|Applicants||Cognis IP Management GmbH|
|USPTO Patent||US 15230126|
Esters of general formula R1—COOR2, where R1=9 to 23 C alkyl and R2=methyl, ethyl, n-propyl or i-propyl are suitable as coalescing agents, in particular for the production of all types of coatings from an aqueous polymer or latex dispersion.
13. A method of coalescing a coating or film of an aqueous dispersion of polymer particles or latex particles comprising:
(a) providing the aqueous dispersion of polymer particles or latex particles, and
(b) adding a coalescing agent to the aqueous dispersion of polymer particles or latex particles to provide a coating material, wherein the coalescing agent consists of one or more esters of the general formula (I),
in which R1 is a saturated alkyl radical having 9 to 23 C atoms and R2 is a saturated alkyl radical selected from the group of methyl, ethyl, n-propyl, and isopropyl,
and wherein a coating or film of the coating composition exhibits an increased hardness compared to a coating or film of a second coating composition containing an ester of general formula (I) in which there is unsaturation in R1, R2, or both.
14. The method of claim 13 wherein the coating material contains 0.1% to 5% by weight of the one or more esters of general formula (I).
15. The method of claim 13 wherein the coating material contains 0.5% to 2% by weight of the one or more esters of general formula (I).
16. The method of claim 13 wherein the one or more esters of general formula (I) is the sole coalescing agent in the coating composition.
17. The method of claim 13 wherein the coating composition is free of an ester having a general formula (I), wherein R1, R2, or both contain unsaturation.
20. The method of claim 13 wherein the one or more esters of general formula (I) is an ester of capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, isotearic acid, nonadecanoic acid, eicosanoic acid, and docosanoic acid.
21. The method of claim 13 wherein the coalescing agent is selected from the group consisting of methyl laurate, methyl myristate, methyl palmitate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, and mixtures thereof.
1. This is a continuation of the U.S. patent application Ser. No. 12/598,505, which is the U.S. national phase of International Application No. PCT/EP2008/003294, filed Apr. 24, 2008, which claims the benefit of German Patent Application No. 10 2007 021 139.4, filed May 3, 2007.
2. The invention relates to the use of esters of the general formula R1—COOR2, in which R1 is an alkyl radical having 9 to 23 C atoms and R2 is a saturated alkyl radical selected from the group of methyl, ethyl, n-propyl, and isopropyl, as coalescents, in particular for the preparation of coating materials.
3. Coalescents (also called film-forming assistants) are known per se. They are added to aqueous coating materials and bring about filming of dispersed polymer particles to form a homogeneous coating film. Adding them is required when the film-forming temperature of the binder is above the temperature of the application.
4. Known film-forming assistants include the following: ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol phenyl ether, propylene glycol tert-butyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (compare “Farbe+Lack”, 101 (July 1995), pp. 606-609).
5. In recent times, for environmental reasons, water-based coatings have become very topical. In latex coatings, based in particular on small particles of synthetic polymers such as polyacrylates, coalescents have traditionally been used in substantial quantities. These coalescents (also called filming assistants) are added to the coatings in order to improve film formation. The function derives from the plasticizing effect exerted by the coalescent on the latex particles, enabling them to coalesce and form a continuous film. This film has optimum properties after the evaporation of the water. Important in the formation of a film is the temperature known as the film-forming temperature, at which (or below which) the polymer particles coalesce to form a film. The customary coalescents lower the film-forming temperature of the polymer.
6. Conventional coalescents are certain esters and ethers; known technical standards are the hydroxyl ester “Texanol” from Eastman (also often called TMB; a 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), and also “EGBE” from Union Carbide (ethylene glycol monobutyl ether).
7. DE 24 43 645 was published back in 1976. Explicitly disclosed therein is benzoic acid 1,2-propanediol monoester, albeit specifically in connection with amino resins. The claims are directed to “modified amino resins” which comprise compounds of the aryl-COO—X—OH type as modifiers.
12. EP 069,839 B1 claims the use of hydroxyl ester mixtures as flow control assistants for aqueous polymer dispersions. The compounds are those obtainable by reacting propylene oxide with aliphatic C7-12 monocarboxylic acids.
13. So-called reactive coalescents were mentioned at an early stage, as for example in U.S. Pat. No. 4,141,864. Dicyclopentenyloxyethyl methacrylate was used therein, but was said to have odor-related drawbacks.
16. The claims of European patent EP 1,169,397 B1 are directed to film-forming compositions where polymers or prepolymers are emulsified in aqueous phase and where the composition comprises a coalescent which is an ester and is characterized by the formula R—COOX. R and X in this formula are hydrocarbyl groups or substituted hydrocarbyl groups. At least one of the two radicals must comprise at least two C═C double bonds.
18. WO 00/56823 discloses film-forming compositions having an aqueous phase and a dispersed phase, the latter comprising a polymer and a coalescent. The latter is an ester subject to the structural proviso that the acid component and/or the alcohol component must comprise at least two C═C double bonds. The technical purpose of this multiplicity of double bonds is that the coalescent itself is reactively crosslinked; it is referred to as a reactive coalescent.
19. Claim 1 of U.S. Pat. No. 6,762,230 B2 is directed to coating compositions comprising a latex polymer and a coalescent of the formula R1—(CO—Xr—O)n—R2. In this formula, R1 is an organic group, X is a divalent organic group, the index r can be 0 or 1, the index n can be in the range from 1 to 10, and R2 is hydrogen or an organic group. Where r adopts a value of 0 and n a value of 1, and where the radicals R1and R2 are alkyl radicals, the stated formula circumscribes fatty acid esters. It is pointed out, however, that fatty acid esters are not specifically disclosed in U.S. Pat. No. 6,762,230 B2. Instead, the coalescents of U.S. Pat. No. 6,762,230 B2 that are specifically discussed are not fatty acid esters.
20. Fatty acid alkyl esters are referred to in the two following texts: in EP 026,982 A1 from 1980, aqueous coating compositions with a polymer and a coalescent are claimed. The latter is to be selected from a trio of “kinds” of esters; one of these kinds is characterized by the formula R1—COOR2. In this formula, R1 is an alkyl or aryl group and R2 is an alkyl group (bar methyl). In the paragraph bridging pages 11 and 12 it is explicitly stated that in the abovementioned ester formula it is preferably the case that R1=C3-7, and R2=C4-8 (both radicals aliphatic). At page 13 lines 10-33, suitable esters are listed by name. At page 13 line 35 et seqq. it is expressly stated that methyl and esters are generally to be avoided on account of their instability (tendency toward hydrolysis) in paint systems. Here, then, the skilled person is explicitly advised against using, as coalescents, esters whose alcohol component is methanol or ethanol, and is implicitly advised against using, as coalescents, esters whose alcohol component has 3 or 4 C atoms (since, in the preferred embodiment, as mentioned above, R2 embraces a range of 4-8 C atoms). In particular there is no specific disclosure of any fatty acid esters whose alcohol component has 1 to 3 C atoms.
21. DE 24,49,471 A1 from 1974 claims esters of straight-chain C2-6 fatty acids, the alcohol component of the esters being aliphatic C3-4alcohols, as solvents for coating materials. There is no reference there to coalescents.
22. There is a constant need for new coalescents. An object of the present invention was therefore to provide coalescents. These coalescents ought to be suitable in particular for producing coatings such as paints, inks, and the like, but also for adhesives. A particularly preferred field for the use of the coalescents to be provided is that of the emulsion paints.
23. The concept of coalescents (in the literature also called filming assistants or film-forming assistants) is to be understood in the sense which is set out above and which is very well known to the skilled person.
24. It is expressly stated that the coalescents to be developed in accordance with the invention are intended particularly for use in aqueous dispersions of polymers or latex particles that are suitable for coating purposes of any kind (for example, for water-based paints and inks).
25. Dispersions of this kind, which are prepared typically by emulsion polymerization and which—in addition to water, the auxiliaries used in emulsion polymerization, and the particles of polymer or of latex—may comprise further constituents which are commonly used for a particularly desired coating purpose, are customarily applied to the surface to be coated; this is followed by evaporation of the water, and, finally, it is essential that the polymer particles or latex particles merge by flowing and form a homogeneous film. This process of film formation requires that at least a minimum temperature be observed, which is referred to by the skilled person as the minimum film-forming temperature (MFFT). Where the MFFT of a system is, for example, 20° C., this means that film formation proceeds successfully only when the temperature is 20° C. or higher. If, on the other hand, film formation is to be produced at lower temperatures, as for example at 10° C. or temperatures even lower, then the stated aqueous dispersions must be admixed with a coalescent in an amount such that the MFFT is lowered to the desired level.
26. In this respect the present invention has made it a goal in particular to develop coalescents which lower as effectively as possible the MFFT of aqueous dispersions of polymer particles or latex particles that are intended for any coating purposes.
37. 10-Undecenoic acid, lauroleic acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, gadoleic acid, erucic acid, and brassidic acid. These fatty acids are among the unsaturated fatty acids, comprising a C═C double bond.
38. As far as the acid component is concerned, the esters (I) derive preferably from fatty acids having 10 to 18 C atoms. These acids may be linear or branched, saturated or monoolefinically unsaturated. Fatty acids of natural origin are preferred.
in which R1 is a saturated alkyl radical having 9 to 18 C atoms. In this case, methyl laurate, methyl myristate, and methyl palmitate, or mixtures thereof (of the kind present, in particular, when the compounds (I-a) are prepared using natural raw materials, in particular based on vegetable triglycerides) are especially preferred.
in which R1 is a saturated alkyl radical having 9 to 18 C atoms.
45. The esters (I) are very efficient as coalescents, as is apparent from their outstanding capacity to lower the minimum film-forming temperature (MFFT) of aqueous polymer dispersions. Moreover, coatings (films) obtainable using aqueous polymer dispersions comprising the ester (I) for use in accordance with the invention, after four weeks of storage, are in general significantly harder, and hence more robust and less susceptible to soiling, than those produced using commercial coalescents. A further advantage of the esters (I) for use in accordance with the invention is that their boiling point is above 250° C., which is classified, in accordance with the EU regulations 1999/42/EC and 2004/42, as “VOC-free”.
46. Also of interest are studies by the applicant into the tendency of the esters (I) of the invention toward hydrolysis, in comparison to esters which are structurally close to them, and/or in comparison to commercial, hydroxyl ester-based coalescents. Thus the applicant has found that, in an aqueous-alkaline medium, methyl laurate and isopropyl laurate have a lower tendency toward hydrolysis than butyl laurate and the commercial 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TMB). The results of these studies by the applicant are surprising and may be seen as the overcoming of a technical prejudice (compare EP 026,982 A1, treated above).
47. The esters (I) for use in accordance with the invention can be used in pure form or in the form of mixtures with one another. If desired, the esters (I) can also be used in combination with known coalescents.
as coalescents, especially in connection with the production of coatings of any kind based on aqueous polymer dispersions or latex dispersions, and preferably in the production of coatings based on emulsion paints.
51. As already stated, the esters (I) for use in accordance with the invention are employed in particular as coalescents for aqueous dispersions of polymer particles or latex particles that are to be filmed. This is the case when the esters (I) are used either alone (in the form of a pure species or a mixture of different species) or in a blend with other coalescents different from them.
52. The esters (I) are used in this case preferably (in accordance with the MFFT of the polymer) in amounts of 0.1% to 40% by weight and more particularly 2% to 6% by weight, based on the amount of the polymer particles or latex particles whose minimum film-forming temperature is to be lowered.
53. From a different viewpoint, the amount of the esters (I) may be based on a completed coating formula which is to be applied to a surface. In this respect, the esters (I) are used preferably (in accordance with the 20 MFFT of the polymer) in amounts of 0.1% to 5% by weight and more particularly 0.5% to 2% by weight, based on the overall coating formula.
54. The skilled person is able to vary the amount of the esters (I) in accordance with the composition of a specific dispersion or of a specific coating formula, and is able, as and when necessary, to use higher amounts of esters (I), particularly if the system comprises polymers with a high minimum film-forming temperature and/or if the MFFT is to be lowered to very low levels.
55. As far as the nature of the polymer particles or latex particles present in the aqueous dispersions is concerned, there are no particular restrictions. It is possible, accordingly, to use all of the polymers and copolymers that are known in this connection to the skilled person for coating purposes.
56. Depending on the desired field of application and/or on the nature of the coating, the aqueous dispersions may, moreover, comprise further adjuvants and additives that are known in this connection to the skilled person.
57. The esters (I) of the invention may be added to the aqueous dispersions immediately after preparation, which is preferably by emulsion polymerization, or else at a later point in time, such as during the preparation of a coating material, for instance.
58. The aqueous dispersions comprising ester (I) for use in accordance with the invention may be applied in principle to any desired surfaces, as for example to wood, metal, plastic, glass, paper, concrete, masonry, and renders.
|Mowilith LDM 7451||Aqueous polymer dispersion based on acrylic ester/methacrylic|
|Mowilith LDM 7717||Aqueous polymer dispersion based on acrylic ester/methacrylic|
|Acronal 290D||Aqueous polymer dispersion based on butyl acrylate/styrene|
|Acronal S 790||Aqueous polymer dispersion based on butyl acrylate/styrene|
|Lipaton AE 4620||Aqueous polymer dispersion based on styrene/acrylic ester|
|Mowilith DM 611||Aqueous polymer dispersion based on styrene/acrylic ester|
|Mowilith DM 2452||Aqueous polymer dispersion based on VAC/VEOVA/acrylic|
|Rhoplex SG 30||Aqueous polymer dispersion based on acrylic ester (Rohm &|
|B1||C12-16 Fatty acid methyl ester (C12 content approximately 70%) =|
|V1||2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate (TMB) =|
60. The addition of the test coalescent (B1 or V1) to the respective polymer dispersion was made with stirring. After an aging time of 24 hours, the systems were applied to glass plates by doctor blade (wet film thickness 150 pm). After drying had taken place (at 20° C. for about 24 hours), the films were assessed, using a variety of test methods.
64. “amount needed for MFFT=0° C.”=amount of coalescent B1 or V1 required, in each case in % by weight, based on the polymer dispersions (in the form as supplied from the manufacturer) to lower the minimum film-forming temperature (MFFT) of the polymer dispersion used to a value of 0° C.
69. Moreover, after 4-week storage, the films, in the case where the inventive ester B1 is used, are significantly harder, and hence more robust and less susceptible to soiling, than those produced using the industrial standard V1.