the composition) is low enough to not substantially impair the activity of the catalyst, thus preferably less than about 2, most preferably less than 1 mg KOH / g. As exemplified by the previously incorporated references, these and other components containing activated unsaturated group, and their methods of production, are generally known to those skilled in the art and need no further explanation here. Preferably, the functionality is 2 - 20, the equivalent weight (EQW: average molecular weight per reactive functional group) is 100 - 2000 and the numerical average molecular weight is preferably Mn 200 - 5000.
    [00039] The advantages of the invention are particularly manifest in critically difficult compositions, comprising not only a high content of solids, but also aiming at a high crosslinking density, with relative high concentrations and functionalities functionalities, for example, in the case of component A is a compound, in particular an oligomer or polymer, comprising an average of 2 to 30, preferably 4 to 20 and, more preferably, 4-10 CH activated by polymer chain.
    [00040] It is also possible that components A and B are present in hybrid molecules containing both types of functional groups.
    [00041] Typically, the concentrations of the functional groups in components A and B, and their relative stoichiometry, are chosen so that good film properties, after curing, can be expected, with efficient use of these functional groups. Typically, C-H / C = C stoichiometries are chosen to be 0.1 to 10, preferably 0.5 to 3, more preferably 0.7 to 3, most preferably 0.8 / 1.5. For this relationship, X-H of component D is added to groups C-H of component A. Component C
    [00042] The base C catalyst can, in principle, be any known catalyst, suitable for catalyzing RMA reactions. Preferably, in order to obtain good shelf life in combination with low temperature curing, the crosslinkable composition comprises a catalyst system C comprising a strong base blocked by a volatile acid, which is activated by evaporation of this acid. A suitable catalyst system C comprises a strong base blocked by a carbon dioxide, or the blocked catalytic species are of the formula ROCO2-, R being an optionally substituted alkyl, preferably C 1 - C 4 radical or hydrogen, preferably the catalyst comprises a basic blocked anion and a non-acidic cation, preferably an ammonium or quaternary phosphonium cation. Suitable C catalysts are described in WO 2011/055463, incorporated herein by reference. It is preferred that the crosslinking catalyst is used in an amount varying between 0.001 and 0.3 meq / g of solids, preferably between 0.01 and 0.2 meq / g of solids, more preferably between 0.2 and 0.1 meq / g of solids (meq / g of solids defined as the basis of mmoles relative to the total dry weight of the crosslinkable composition, not counting particulate charges or pigments). Alternatively, catalyst system C is activated by reacting an epoxy component with a tertiary amine, or an anion.
    [00043] For catalytic breakdown systems CO2, it was surprisingly found that significantly better shelf life could be achieved in a composition in which component A is a malonate, composition still comprising 0.1 - 10% by weight, preferably 0 , 1 - 5, more preferably 0.2 - 3 and most preferably 0.5 - 2% by weight of water (relative to the total weight of the coating composition). Preferably, the amount of agar is chosen in an amount effective to increase the gel time by at least 15 minutes, preferably at least 30 min, more preferably at least 1 h, even more preferably at least 5 h, and most preferably at least 24 h, 48 h or at least 10%, 50% or 100%, compared to the same composition without water.
    [00044] The crosslinking composition can comprise a solvent. For catalyst systems for CO2 de-aggregation, the inventors have also found that advantages can be achieved in pot life if in the crosslinkable composition at least part of the solemn is a primary alcohol solvent. The solvent can be a mixture of a non-alcoholic solvent and an alcohol solvent. Preferably, the alcohol is present in an amount of at least 1, preferably 2 more preferably 3, most preferably at least 5, even more preferably at least 10% by weight relative to the total weight of the crosslinkable composition and, in view of VOC restrictions , preferably at most 45, preferably at most 40% by weight, most preferably less than 30% by weight.
    [00045] The alcohol solvent is preferably one or more primary alcohols, more preferably a mono-alcohol having 1 to 20, preferably 1-10, more preferably 1-6 carbon atoms, preferably selected from the group of ethanol, n-propanol, n-butanol, n-amyl alcohol and butylglycol.
    [00046] The crosslinkable composition according to the present invention comprises between 5 and 95% by weight of a component A with at least 2 CH acid protons in methylene or activated methyl, and between 5 and 95% by weight of a component B with at least 2 activated unsaturated groups (% by weight relative to the total weight of the crosslinkable composition) and a C catalyst system that contains, or is capable of generating a basic catalyst capable of activating the RMA reaction between A and B components, at levels of 0, 0001 and 0.5 meq / g of solid components, an amount of component D present in quantities of at least 50 mol% relative to the base generated by component C and less than 30 mol% of active CH groups of component A optionally between 0.1 and 80% by weight of solvent (preferably less than 45% by weight), preferably an organic solvent, preferably containing at least 1% by weight of a primary alcohol and preferably also containing 0.1, preferably 0, 5 - 10% by weight of water The.
    [00047] Whereas the crosslinkable composition is a 2K composition that is only formed immediately before actual use, the invention also relates to a kit of parts for the manufacture of the composition according to the present invention, comprising a part 1 comprising components A and B and part 2 comprising component C and wherein one or more components D or optional components A2 can be included in part 1 or part 2 or both. The invention also relates to the use of component D, optionally in combination with component A2, as described above, as an additive for crosslinkable RMA compositions for improving the open time of the crosslinkable composition and for improving the appearance and hardness of the composition resulting cured, in particular a coating.
    [00048] The invention also relates to the use of the crosslinking composition according to the present invention in a method for the manufacture of coating, films or inks and to coating compositions, inks or films comprising the crosslinking composition according to application-oriented additives, for example, one or more coating additives such as pigments, coagglutinants, solvents, etc.
    [00049] The invention also relates to the use of crosslinkable compositions as described here, for the preparation of a coating in which component D preferably produces in said coating an increase in time to obtain a conversion level of 30% of at least 3 , preferably 5, more preferably 10 minutes, preferably less than 60, more preferably less than 30 minutes, when compared to the same coating without component D.
    [00050] The preceding more general discussion of the present invention will be further illustrated by the following specific examples, which are exemplary only.
    [00051] Molecular weights were measured by GPC in THF and expressed in equivalent weights of polystyrene.
    [00052] Viscosities were measured with a TA Instruments AR 2000 Rheometer, using a cone and silver installation (cone 4 cm Io) at a voltage of 1 Pa.
    [00053] Tube and sphere method for determining pot life: A flat-bottomed test tube (internal diameter 15 mm, depth 12.5 cm), containing two marks, 5 cm apart, are filled with 20 ml of paint. A steel ball with a diameter of 8 mm is added and the tube is closed with a pressure cap. The tube is held at an angle of 10 ° and the steel ball is allowed to roll over the test tube wall. The time required to roll between the two marks is noted as a measure for viscosity. The time required to double in viscosity is considered to be life and pot. If necessary, this time is calculated by linear interpolation between two measurements. This method was used for pigmented formulations. For transparent formulations, a glass test tube (length 12 cm, diameter 13 cm) was filled with a stainless steel sphere 12 mm in diameter and the formulation to be, leaving a very limited air space, and closed. The time was recorded for the sphere to fall and travel a distance of 5 cm when the tube was tilted vertically. An average was recorded during 2 measurements.
    [00054] Drying time by the drying recorder: To determine the drying time by the recorder, the paint was applied to a glass panel with a scalpel with a span of 90 p. The drying time was measured with a Gardico electronic drying time recorder, type DT-5020, adjusted in a cycle time of 60 minutes. The drying time was recorded as the time when the stylus left no visible trace on the film.
    [00055] Drying times of TNO cotton ball: Dust-free and handle-free times were measured according to the so-called TNO method, with a cotton pad. Dry powder time means the time required for the coating, after the pad has dropped onto the surface of the coating and after leaving it there for 10 seconds, do not catch any cotton residue sticking to the surface after blowing the pad away. For free holding time, the same applies, but now a weight load of 1 kg is applied to the pad for 10 seconds.
    [00056] Persoz hardness measurement: The Persoz pendulum hardness was measured in an air-conditioned room at 23 ° C and 55 + 7-5% relative humidity. Hardness is measured with a Persoz pendulum acc. as described in ASTM D 4366. For gradient layer thickness panels, hardness is measured at different points and the corresponding layer thickness is measured. If necessary, the hardness at a certain layer thickness is calculated by linear interpolation of the measurement at two different layer thicknesses. The layer thicknesses were measured with a Fischer Permascope MP40E-3.
    [00057] Pigmented inks sprayed from optical evaluation: Paint was sprayed with a devilbiss spray gun, FF-1.4 nozzle with an air pressure of 3.5 bar. The paint was sprayed in a continuous layer over the entire surface of a 55 x 10 cm steel panel. A consecutive layer was sprayed, starting at 10 cm from the right edge. Several layers were built, moving to the right, so that a layer thickness gradient was built from left to right. Films were allowed to dry horizontally at 23 ° C, 4% RH. The layer thicknesses were measured with a Fischer Permascope MP40E-S. At a layer thickness of 100 p, an image was taken with an Olympus SZX10 microscope (ampl. IX) equipped with a digital camera.
    [00058] Wavescan analysis: The panels, as described above, were analyzed using the Wavescan II of Byk instruments. Data was stored using Autochar software from Byk. Analysis was performed in the direction perpendicular to the thickness gradient. In this instrument the light of a small laser diode is reflected by the sample surface at an angle of 60 ° and the reflected light is detected at the angle of brightness (60 ° opposite). During the measurement, the “wave scan” is moved across the sample surface by a scan length of approximately 10 cm, with a data point being recorded every 0.027 mm. The surface structure of the sample modulates the light from the laser diode. The signal is divided into 5 wavelength bands in the range of 0.1 -30 mm and processed by mathematical filtering. A characteristic value for each of the 5 ranges (Wa 0.1 - 0.3 mm, Wb 0.3 - 1.0 mm, Wc 1.0 - 3.0 mm, Wd 3.0 - 10 mm, We 10 -30 mm), as well as the long wave (LW, approx. 1 - 10mm) and short wave (SW, approx. 0.3 - 1 mm) of wave scan values are calculated. Low values mean a smooth surface structure. In addition, an LED light source is installed in a wave-scanning DOI and illuminates the surface under 20 degrees after passing through an opening. The scattered light is detected and a value called dullness (du, <0.1 mm) is measured. Using the three values of the short wave range Wa, Wb and du a DOI value is calculated (See Osterhold e.a., Progress in Organic Coatings, 2009, vol. 65, no4, pages 44 - 443).
    [00059] The following abbreviations were used for chemicals used in the experiments: DiTMPTA is di-trimethylolpropane-tetracrylate (obtained from Aldrich (MW = 466 g / mol)) or used as Sartomer SR355 (commercially supplied by Sartomer); Dysperbyk 163 is a commercial dispersant supplied by Byk; Byk 310 and 315 are additives commercially supplied by Byk; Kronos 2310 is a TiO2 pigment commercially supplied by Kronos, TBAH is tetrabutylammonium hydroxide, BuAc is Butyl acetate, MEK is Methyl ethyl ketone (2-Butanone); Et Ac Ac is ethyl acetoacetate; DEC is diethyl carbonate; IPA is isopropanol; TA is room temperature. Preparation of malonate polyester A
    [00060] Into a reactor provided with a distillation column filled with Raschig rings, 17.31 mol of neopentyl glycol, 8.03 mol of hexahydrophthalic anhydride and 0.0047 mol of butyl ethanoic acid were brought. The mix was polymerized at 240 ° C under nitrogen at an acid value of 0.2 mg KOH / g. The mixture was cooled to 130 ° C and 10.44 mol of diethylmalonate was added. The reaction mixture was heated to 170 ° C and ethanol was removed under reduced pressure. The almost colorless material was cooled and diluted with 420 g of butyl acetate to a solids content of 90%. The final resin had an acid value of 0.3 mg KOH / g of solids, an OH value of 20 mg KOH / g of solids and an average molecular weight of 3400 Da. Catalyst solution C
    [00061] A catalyst solution was prepared by reacting 59.4 g of a TB AH solution (40% in water) with 13.5 g DEC (reacting overnight in RT), with 14.5 g of isopropanol as a co-solvent, followed by the corresponding development of the etocarbonate species. Titration indicated that the block was complete and that the blocked base concentration was 0.83 meq / g of solution. C2 catalyst solution
    [00062] In 43.6 g of a 45% aqueous solution of TBAH, 36.6 g of isopropanol and 60 g of DEC were added. After standing overnight, the mixture was filtered through paper. Titration showed that the catalyst contained 0.52 meq of blocked base per gram of solution. C3 catalyst solution
    [00063] C3 catalyst solution was prepared by reacting 39.9 g of a TBAH solution (40% in methanol) with 8.6 g DMC and an additional 6.5 g of methanol (reacting overnight in RT). The light turbidity solution was filtered through a folded paper filter, resulting in a clear solution. Titration indicated that the block was complete and that the blocked base concentration was 1.14 meq / g of solution. Comparative example formulation 1, example formulations 1-4
    [00064] Formulations were prepared based on a malonate A donor resin, DiTMPTA as an acryloyl donor resin, and the indicated amount of succinimide and tuned to a viscosity of 160 mPa.s with a 1: 1 MEK / BuAc mixture in volume. These were mixed with an amount of Cl catalyst solution. Table A lists the details of the total composition. Catalyst amounts are 50 ueg / g of solids, water levels are 1.8% by weight, isopropanol at 0.7% by weight, estimated ethanol level at 0.2% by weight. Table A

    [00065] Of these formulations, the drying behavior at room temperature, for films leading to a dry film thickness around 70 - 75 mu, was followed with TNO cotton ball drying tests and the development of Persoz pendulum hardness. It was determined; these results are also listed in Table B. Table B

    [00066] It can be seen that, while comparative example 1 shows extremely fast drying, the actual Persoz hardness levels are low, presumably due to solvent trapping in the system. In addition, the appearance of this comparative example 1 is poor. In the addition of low levels of succinimide (slightly higher than the levels of the used catalyst), some drying delay is seen, but still providing drying times considered to be fast; however, it can also be seen that the development of Persoz hardness is greatly improved. At the same time, the example films with succinimide exhibit a better appearance than those of comparative example 1.
    [00067] Example formulations 5-7 and comparative example formulations 2-3 were prepared as pigmented inks, with compositions as tabulated in Table C (gram quantities). Table C

    [00068] The pot life of these pigmented inks was measured and the drying times of these inks brought to the ink panels were determined with a drying recorder. These paints were also applied by spraying on a steel panel to obtain a gradient film thickness panel. Persoz hardness at 50 mu dry film thickness was determined after 24 h curing at room temperature; microscopic images were taken of the resulting coatings on these panels at approximately 100 mu of dry film thickness (Appendix: Photographs). Pot life of these paints was also measured. The results are included in table C.
    [00069] It can be seen, by comparing comparative example 3 with examples 6 and 7, that the addition of succinimide to the formulation provides clear advantages in building Persoz hardness and some advantage in pot life. Example 7, with a higher level of succinimide, shows a significant increase in drying time, the value of 44 minutes, which can, however, still be considered as an acceptable to good value. The panels in examples 6 and 7 look much better than the panels in comparative example 3, as can be judged by comparing microscopic photographs, comparative example 3 showing many more defects (Appendix: Photographs).
    [00070] Similar conclusions can be drawn from a comparison of comparative example2, with example 5, now based on a formulation with included acetoacetate, in addition to malonate, as RMA donor groups. Example 5 (with added succinimide) exhibits higher Persoz hardness, better pot life and better appearance (Appendix: Photographs) than that of comparative example 2 (not containing succinimide).
    [00071] Example 8 was prepared and evaluated in a similar manner, as discussed above for examples 5 - 7, the composition and results being given below in table D (gram quantities). It can be seen that the additional presence of 1,2,4-triazole (when compared to example 6) results in a significant improvement in shelf life, other benefits being retained. Table D

    [00072] Example formulations 9 and 10 and comparative example formulations 4 and 5 were formulated and evaluated along similar lines, now also including Wavescan analysis, to have a quantitative indication of the quality of appearance. Compositions and results are given in Table E (quantities in grams). Table E

    [00073] The formulation example 9 can be compared with the comparative formulation and example 4, the formulation example 10 can be compared with the comparative formulation of example 5, the difference being the presence of low amounts of succinimide. It can be concluded from both comparisons that the presence of succinimide, in addition to the improved Persoz hardness, results in significantly improved values for long and short wave roughness, dullness and DOI. Example 11: Impact on conversion kinetics
    [00074] The conversion of the acryloyls in the system can be followed by FTIR, focusing on the 809 cm-1 band characteristic of the acryloyl. By doing this, the impact of the added succinimide on the total conversion can be made visible. Two systems were formulated (according to the compositions of comparative example 1 (without succinimide) and formulation example 1 (with 150% succinimide relative to solids). Figure 1 compares the conversion of these systems after application on top of an ATR crystal, the IR beam probing the deeper layers, close to the substrate. Initial conversion of the formulation without succinimide is rapid, which is also the cause of solvent entrapment and potential appearance problems. It can be seen that the addition of succinimide, even at these levels very low, results in a significant delay of the initial conversion; simultaneously, this illustrates that, after this period of initial delay, the conversion rate is accelerating, so that the cure rate in relation to higher conversions is still fast after this initial delay. Example 12. Determination of Michael adductivity of succinimide
    [00075] 5 grams of sccinimide (50.5 mmol) were dissolved in a mixture of 42 grams of butyl acrylate and 42 grams of methanol and kept at room temperature as such, or after adding a strong base (9.82 g of 1 , 12 meq / g of solution of etrabutylammonium hydroxide in methanol, 11 meq). Subsequently, the succinimide concentration is determined as a function of time by obtaining samples, neutralizing with a known excess of HCl in water and back-titrating with a KOH solution. Without baseline initiation, no significant loss of NH succinimide in this solution is seen in two weeks. With the base added, the succinimide concentration can be seen to decrease over time, as illustrated in table F below. The concentration of succinimide is expressed as% relative to the theoretical level, based on quantities used. Table F

    [00076] At this level of catalyst ([succinimide] / [base] = 5), it takes about an hour to lose 25% of the acidic protons of succinimide to be consumed.
    [00077] Using the same method, the reactivity for several other components was also determined; as a reference, a similar construction was used for dimethylmalonate reactivity under these conditions (only in this case the remaining DMM level was determined with GC). Table G lists the results of the relative Michael addition reactivities, expressed as a number indicating the initial increase in conversion%, per minute, under these conditions. It can be seen that in all cases this intrinsic reactivity is significantly less than that of a malonate, but still present. Table G Conversion rates relative
    Example 13:
    [00078] In Table H, additional results have been listed that illustrate the beneficial effect on the hardness construction of various compositions according to the present invention.
    [00079] The formulations were prepared from 15 g of polyester malonate A, 6.1 g of DTMPTA, 1.5 g of n-propanol, 0.84 g of catalyst solution C-3 (1.14 meq base / g solids in formulation) and an amount of component XH given in table 103 below; the films were applied by stretching on glass with a dry film thickness of ca. 60 mu, or 80 mu, and Persoz hardness (s) was determined after 1.7 and 28 days at room temperature: the results are shown in table H. The beneficial impact on hardness construction in the examples according to the present invention is illustrated. Table H
    Example 14
    [00080] Formulations were prepared with components as indicated in table 104. Persoz hardness of one day after application (spraying on joint panels) at room temperature is given. Typical layer thicknesses were 60 - 80 mu. The hardness value of the comparative example, without NH components, was 64 sec. It can be seen that the use of succinimide, ethosuximide, isatin and 2-methyl-4-nitroimidazole is favorable for the construction of hardness. The thinner used was a 1: 1 (by weight) mixture of butylacetate and MEK; catalyst solution was prepared similar to Cl and had a base concentration of 0.7 meq / g. The results and compositions are listed in Table 1. Table I
    Example 5
    [00081] Formulations were prepared, sprayed on junction panels and dried at room temperature. The appearance of the panels was analyzed with a Byk Wavescan instrument, pendulum hardness (in sec, after 1 day) and the long wave / short wave numbers (lower is better) are reported in Table J, along with composition data. The advantageous effect of the formulations according to the present invention on hardness and appearance can be seen. The catalyst solution was as in example 14; the thinner used was a 1: 1 (by weight) mixture of butylacetate and MEK. Table J (example 15)
    权利要求:
    Claims (29)
    [0001]
    1. Crosslinkable composition comprising: a. a component A with at least 2 RMA donor groups being C-H acid protons in methylene or activated methyl groups, and b. a component B with at least 2 RMA donor groups being activated unsaturated groups, and c. a catalyst system C that contains, or is capable of generating, a basic catalyst capable of activating the RMA reaction between components A and B, d. characterized by the fact that the crosslinkable composition additionally comprises an XH group containing component D, which is also a Michael addition donor, reactive with component B under the action of catalyst C, where X is N, P, O, S or where X is C, as part of a methyl acid group, where component A is malonate or acetoacetate and where the XH group of component D has a higher acidity than the CH group of component A, where component D has a pKa, defined in an aqueous medium, of at least one unit smaller than the CH group of component A.
    [0002]
    2. Crosslinkable composition according to claim 1, characterized by the fact that the RMA accepting groups of component B are acryloyl groups.
    [0003]
    3. Crosslinkable composition according to claim 1, characterized by the fact that component A RMA donor groups originate predominantly from malonate groups.
    [0004]
    4. Crosslinkable composition according to claim 3, characterized by the fact that more than 50% of components A are malonate groups.
    [0005]
    5. Crosslinkable composition according to claim 1, characterized by the fact that the X-H group of component D has a pKa, defined in an aqueous environment, of at least two units less than that of the predominant C-H groups in component A
    [0006]
    6. Crosslinkable composition according to claim 1, characterized by the fact that the pKa of the X-H group of component D is less than 13.
    [0007]
    7. Crosslinkable composition according to claim 1, characterized by the fact that the XH groups of component D are present in an amount corresponding to at least 50 mol% in relation to the amount of base to be generated by catalyst C, in which the XH groups of component D are present in an amount corresponding to no more than 30 mol% relative to donor groups C-H of component A.
    [0008]
    Crosslinkable composition according to claim 1, characterized by the fact that in component D containing group X-H, X is C as part of a CH3 acid methyl group, a nitromethane or where X is O.
    [0009]
    A crosslinkable composition according to claim 1, characterized by the fact that component D is an acid-aza compound comprising a molecule containing N-H, as part of an -Ar- NH- group (C = O). - (C = O) -NH- (C = O) -. or an -NH- group (O = S = O) or a heterocycle in which the nitrogen of the N-H group is contained in a heterocyclic ring.
    [0010]
    10. Crosslinkable composition according to claim 9, characterized by the fact that component D is an imide derivative, a cyclic imide derivative, a succinimide or glutarimide or in which component D is a hydantoin derivative, 5-5- dimethylhydantoin or where component D is a sulfonamide, aromatic sulfonamide, benzene or toluenesulfonamide or where component D is an NH in group containing heterocycle, a triazole, pyrazole on substituted or unsubstituted imididazole.
    [0011]
    Cross-linkable composition according to claim 9, characterized in that component D is 1,2,4-triazole, benzotriazole or 2-methyl-4-nitroimidazole.
    [0012]
    12. Crosslinkable composition according to claim 1, characterized in that the crosslinkable composition comprises close to one or more different D components, an A2 component comprising CH acid protons in activated methylene or methyl groups having a higher acidity than the component A and which is also reactive of RMA in relation to component B.
    [0013]
    13. Crosslinkable composition according to claim 12, characterized in that A2 is an acetoacetate or acetylacetone.
    [0014]
    14. Crosslinkable composition according to claim 12, characterized in that the A2 component C-H groups are present in an amount between 1 and 50 mol% for the total C-H in the RMA donor A.
    [0015]
    15. Crosslinkable composition according to claim 1, characterized by the fact that it comprises a. one or more components selected from the group of substituted or unsubstituted triazoles and A2 components, and additionally b. one or more components selected from the group of non-triazole components D.
    [0016]
    16. Crosslinkable composition according to claim 15, characterized by the fact that a. o one or more components selected from the group of substituted or unsubstituted triazoles and A2 components are benzotriazoles, acetoacetate or acetylacetone, and additionally b. the one or more components selected from the component D group of non-triazoles are acidic N-H compounds.
    [0017]
    17. Crosslinkable composition according to claim 15, characterized by the fact that it comprises: a. one or more components selected from the group of substituted or unsubstituted triazoles and b. one or more A2 components and, in addition, c. one or more components selected from the group of non-triazole D components.
    [0018]
    18. Crosslinkable composition according to claim 1, characterized by the fact that it comprises a. between 5 and 95% by weight of a component A with at least 2 C-H acid protons in methylene or activated methyl, and b. between 5 and 95% by weight of a component B with at least 2 unsaturated groups activated,% by weight relative to the total weight of the crosslinkable composition, and c. a catalyst system C that contains or is capable of generating a basic catalyst, capable of activating the RMA reaction between components A and B, at levels of 0.0001 and 0.5 meq / g of solid components, d. an amount of component D present in amounts of at least 50 mol%, relative to the base generated by component C, and less than 30 mol% of active groups C-H of component A e. between 0.1 and 80% by weight of solvent.
    [0019]
    19. Crosslinkable composition according to claim 18, characterized in that it is an organic solvent containing at least 1% by weight of a primary alcohol.
    [0020]
    20. Crosslinkable composition according to claim 18, characterized by the fact that it still contains 0.1% by weight of water. sπ
    [0021]
    21. Kit of parts for the manufacture of the composition as defined in claim 1, characterized in that it comprises a part 1 comprising components A and B, and a part 2 comprising component C, and in which one or more components D or components A2 can be included in part 1 or part 2 or both.
    [0022]
    22. Mixture of RMA coating additives, characterized by the fact that it comprises: a. one or more components selected from the group of components A2, comprising C-H acid protons in activated methylene or methyl groups and additionally substituted or unsubstituted triazole components b. one or more components selected from the group X-H non-triazoles containing components D, where X is N, P, O or S or where X is C, as part of a CH3 methyl acid group.
    [0023]
    23. Mixture of RMA coating additives according to claim 22, characterized in that it comprises: a. one or more components selected from the group of acetoacetate or acetylacetone, triazole or benzotriazole and b. one or more components selected from component group D containing non-triazole N-H.
    [0024]
    24. Mixture of RMA coating additives according to claim 22, characterized in that it comprises: a. one or more A2 components and additionally b. one or more components selected from the group of substituted or unsubstituted triazoles and c. one or more components selected from the group of non-triazole D components.
    [0025]
    25. Mixture of RMA coating additives according to claim 22, characterized in that it comprises: a. one or more A2 components that are acetoacetate or acetylacetone and b. one or more components selected from the group of substituted or unsubstituted triazoles which are benzotriazoles or triazoles.
    [0026]
    26. Mixture of RMA coating additives according to claim 22, characterized in that the pKa of the X-H group of component D is between 7 and 13.
    [0027]
    27. Method for improving the appearance and strength of the cured coating, characterized by the fact that it comprises providing a cross-linkable composition comprising: to an A component with at least 2 RMA donor groups being CH acid protons in activated methylene or methyl groups and b one component B with at least 2 RMA donor groups being unsaturated activated groups and a catalyst system C that contains, or is capable of generating, a basic catalyst capable of activating the reaction between RMA and components A and B, in which the composition The crosslinker further comprises a component D containing the group XH which also donates the addition of Michael reactive with component B under the action of catalyst C, where X is N, P, O, S or where X is C as part of acid methyl group, in which component A is a malonate or acetoacetate, and in which the XH group of component D has a pKa, defined in aqueous medium, of at least one unit smaller than the CH group of component A, alone or in co combination with component A2 comprising acidic C-H protons in activated methylene or methyl groups having a greater acidity than component A and which is also the reactive RMA for component B, or a mixture of RMA coating additives comprising a. one or more components selected from the group of components A2 comprising C-H acid protons in activated groups of methylene and methyl, and substituted and unsubstituted triazole components, and additionally b. one or more components selected from the group of components D containing non-triazole X-H, where X is N, P, O or S or where X is C as part of the CH3 methyl acid group.
    [0028]
    28. Method for manufacturing coating compositions, films or paints, characterized by the fact that it provides the crosslinkable composition as defined in claim 22.
    [0029]
    29. Coating composition, characterized by the fact that it comprises the crosslinkable composition as defined in claim 1 and additionally comprises one or more coating additives such as coagglutinants or solvents.
    类似技术:
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    同族专利:
    公开号 | 公开日
    AU2012320414A1|2014-05-01|
    CN103890049B|2016-03-09|
    SG11201401427QA|2014-09-26|
    AU2012320414B2|2016-07-28|
    JP5910952B2|2016-04-27|
    EP2764038B9|2017-03-01|
    TWI570166B|2017-02-11|
    CN103890049A|2014-06-25|
    EP2764038A1|2014-08-13|
    KR102068850B1|2020-01-21|
    TW201335247A|2013-09-01|
    KR20140080499A|2014-06-30|
    ES2623427T3|2017-07-11|
    IN2014CN03334A|2015-07-03|
    EP2764038B1|2016-12-07|
    RU2014111980A|2015-11-20|
    JP2014529001A|2014-10-30|
    US9284423B2|2016-03-15|
    BR112014008233A2|2017-04-11|
    RU2625122C2|2017-07-11|
    PL2764038T3|2017-08-31|
    US20140235785A1|2014-08-21|
    WO2013050623A1|2013-04-11|
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    法律状态:
    2018-05-02| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-05-08| B25D| Requested change of name of applicant approved|Owner name: ALLNEX NETHERLANDS B.V. (NL) |
    2020-06-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11184426|2011-10-07|
    EP11184426.2|2011-10-07|
    PCT/EP2012/069905|WO2013050623A1|2011-10-07|2012-10-08|Crosslinkable composition crosslinkable by real michael additionreaction|
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