TW201012836A - Monomer mixtures, polymers and coating compositions - Google Patents

Abstract

The present invention relates to a monomer mixture comprising at least one monomer A of the general formula (I) in which R is hydrogen or a methyl group, X1 and X2 independently are oxygen or a group of the formula NR' in which R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X1 and X2 is a group of the formula NR' in which R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R1 is an unsaturated radical having 9 to 25 carbon atoms, and at least one monomer B of the general formula (II) in which R is hydrogen or a methyl group, X1 and X2 independently are oxygen or a group of the formula NR' in which R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X1 and X2 is a group of the formula NR' in which R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R2 is a saturated radical having 9 to 25 carbon atoms. The present invention further relates to a process for preparing the above monomers, to polymers obtainable from this monomer mixture and to coating compositions which comprise the stated polymers.

Description

201012836 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a monomer mixture and also to a polymer obtainable from a monomer mixture. The invention is further directed to coating compositions comprising these polymers. Furthermore, the invention relates to the preparation of these monomers. [Prior Art] • Coatings, especially lacquers and varnishes, have been synthetically produced for a long time. Many of these coatings are based on so-called alkyd resins which are produced using polybasic acids, alcohols and fatty acids and/or fatty acid derivatives. A particular group of these alkyd resins forms a crosslinked film by violent oxygen, which is carried out by an oxidation reaction with an unsaturated group. Many of these alkyd resins contain an organic solvent or dispersion medium to allow the resin to be applied to the coating assembly as a film. However, based on environmental protection and home security, the use of these solvents must be abandoned. Therefore, related resins based on φ based on aqueous dispersions have been developed, but their storage stability is limited. In addition, many alkyds are too absorbent or their solvent resistance and their hardness are too low. Accordingly, attempts have been made to modify or replace the conventional alkyd based coatings described above. For example, 'US 4,010,126 discloses a composition comprising an alkyd resin modified with a (meth) acrylate polymer and then used for emulsion polymerization. The composition is manufactured in several steps' so that the cost of the resin is high and the preparation is inconvenient. A coating composition based on a solution polymer based on an ethyl styrene monomer is disclosed in DE-A-l 01 06 561, for example. However, this composition includes a high proportion of organic solvents. In addition, aqueous dispersions based on (meth) acrylate polymers are also known. For example, document DE-A-41 05 134 describes an aqueous dispersion which can be used as a binder in coatings. However, the preparation of those adhesives is carried out in several stages, in which a solution polymer is first prepared, which is used for emulsion polymerization after neutralization. Furthermore, DE-A-25 13 516 describes aqueous dispersions comprising polymers based on (meth)acrylates, here some (meth) acrylates are derived from unsaturated alcohol moieties. A particular disadvantage of the dispersion is its high cost and inconvenience to prepare. The polymer is obtained by solution polymerization on a (meth) acrylate basis. In this case, the proportion of the acid groups of these polymers is high, in the range of 5 to 20% by weight based on the solution polymer. The publication DE-A-26 3 8 544 describes an oxidatively dry aqueous dispersion comprising a (meth) acrylate based emulsion polymer, some of which are unsaturated with (meth) acrylates Alcohol residue. However, chain transfer agents have been used to prepare emulsion polymers, and thus the solubility of the emulsion polymer is also high. Further, an aqueous dispersion comprising an oxidatively dry polymer is described in F. -B. Chen, G. Bufki n, "Crosslinkable Emulsion Polymers by Autooxidation II", Journal of Applied Polymer Science, V〇l. 30, 4551-4570 (1985). The polymer contains 2 to 8% by weight of a unit derived from a (meth) acrylate having an unsaturated long-chain alcohol moiety. For many applications, the shelf life of these dispersions and the hardness of the coating -6 - 201012836 are insufficient. Further, the 'US Pat. No. 5,750,751 describes a polymer based on a vinyl monomer' which can be crosslinked at room temperature. This polymer can be obtained by both solution polymerization and emulsion polymerization. In particular, the monomer mixture used in the polymerization may comprise a (meth) acrylate whose alcohol moiety is modified with an unsaturated fatty acid. The polymer obtained by solution polymerization and emulsification polymerization of the modified (meth) acrylate exhibits high solubility due to the use of a chain transfer agent. However, the disadvantage of the coatings described in US 5,7 50,75 1 is that plasticizing solvents must be added and this addition should be avoided in an environmental standpoint. This aspect can be improved by the experience of the publication EP-A-1 044 993. This document describes aqueous dispersions based on (meth) acrylates. The mixture for the polymerization reaction comprises a (meth) acrylate modified with an unsaturated fatty acid. A key to this solution is the use of polymers having a particularly broad molecular weight distribution and a number average molecular weight between 300 and 3000 g/mole. However, for many applications, the disadvantage of these systems is that the resulting φ film is too soft. Furthermore, document WO 2006/0 1 3061 describes a dispersion comprising particles based on (meth) acrylate. The monomer mixture used to prepare the particles comprises a (meth) acrylate modified with an unsaturated fatty acid. However, the monomer containing an acid group was not polymerized in the examples. Furthermore, the proportion of (meth) acrylate modified with unsaturated fatty acids is very high. Disadvantages of the dispersions described in WO 2006/01 3061 are more particularly due to their complex process and high proportion of residual monomers. Furthermore, the coating obtained from this dispersion has low stability to some solvents. -7- 201012836 Further, the prior art also discloses a dispersion which, like the polymer based on (meth)acrylic acid vinegar, may also contain an alkyd resin. For example, document WO 98/22545' describes a polymer having units derived from (meth) acrylate having an unsaturated alcohol moiety. These polymers can be used together with alkyd resins. However, a solvent is used to prepare the coating from the polymer. Aqueous dispersions are not described in WO 98/22545. Accordingly, these compositions are hindered by the aforementioned disadvantages. Further, the Japanese publication JP 59011376 describes an emulsion polymer based on (meth) acrylate. The dispersion (solids content of about 40%) has a dynamic viscosity of at least 200 mPas. This bulletin does not specify the particle size. However, due to the high viscosity of the dispersion, it can be assumed that the particle size of the emulsified polymer is less than 40 nm. A disadvantage of the dispersions described in this publication is that they have a short shelf life. In addition, the resulting coatings have the stability that is insufficient for the increased demand associated with each solvent. Furthermore, US 6,599,972 discloses a polymer based coating composition on which the alcohol portion of the (meth) acrylate based is derived from an unsaturated fatty acid derivative. It is expressly stated herein that the coating compositions have the disadvantage of their shelf life and the stability of the coatings obtainable from the composition. SUMMARY OF THE INVENTION Therefore, in view of the prior art, it is an object of the present invention to provide a monomer mixture which can be processed into a polymer having excellent properties. More particularly, 'these properties include significant characteristics for coatings and coatings obtainable from coatings-8 - 201012836. The monomer mixture must be particularly capable of being processed into dispersions or polymers with very low residual monomer content (eg emulsification) polymer). Thus, in addition, the subject matter of the present invention provides a coating having a particularly long shelf life and durability. Moreover, the object is that the hardness of the coating obtainable from the coating can vary over a wide range. In particular, this purpose is to obtain a particularly hard scratch-resistant coating. I. Another standard is to provide a polymer that can be used to obtain a coating without a volatile organic solvent. Coatings obtainable from aqueous dispersions must have high weathering stability, more particularly high UV stability. In addition, membranes obtainable from aqueous dispersions must exhibit low viscosity after a short period of time. Furthermore, the coatings obtainable from the polymer and monomer mixture must have a particularly high solvent resistance. Here, this stability must be high stability associated with a variety of different solvents. By means of a monomer mixture φ having all the features of claim 1 of the patent application, these and other objects are simply reasoned or derived from the circumstances discussed in the introduction, although not explicitly stated. The ambiguous modification of the monomer mixture of the present invention is protected by the dependent patent application. As for the polymer, the composition for producing the coating, and the method for producing the monomer mixture, the following subject solutions are provided in the scope of claims 20, 24 and 26, respectively.

The subject matter of the invention is a monomer mixture comprising at least one monomer A of the formula (I)

(I), -9 - 201012836 wherein R is hydrogen or methyl 'X1 and X2 are independently oxygen or a group of the formula NR, wherein R' is hydrogen or a group having 1 to 6 carbon atoms), but At least one of the groups X1 and X2 is a group of the formula NR' (wherein R is hydrogen or a group having 1 to 6 carbon atoms), Z is a linking group, and R1 is 9 to 25 carbons Atomic unsaturated group,

And at least one monomer B of the formula (II)

(II), wherein R is hydrogen or methyl, and X1 and X2 are independently oxygen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), but the group X1 and At least one of X2 is a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), Z is a linking group, and R2 is a saturated group having 9 to 25 carbon atoms group. [Embodiment] By the means of the present invention, the following advantages are additionally obtained: The monomer mixture of the present invention can be processed into a polymer, a coating, and a coating having a very low residual monomer content. The hardness of the coatings obtainable from the coatings of the invention based on the polymer and monomer mixture can vary over a wide range. According to the invention, a particularly strong scratch-resistant coating is obtained in a preferred modification. The coatings obtainable from the coatings of the present invention have surprisingly high solvent resistance, which is more particularly demonstrated in tests using methyl isobutyl ketone (MIBK), ammonia solution or ethanol. Therefore, in the experiments according to DIN 6886 1 -1 倶 -10- 201012836, the resulting coatings are particularly distinguished by their classification. The coatings which can be obtained using the monomer mixtures of the invention generally do not require any volatile organic solvents. In addition, the coating of the present invention has high storage stability, high durability and excellent shelf life. More specifically, there is virtually no formation of aggregates. The coatings obtainable from the coatings of the invention have a high weathering stability, more particularly a high UV stability. In addition, the film that can be obtained from the coating is short

The viscosity after time is low. The monomer mixtures, polymers and coatings of the present invention can be produced on a large scale in a manner that is inexpensive. The coatings of the present invention are prepared and processed in a manner that is eco-friendly and safe and cost and complexity. In this respect, the coating of the present invention has an extremely high shear stability.

The monomer mixture comprises at least one monomer A of the formula (I)

Wherein R is hydrogen or a group in which the radicals 'X1 and X2 are independently oxygen or a formula NR (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), but at least at least one of the groups χι and X2 One is a group of the formula NR' (wherein R is ammonia or a group having from j to 6 carbon atoms), Z is a linking group, and R1 is an unsaturated group having 9 to 25 carbon atoms.

According to a preferred system, the monomer mixture comprises at least one monomer A -11 - (III) of the formula (III), 201012836

Wherein R is hydrogen or methyl 'X1 is oxygen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms) 'Z is a linking group 'R' is hydrogen or has 1 to a group of 6 carbon atoms and R1 is an unsaturated group having 9 to 25 carbon atoms. The phrase "a group having 1 to 6 carbon atoms" represents a group having 1 to 6 carbon atoms. It includes aryl and heteroaryl groups and alkyl, cycloalkyl, alkoxy@, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic fluorenes. The group can be straight or branched. Further, these groups may contain a substituent, particularly a halogen atom or a hydroxyl group. Preferably, the group R' is an alkyl group. Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl and tert-butyl groups Z to contain from 1 to 10,1 to 5 is preferable and 2 to 3 is more preferable, and a bonding group of one carbon atom is preferred. The group particularly includes straight-chain or branched, aliphatic or cycloaliphatic groups, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and Tributyl or cyclohexyl groups are particularly preferred. In particular, monomer A having the group Z containing at least one hydroxyl group as in the formula (I) exhibits surprising advantages. These groups preferably contain from 5 to 6 carbon atoms. According to a particular modification of the invention, the linking group Z having at least one hydroxyl group conforms to the formula (la) -12- 201012836

OH /J\ /χ3—Z~ (la). A CH2 CH2 wherein x3 is oxygen or a group of the formula NR' (wherein r' is hydrogen or a group having from i to 6 carbon atoms) 'Z1 is a linking group (It preferably contains 1 to 5 carbon atoms, 2 or 3 carbon atoms are more preferred, and 2 carbon atoms are excellent). In particular, it includes straight-chain or branched, aliphatic or cycloaliphatic groups, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and Tri-φ butyl or cyclohexyl group, especially excellent for stretching ethyl. The linking group having at least one hydroxyl group includes, in particular, 2-hydroxy-4-oxahexanyl, 2-hydroxymethyl-3-oxahetopenyl and 2-hydroxy-4-oxa-5-methylexylhexyl, Particularly preferred is 2-hydroxy-4-oxaexene. The group R1 in the formula (I) is an unsaturated group having 9 to 25 carbon atoms. These groups may especially include alkenyl, cycloalkenyl, alkenyloxy, cycloalkenyloxy, olefinic and heteroaliphatic groups. These groups may additionally contain a substituent, in particular a halogen atom or a hydroxyl group. Preferred groups include, in particular, alkenyl groups such as 壬® alkenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, Hexadecenyl, heptadecyl, octadecenyl, pentadecenyl, eicosyl, twenty-carbonalkenyl, behenyl, octadienyl, anthracene Dienyl, decadienyl, undecadienyl, dodecadienyl, tridecadienyl, tetradecadienyl, pentadecadienyl, hexadecadienyl , heptadecadienyl, octadecadienyl, decadecendienyl, eicosadienyl, icosyldienyl, docosadienyl, twenty-three carbon two Alkenyl and/or heptadecatrienyl. Preferred monomers A of the formulae (I) and (III) include, in particular, heptadecene-13- 201012836 decyloxy-2-ethyl(meth) acrylamide, heptadecadecyloxy-2 -ethyl (meth) acrylamide, heptacostrienyloxy-2-ethyl (meth) acrylamide, heptadecene decyloxy-2-ethyl (meth) propylene oxime Amine, (meth) propylene oxime 2 - ethyl - palm amide, (methyl) propylene oxy-2-ethyl decylamine, (methyl) propyl decyloxy 2 _Ethyl-eicylamine, (meth)propenyloxy-2-ethylf-decylamine, (meth)acryloxy-2-ethyl-erucamide, ( Methyl) propylene oxy-2-ethyl linoleamide, (meth) propyl decyloxy 2 ethyl eutrophic acid amide amine (meth) propylene oxime _2 · C Palmitoin, decylamine, (meth) propylene oxime-2-propyl oleylamine, (methyl) propyl decyloxy-2-propyl eicosylamine, (methyl) propylene醯 _2 _ _ 馆 馆 馆 稀 、 、 、 、, ( ( ( 和 和 和 和 和 和 和 和 和 和 和(methyl) propyl Iridinoxy-2-propyl linoleamide. Further, of particular interest is the fact that the group Ζ containing at least one hydroxyl group such as the formula (I) or (111) is preferably in particular

(V) wherein R is hydrogen or methyl, and X1 and X3 are independently hydrogen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms) 'Z1 is 1 to 5 A linking group of carbon atoms, R' is hydrogen or a group having 1 to 6 carbon atoms and R1 is an unsaturated group having 9 to 25 carbon atoms. The preparation of monomer A of formula (V) often also produces (methyl-14-201012836) acrylate of formula (Va)

Wherein R is hydrogen or methyl, and X1 and χ3 are independently hydrogen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms) 'Z1 is 1 to 5 carbon atoms The linking group 'R' is hydrogen or a group 9 having 1 to 6 carbon atoms and R1 is an unsaturated group having 9 to 25 carbon atoms. These monomers of the formula (Va) can be used in admixture with the aforementioned monomers. For example, the weight ratio of the monomer of the formula (V) to the monomer of the formula (Va) may be in the range of from 1 〇〇〇 1 to 1: 1000, preferably in the range of from 100:1 to 1:1. It is particularly good in the range of 50:1 to 10:1. The monomer A having the group Z containing at least one hydroxyl group such as the formula (I) or (V) includes, in particular, (meth)acryloxy-2-hydroxypropoxy-2-ethyl palmitoleguanamine, (Meth)acryloxy-2-hydroxypropoxy-2-vinylindole® amine, (meth)acryloxy-2-hydroxypropoxy-2-ethyleicylguanamine, (Meth) propylene oxime-2-hydroxypropoxy-2-ethyl cetyl decylamine, (meth) propylene oxime-2-hydroxypropoxy-2-ethyl erucic acid decylamine , (methyl) propylene oxime-2-hydroxypropoxy-2-ethyl linoleamide, (meth) propylene oxy-2-hydroxypropoxy-2-ethyl linoleene Indoleamine, (meth)acryloxy-2-hydroxypropoxy-2-propyl palmene decylamine, (meth) propylene oxime-2-hydroxypropoxy-2-propenylamine, (Meth)acryloxy-2-hydroxypropoxy-2-propyl eicosylamine, (meth)acryloxy-2-hydroxypropoxy-2-propyl cetyl Enamine, (meth) propylene oxime-15- 201012836 yl-2-hydroxypropoxy-2-propyl erucic acid decylamine, (meth) propylene oxirane - 2 hydroxypropoxy-2- Propyl linoleyl guanamine and Yl) oxy-2-Bing Xixi -2-hydroxypropoxy sulfoxide oleyl Amides. The "(meth)acrylic"" represents an acrylic or methacrylic group, and a methacrylic group is preferred. Particularly preferred monomers of the formula (〖) and (ΙΠ) are methacryloxy-2-ethylamine, methacryloxy-2-ethyl-linoleamine and/or Acryloxy-2-phenylethyl linoleamide. In a particular system of the invention, monomer A of formula (I) has an iodine number in the range of 50 to 300 grams of iodine per 100 grams, more preferably in the range of 1 to 2 grams of iodine per 100 grams. . In particular, a particular advantage can be achieved by the monomer A of the formula (I) containing at least one double bond in at least some of the unsaturated groups R1. According to a further feature of the invention, at least some of the unsaturated groups R1 of monomer A of formula (I) contain two or more double bonds. It may be preferred to use a mixture of monomers A. These mixtures may contain not only monomer A having exactly one double bond in the group Ri but also monomer A having two or more double bonds in the group R1. Here, the weight ratio of the monomer A of the formula (I) having exactly one double bond in the unsaturated group R1 to the monomer A of the formula (I) having two or more double bonds in the unsaturated group R1 In the range of 1〇〇:1 to 1:1〇, it is better in the range of 1〇:1 to 1:5. The monomers A of the formulae (I) and (III) are in particular obtainable by a multistage process. In the first stage, for example, one or more unsaturated fatty acids or fatty acid esters can be reacted with an amine (e.g., 'ethylenediamine, ethanolamine, propylenediamine or propanolamine), -16-201012836 to form a guanamine. In the second stage, the hydroxyl or amine group of the indoleamine is reacted with a (meth) acrylate (e.g., methyl (meth) acrylate) to give a monomer of the formula (I) or (III). Useful information for preparing these monomers can be found in the information including examples of the present specification. Accordingly, to prepare a compound wherein X1 is a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms) and X2 is oxygen, the alkyl (meth)acrylate may be singulated (for example) , (methyl methacrylate) reacts with one of the aforementioned amines to form a (meth) acrylamide having a hydroxy group in the alkyl group, and then reacting the (meth) acrylamide with an unsaturated fatty acid to form A monomer. The transesterification of an alcohol with a (meth) acrylate, or the preparation of a (meth) acrylamide, further described in CN 1355161, DE 21 29 425 (Application to the German Patent Office at 14.06.71, Application No. P 2 1 29425.7 ) , DE 34 23 443 (applies to the German Patent Office on 26.06.84, application number P 3423443.8) or ΕΡ-Α-0 534 666 (applies to the European Patent Office at 16.09.92, application number EP 92308426.3), the reaction conditions described in these φ documents and the catalysts listed in the text are incorporated herein by reference. Furthermore, these reactions are described in "Synthesis of Acrylic Esters by Transesterification", J. Haken, 1967. Particularly preferred groups Z comprising at least one hydroxyl group, such as monomer A of formula (I), may especially be grafted with (meth)acrylic acid. The reaction of glycidyl ester with an unsaturated fatty acid decylamine which has a hydroxyl group or an amine group and which has been obtained by the aforementioned reaction of a fatty acid or a fatty acid ester with an amine (for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine) The reaction of epoxides with alcohols or amines is found in the literature, including "Epoxy Resins Chemistry and Technology'', CAMay, -17-201012836 (Marcel Dekker), 1 98 8 and "Synthetically Useful"

Reactions of Epoxides'', Januce Gorzynski Smith, Synthesis, 1984 and "Mechanisms of Epoxide Reactions", RE Parker et al., Chem. Rev., 1 9 5 9 and "Epoxides", Gunther Sienel et al., Ullmann's Encyclopedia of Industrial Chemistry, Wiley, and "Epoxy Resins", HQ Pham et al., Kirk-Othmer Encyclopedia of Chemical Technology, Wiley o by reaction of a hydroxyl or amine-containing unsaturated fatty acid decylamine with (meth)acrylic anhydride Monomer A as in formula (I) in particular exhibits surprising advantages. This surprising advantage includes, inter alia, relatively low film formation temperatures and high scratch and chemical resistance of the resulting polymeric film portion. The molar ratio of the OH group and the NH group of the (meth)acrylic anhydride to the fatty acid decylamine is preferably in the range of 2:1 to 1:1, respectively, based on the amine and/or hydroxyl fraction to be reacted, respectively. : 1 to 1.05: 1 is more preferred. The reaction can occur at super-atmospheric or sub-atmospheric pressure. According to a particularly advantageous modification of the invention, the reaction can be carried out at a pressure in the range from 200 to 2000 mbar, more preferably in the range from 500 to 1300 mbar, preferably at a temperature of at least 60 ° C. . According to a particular system of the invention, the temperature at which the reaction takes place is preferably in the range of 7 (TC to 120 ° C, more preferably in the range of 80 ° C to 100 ° C. The reaction can take place in the presence of a catalyst. Compounds and/or Yuean-18-201012836 generally catalyze the reaction of (meth)acrylic anhydride with a hydroxyl or amine group. Metal compounds and amines are known to the art and are found, for example, in Ullmanns Encyclopedia of Industrial Chemistry (6th Edition).

Wiley-VCH, Weinheim 2 0 0 3 or Rompp C h e m i e 1 e x i k ο n, 2nd Edition CD-ROM version. The metal compound more particularly includes a salt such as an alkali metal halide, hydroxide or oxide such as LiOH, KOH, or a pin compound. The amine includes, for example, ammonia, triethylamine, tributylamine, and the like.

In the reaction, it is preferred to use a polymerization inhibitor. These compounds, such as hydroquinone, hydroquinone ether (such as hydroquinone monomethyl ether) or di-t-butyl pyrocatechol, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylper Pyridin-1-oxy, methyl blue or sterically hindered phenols (an example being 2,4-dimethyl-6-tert-butylphenol) are widely known in the art. These compounds may be used singly or in the form of a mixture and are usually commercially available. Further details can be found in the current technical literature 'especially Rompp-Lexikon Chemie: Editors: J, Falbe, Μ. Regitz; Stuttgart, New York; 10th Edition (1 996): the headline "Antioxidants" and the references listed therein . Particularly preferably, phenol is used as a polymerization inhibitor. A particularly surprising advantage can be obtained using a mixture comprising hydroquinone monomethyl ether and/or 2,4-dimethyl-6-tert-butylphenol. More preferably, here, the molar ratio of hydroquinone monomethyl ether to 2,4-dimethyltributylphenol is in the range of 2:1 to 1:2. The ratio of inhibitor (individual or mixture) is usually 〇 · 〇 1 % - 0 5 % (weight / weight) based on the total weight of the reaction mixture. These polymerization inhibitors may be added to the reaction mixture before or at the beginning of the reaction to -19-201012836. Further, a plurality of added polymerization inhibitors may be added during the reaction period. According to a feature of the invention, the reaction is preferably carried out in the presence of oxygen, particularly atmospheric oxygen. Furthermore, the reaction can also be carried out in an oxygen deficient environment, more particularly under nitrogen. The reaction can be carried out in a continuous or batch manner. The process of the present invention can be carried out as a whole (i.e., without the use of other solvents). An inert solvent can also be used as desired. The solvent includes petroleum ether, benzene, toluene, n-hexane, cyclohexane and methyl isobutyl (MIBK), and methyl ethyl ketone (MEK). If the reaction mixture used contains at least 90% by weight of an unsaturated fatty acid decylamine (having a hydroxyl group or an amine group) and (meth)acrylic anhydride, at least 95% by weight of the fatty acid guanamine and (meth)acrylic anhydride are more preferred, Particular advantages are obtained, in particular with regard to the purification of the product and the advantages of product purity. Thus, according to this preferred system of the process of the present invention, only a small amount of solvent is used, and particularly preferably no solvent. In a particularly advantageous variant of one of the transesterification reactions of the invention, all of the components (for example, fatty acid decylamine, (meth) acrylamide and polymerization inhibitors) are mixed and then present in ambient oxygen or inert The reaction mixture is heated to a temperature of at least 60 ° C, preferably from about 80 to 100 ° C, in a gaseous environment (for example, under nitrogen). The reaction time depends on factors including the selected parameters (eg, pressure and temperature). However, in general, they are preferably in the range of 1 to 24 hours, preferably 2 to 20 hours, and excellent in 4 to 8 hours. In the continuous process, the residence time is usually in the range of from 55 to 24 hours, preferably from 1 to 12 hours and from 4 to 8 hours. -20- 201012836 The reaction is preferably carried out while stirring, wherein the stirring rate is preferably in the range of 50 to 2000 rpm, and the pH in the range of 100 to 500 rpm is excellent, and the pH can be in a wide range. However, (meth)acrylic acid was formed during the reaction, and a low amount of the metal compound was observed to cause a decrease in pH. Advantageously, the reaction can be carried out at a pH in the range of from 0 to 8, preferably from 2 to 7, as measured based on a mixture of the reaction mixture and more than 1 Torr of water. Suitable units for carrying out this transesterification reaction may comprise, for example, a stirred tank reactor with a stirrer mechanism and steam heating. Such a unit is known per se and is described in Ullmann's Encyclopedia of Industrial Chemistry (6th Edition), Wiley-VCH, Weinheim 2003, Volume 10, p. This method can be performed on a laboratory scale and an industrial scale. According to one feature, the stirred tank reactor can have a tank volume in the range of 1 cubic meter to 30 cubic meters, preferably 3 cubic meters to 20 cubic meters. The agitation mechanism of the reactor tank may in particular be in the form of an anchor agitator, a fan blade, an paddle agitator or an Inter-MIG agitator. In many cases, the (meth)acrylic acid or salt of this acid present in the reaction mixture may remain in the resulting reaction mixture without any adverse effect on the polymer from which it can be obtained. Depending on the intended use of the polymer, the resulting (meth)acrylic acid may also be separated from the reaction mixture by extraction or distillation. In many cases, the composition obtainable according to the present invention can be used without separating the released (meth)acrylic acid. In addition, the (meth)acrylic acid from -21 - 201012836 can be separated from the composition. In many cases, the particular (meth) acrylates obtained have met the exact requirements of the preceding list and, in many cases, no further purification is required. To further improve the quality, the resulting mixture can be purified by known methods. According to a system of the process of the invention, the resulting product mixture can be purified by filtration. Suitable methods are known from the prior art (W. GSsele, Chr. Alt, Ullmann^ Encyclopedia of Industrial Chemistry, (6th Edition), Wiley-VCH, Weinheim 2003, Volume 13, p. 73 1 and 746), wherein Typical filtration aids can be used, for example, bleaching earth and aluminum niobate (perlite). In particular, for example, a continuously operable filter can be used for the pre-filtering. The intermediate product obtained according to various methods, for example, a carboxamide having an alkyl group or a guanamine moiety having a hydroxyl group, is purified. According to a particular system of the invention, the intermediate obtained can be converted to monomer A of formula (I) by inexpensive and convenient purification. Expensive and inconvenient (or included) purification methods are particularly preferred for purification with relatively high energy use or investment costs. This includes, inter alia, an extraction step or a distillation step for purifying the resulting product. Compared to the proposed example, the relatively low cost filtration process is not a complicated purification process. Surprisingly, complex purification treatments can be prevented, especially when using fatty acid esters derived from alcohols having from 1 to 4 carbon atoms, especially when using commercially available fatty acid methyl esters as biodiesel . Preferred unsaturated fatty acids which may be employed in the manufacture of the monomers of formula (I) include, in particular, undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, anti-i1 octadecenoic acid, eicosenoic acid , whale oleic acid, erucic acid, tetracosenoic acid-22- 201012836, linoleic acid, linoleic acid, peanut oleic acid, timnodonic acid, oleic acid and/or twenty Cervonic acid. Preferably, these acids may also be used as esters of alcohols having from 1 to 4 carbon atoms, for example in the form of ethyl, propyl, butyl and especially methyl esters. The aforementioned fatty acid esters of alcohols having 1 to 4 carbon atoms, particularly the methyl esters of these fatty acids, are commercially available as biodiesel, especially mixtures with saturated fatty acids. Thus, for example, it is possible in particular to use the biodiesel according to standard EN 14214 or ASTM D 675 1 for the preparation of the monomer A and/or monomer mixture of the formula (I) according to the invention. A typical vegetable oil can be used as a starting material for the manufacture of the aforementioned fatty acid esters of alcohols having 1 to 4 carbon atoms, particularly the methyl esters of these fatty acids. These oils include, inter alia, palm oil, rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil and mustard oil. Other examples include oils derived from cereals, wheat, ramie, sesame, rice husk, jatropha, groundnut oil, and linseed oil. Preferably, the fatty acid alkyl esters used are obtainable from these oils by methods known in the art. Preferably, an oil containing a high proportion of unsaturated (preferably polyunsaturated) fatty acids, such as linseed oil or rapeseed oil, is used. By using fatty acid esters derived from alcohols having 1 to 4 carbon atoms, more particularly fatty acid methyl esters (FAME), surprisingly, it is possible to obtain particularly good processing properties (especially low minimum formation). A coating composition of film temperature, particularly high solvent resistance and excellent pendulum hardness. -23- 201012836 Particularly preferred amines for the reaction of fatty acids or fatty acid esters include ethylenediamine, ethanolamine, propanolamine and propylenediamine. It can be obtained by a monomer mixture containing monomer A having 17 to 21 carbon atoms in the unsaturated group R1 of at least 2% (at least 5%, preferably at least 10% more preferably) based on the total weight of the monomer mixture. The advantages that are not apparent to the person skilled in the art themselves. In addition to at least one of the foregoing monomers A, the monomer mixture of the present invention

Containing at least one monomer B of the formula (II)

(II), wherein R is hydrogen or methyl, and X1 and X2 are independently oxygen or a group of the formula NR, wherein R' is hydrogen or a group having 1 to 6 carbon atoms, but the group X1 and At least one of X2 is a group of the formula NR' (wherein R is hydrogen or a group having 1 to 6 carbon atoms), Z is a linking group, and R2 is a saturated group having 9 to 25 carbon atoms group. Preferably, the monomer mixture comprises at least one formula according to formula (IV)

Monomer B

(IV), wherein R is hydrogen or methyl, X1 is oxygen or a group of the formula NR' (wherein R is hydrogen or a group having 1 to 6 carbon atoms) 'z is a linking group, and R' is hydrogen Or a group having 1 to 6 carbon atoms and R 2 is a saturated group having 9 to 25 carbon atoms-24- 201012836 The groups R1 and Z in the formula (II) have been previously described for the formula (I) Body A is preferably described in relation to monomer B of formula (Π). The group R2 in the formulae (Π) and (IV) is a saturated group having 9 to 25 carbon atoms. These groups include, in particular, alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. These groups may additionally contain a substituent, particularly a halogen atom or a hydroxyl group. Preferred groups include, in particular, alkyl groups such as fluorenyl, fluorenyl, undecyl, dodecyl, thirteen carbon φ, tetradecyl, pentadecyl, hexadecanyl, and seventeen. Carbon, octadecyl, ninthylene, icosyl and docosa. Preferred monomers B of the formulae (II) and (IV) include, in particular, pentadecyloxy-2-ethyl-(meth)acrylamide, heptadecaoxy-2-ethyl-(A) Base) acrylamide, (meth) propylene oxime-2-ethyl-laurylamine, (meth) propylene oxime-2-ethyl myristamide, (meth) propylene oxime Benzyl-2-ethyl palmitoylamine, (meth)propenyloxy-2-ethyl-stearylamine, (meth)acryloxy-2-propyl-lauric acid, (φ Methyl)propenyloxy-2-propyl-myristylamine, (meth)acryloxy-2-propyl palmitoylamine and (meth)acryloxy-2-propyl-hard Lipidamine.

Further, of particular interest are monomers B in which the group Z comprises at least one hydroxyl group such as formula (II) or (IV). Preferably, in particular, monomer B as in formula (VI)

Η Ο -25- 201012836 wherein R is hydrogen or methyl, X1 and X3 are independently a group of the formula NR (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), 21 is 1 A linking group of up to 5 carbon atoms, R' is hydrogen or a group having 1 to 6 carbon atoms and R2 is a saturated group having 9 to 25 carbon atoms. The monomer B in which the group Z contains at least one hydroxyl group such as the formula (11) or (VI) includes, in particular, (meth) propylene decyloxy-2-hydroxypropoxy-2-ethyllaurylamine, (Meth) propylene decyloxy-2-hydroxypropoxy-2-ethyl myristamide, (meth) propylene oxy-2-hydroxypropoxy-2-ethyl palm amide, ( Methyl)propenyloxy-2-hydroxypropoxy-2-ethylstearylamine, (meth)acryloxy-2-hydroxypropoxy-2·propyl laurylamine, (A) Acryloxy-2-hydroxypropoxy-2-propyl myristylamine, (meth)propenyloxy-2-hydroxypropoxy-2-propyl palmitoylamine and (methyl Acryloxy-2-hydroxypropoxy-2-propylstearylamine. The preparation of the monomer B of the formula (VI) usually also produces the (meth) acrylate of the formula (VIa)

VR Ο (Via) wherein R is hydrogen or methyl, and X1 and X3 are independently oxygen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), and Ζ1 is 1 The linking group 'R' to 5 carbon atoms is a nitrogen or a group having 1 to 6 carbon atoms and R2 is a saturated group having 9 to 25 carbon atoms. These monomers of the formula (Via) can be used in admixture with the aforementioned monomers. For example, the weight ratio of the monomer of the formula (VI) to the monomer of the formula (Via) may be in the range of from 100:1 to 1:26 to 201012836 1000, in the range of from 100:1 to 1:1. It is better and is particularly good in the range of 50:1 to 1 0:1. Particularly preferred monomers B of the formulae (II) and (IV) include methacryloyloxy-2-ethyl-palmitoleamine and methacryloxy-2-ethyl-stearylamine. In a particular modification of the invention, it is preferred to use a monomer B of the formula (II) having a group R2 of 15 or 17 carbon atoms. Preferably, 2 or more monomers B of the formula (II) having a different number of carbon atoms of the group R2 are used in the monomer mixture. In the preferred mixture herein, the group R2 of the monomer B of the formula (II) has not only 15 but also 17 carbon atoms. The weight ratio of the monomer B of the formula (II) having 15 carbon atoms to the monomer B of the formula (II) having a saturated group R2 of 17 carbon atoms is from 100:1 to 1:10 The range is better, preferably in the range of 10:1 to 1:2. According to a particular system of the invention, the mono-body mixture may contain at least 0.5%, preferably at least 1% and more preferably at least 3% by weight, based on the total weight of the monomer mixture, the saturated group R2 having 1 1 Monomer B to 1 to 7 carbon atoms. The monomer B of the formulae (II) and (IV) can be produced in a similar manner to the monomer A used in the above formula (I), but a saturated fatty acid or a fatty acid ester is used herein. Preferred fatty acids include, in particular, capric acid, lauric acid, myristic acid, palmitic acid, n-heptadecanoic acid, arachidic acid, behenic acid, tetracosic acid, hexamic acid and stearic acid. These acids may also preferably be used in the form of esters of alcohols having 1 to 4 carbon atoms (e.g., ethyl ester, propyl ester, butyl ester, and especially methyl ester). -27- 201012836 A monomer mixture comprising monomer A of formula (I) and monomer B of formula (II) can be obtained by mixing monomer A and monomer B. Preferably, these mixtures can also be reacted with an amine in the manner described above by a mixture of fats or fatty acid esters comprising unsaturated and saturated fatty acids and/or fatty acid esters, and thereafter having a hydroxyl group with the alkyl moiety ( Methyl) acrylate or reacted with (meth) acrylamide.

As already mentioned, the monomer B and monomer mixtures of the formula (II) according to the invention can be used in a particularly simple manner by fatty acid esters of alcohols having from 1 to 4 carbon atoms, which are especially commercially available as a raw Produced by the reaction of the quality diesel. In general, the preferred monomer mixtures of the present invention can be obtained in a particularly cost effective manner by the following steps: A) Fatty acids of alcohols having from 1 to 4 carbon atoms (particularly fatty acid methyl esters (FAME), which are commercially available Preferably, the biodiesel is reacted with an amine to provide a mixture of carboxyguanamines.

B) The resulting mixture of carboxyguanamines provides a monomer mixture comprising monomer A of formula (I) and monomer B of formula (II). In this case, the reaction of the step B) is carried out in particular in the form of a transesterification reaction with an alkyl (meth)acrylate (more particularly, ethyl or methyl (meth)acrylate). Further, this reaction can be carried out using the preceding (meth)acrylic anhydride. The monomer B of the formula (II) or (VI) having a hydroxyl group in the linking group z can be obtained by reacting glycidyl (meth)acrylate with a saturated fatty acid decylamine having at least one hydroxyl group or one amine group. -28- 201012836 There is no strict weight ratio of monomer A to monomer B. The weight ratio of bulk A to monomer B is in the range of 1 〇 0: ! to 1: 1 〇 10: 1 to 1: 3 Good and good at 3 · 1 to 1 : 1 for amazing advantages. In addition to the monomers of the above formulae (I) and (II), the present mixture may contain other monomers which may be copolymerized with monomers A and B. These copolymerizable monomers include, in particular, monomers having an acid group Φ and with formula I or hydrazine The monomer alone is different from the monomer C, and the benzene is a compound. The single system containing an acid group may preferably be a compound copolymerized with the radicals A and B. These include, for example, monomers such as vinylsulfonic acid; monomers having a phosphonic acid group; phosphonic acid; and unsaturated carboxylic acids such as methacrylic acid, acrylic acid and maleic acid. Monomers in which methacrylic acid and acrylic acid are specific acid groups may be used singly or in combination of two, three or more. Preferably, the monomer C containing an ester group specifically comprises, for example, a different (meth) acrylate and fumarate, cis and/or vinyl acetate. The so-called (meth) acrylate esters and acrylates and mixtures of the two. These monomers are more particularly 'partially' include (meth) acrylates having from 1 to 6 derived from a saturated alcohol in the alkyl group, such as (methyl, ethyl (meth) acrylate, (methyl) Isopropyl methacrylate, butyl butyl (meth) acrylate, and butyl (meth) acrylate, (but if in a single range, the monomer invented in the range) And containing an ester group _ body. The formula is the same as the above-mentioned mono-sulfonic acid group, such as vinyl acid, anti-butene, etc. The acid group-containing mono-body or phthalic acid ester includes methyl group. Acrylic is known as a carbon atom-based) n-propyl acrylate, (, (meth) methacrylate -29- 201012836 hexyl ester; (meth) acrylate cycloalkyl ester, such as (meth) acrylate cyclopentane Ester, cyclohexyl (meth)acrylate; and (meth) acrylate derived from an unsaturated alcohol, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and (methyl) ) Vinyl acrylate. Particularly preferably, a mixture comprising methacrylate and acrylate is used. Thus, more particularly, a mixture of methyl methacrylate and an acrylate having 2 to 6 carbon atoms (e.g., ethyl acrylate, butyl acrylate and hexyl acrylate) is used. These comonomers further include, for example, (meth) acrylates having at least 7 carbon atoms in the alkyl group derived from a saturated alcohol, for example, 2-ethylhexyl (meth) acrylate, (meth) acrylate Heptyl ester, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl (meth)acrylate, bismuth (meth)acrylate Ester, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, Tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (meth)acrylic acid Hexadecane ester, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecane (meth)acrylate, 4-(meth)acrylate Third butyl octadecyl ester, 5-ethyl octadecyl (meth) acrylate, 3 · isopropyl octadecane (meth) acrylate , octadecyl (meth) acrylate, pentadecanyl (meth) acrylate, eicosanyl (meth) acrylate, cetyl eicosyl (meth) acrylate, (meth) acrylate Fatty 30-201012836 Eicosyl ester, behenyl (meth)acrylate and/or eicosyltrimethyl (meth)acrylate; cycloalkyl (meth)acrylate, such as '3-vinylcyclohexyl (meth)acrylate, decyl (meth)acrylate, borneyl (meth)acrylate, cycloalkyl (meth)acrylate, such as (meth)acrylic acid 2,4, 5-tri-tert-butyl-3-vinylcyclohexyl ester, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; heterocyclic (meth) acrylate For example, 2-(1-imidazolyl)ethyl (meth)acrylate φ 2-(4-morpholinyl)ethyl (meth)acrylate and 1-(2-methacryloylethyl)-2 - pyrrolidone; nitriles of (meth)acrylic acid and other nitrogen-containing methacrylates, such as N-(methacryloyl)diisobutyl ketone imine, N-(methacrylic acid B Di(hexadecyl) Imine, methacryl fluorenyl guanamine acetonitrile, 2-methyl acrylate ethyl methyl cyanamide, cyanomethyl methacrylate; aryl (meth) acrylate, such as benzyl (meth) acrylate Ester or phenyl (meth) acrylate, each of which may be unsubstituted or substituted at up to four; (meth) acrylate containing two or more φ (meth) acrylate groups, a glycol methacrylate such as 'ethylene (di) methacrylate, diethylene glycol di(methyl) propyl sulphate, triethylene glycol di(meth) acrylate, bis (A) Tetra- and polyglycol acrylate, bismuth (meth) acrylate, 3-butanediol ester, (meth) acrylate 1,4-butanediol ester, di(meth)acrylic acid 1, 6-hexanediol ester, glycerol di(meth)acrylate; dimethacrylate of ethoxylated bisphenol A; (meth) acrylate having three or more double bonds, eg, three (a) Glyceryl acrylate, hydroxymethylpropane tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, five-31 - 2010 12836 Dipentaerythritol (meth)acrylate. The monomer C containing an ester group further includes a vinyl ester such as ethylene acetate; a maleic acid derivative such as maleic anhydride or an ester of maleic acid (eg, maleic acid) Dimethyl methoxide), methyl maleic anhydride; and fumaric acid derivatives such as dimethyl fumarate. Other preferred groups of comonomers are styrene monomers, such as substituted styrenes having a phenyl group and an alkyl substituent in the side chain, such as alpha-methyl styrene and alpha-ethyl styrene. a substituted styrene having an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrene, such as monochlorostyrene, dichlorostyrene, tribromostyrene, and Tetrabromostyrene. In addition to the foregoing monomers, the polymer of the present invention obtained by polymerization of a monomer mixture may contain other monomers. These include heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-di Methyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine '9-vinylisobutazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl- 1-vinylimidazole, anthracene-vinylpyrazolone, 2-vinylpyrazolone, anthracene-vinylpyrazole, 3-vinylpyrazole, anthracene-vinylcaprolactam, anthracene -vinyl butyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinyl thiolane, vinylthiazole and hydrogenated vinylthiazole; maleicene Amine, methyl maleimide; vinyl and iso-p-pentadienyl ether; -32- 201012836 vinyl halides, such as chloroethylene, fluoroacetamidine, chloroethene and vinylidene fluoride . Preferred monomer mixtures of the present invention comprise 'each amount, preferably from 0.1 to 50, from 0.5 to 30% by weight, based on the total weight of the monomers, of monomer A, from 0.1 to 50, from 0.5 to 30% by weight, preferably. Monomer B, 30 to 95, 40 to 90% by weight, preferably monomer C containing an ester group, preferably from 0 to 10, from 1 to 8 % by weight, preferably having an acid group, from 50 to 50% by weight. % by weight of styrene monomer 'and hydrazine to 50% by weight of other comonomers. In particular, surprising advantages are obtained by using a monomer mixture obtainable by reacting a fatty acid ester derived from an alcohol having 1 to 4 carbon atoms, particularly fatty acid methyl ester (FEMA). As a result, the coating obtained from the polymer and the coating composition has surprisingly low organic solvent absorption. Furthermore, the compositions obtained using these polymers have particularly good processing properties, especially low minimum film forming temperatures. In addition, the coating obtained from the coating composition exhibits particularly high solvent resistance (for example, can be determined according to the DIN 68861-1 furniture test) and excellent pendulum hardness. Further, 'preferably, the ratio of the (meth) acrylate having two or more carbon-carbon double bonds of the monomer mixture and having the same reactivity as the (meth) acrylate group is extremely small. According to a particular modification of the invention, the proportion of the compound having two or more (meth) propyl ester groups is preferably limited to not more than 5% by weight, in particular not more than 2% by weight, based on the total weight of the monomers, Not more than 1% by weight is particularly good 'not more than 〇. 5% by weight is particularly good and does not exceed 〇. 1 weight -33- 201012836% is particularly good. The monomer mixture of the present invention is particularly useful for making or for modifying polymers. The polymerization can be carried out in any known manner. This method includes, in particular, 'free radical, cationic or anionic polymerization, in which variants of these polymerization methods can also be used, such as ATRP (=Atom Transfer Radical Polymerization), NMP (polymerization of NOx media) Method) or raFT (= reversible addition splitting chain transfer). The aforementioned monomer or monomer mixture can be obtained by, for example, a solution polymerization method, an overall polymerization method or an emulsion polymerization method, and a radical polymerization polymerization method can achieve surprising advantages. The method of emulsion polymerization is found in Ullmann, s Encyclopedia of Indusrial Chemistry, Fifth Edition. To use this method, an aqueous phase is generally produced, which may include, in addition to water, typical additives, more particularly emulsifiers and protective colloids for stabilizing the emulsion. This aqueous phase is then blended with the monomer and the polymerization reaction is carried out in the aqueous phase. When preparing uniform polymer particles, the monomer mixture can be added batchwise or continuously during the time period. The emulsion polymerization can be carried out as a small emulsion or microemulsion, and this detail can be found in Chemistry and Technology of Emulsion Polymerisation, AM van H erk (editor), B1 ack we 11 Pub 1 i shi ng, Ox for d 2005 and J. O'Donnell , EW Kaler, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454. Small emulsions are typically characterized by the use of an auxiliary stabilizer or swelling agent, and typically employ long chain alkanes or alkanols. The droplet size of the small emulsion is preferably 201012836 in the range of 5 to 20 microns. The droplet size of the microemulsion is preferably less than 1 micron such that the resulting particle size is less than 50 nanometers. In the microemulsion, an additional surfactant such as hexanol or a similar compound is often used. The dispersion of the monomer-containing phase in the aqueous phase can be carried out using known reagents. This includes, more particularly, mechanical methods and application of ultrasound. In the production of a homogeneous emulsion polymer, it is preferred to use a monomer mixture comprising 10 to 40% by weight of the monomer A of the formula (I). ^ When preparing a core-shell polymer, the composition of the monomer mixture can be gradually changed. Preferably, before the composition is changed, polymerization is carried out until the conversion is at least 80% by weight, and at least 95% by weight is more preferable. Based on the total weight of the monomer mixture used. The progress of the polymerization in each step is detected by known means (e.g., gravity or gas chromatography). The monomer mixture used to prepare the core preferably comprises from 50 to 100% by weight of (meth) acrylate, and a mixture of acrylate and methacrylate is particularly preferred. After the core has been produced, it can be grafted or polymerized on the core Φ, and the monomer mixture preferably comprises from 15 to 40% by weight of monomer A of formula (I). The temperature at which the emulsion polymerization is carried out is preferably in the range of 〇 to 120 ° C, more preferably in the range of 30 ° C to 10 ° C. It has been confirmed that the polymerization temperature here is at more than 60 ° C to low. It is particularly advantageous in the range of 90 ° C, preferably in the range of more than 70 ° C to less than 85 ° C, more preferably in the range of more than 75 ° C to less than 85 ° C. Emulsion polymerization A commonly used initiator initiates this polymerization. Suitable organic initiators are, for example, hydrogen peroxide, such as, for example, tert-butylperoxy-35-201012836 hydrogen or cumene hydroperoxide. Suitable inorganic initiators are Alkali metal salts and ammonium salts of hydroperoxides and peroxydisulfates, more particularly ammonium, sodium and potassium peroxydisulfates. Suitable redox initiator systems are, for example, tertiary amines and peroxides. Or a combination of an alkali metal salt of ammonium disulfite and peroxydisulfuric acid and an ammonium salt, more particularly sodium and potassium peroxydisulfate. Further details can be found in the technical literature, more particularly H. Rauch-Puntigam, Th. ©

Volker, "Acryl-und Methacrylverbindungen'', Springer, Heidelberg, 1 9 6 7 or Kirk-Othmer, Encyclopaedia of Chemical Technology, V ο 1. 1, pages 3 86ff, J. Wiley, New York, 1 97 8. Particularly preferred in the invention are organic and/or inorganic initiators.

The initiators may be used individually or in a mixture. The amount thereof is preferably from 5% to 3.0% by weight based on the total weight of the monomers in each stage. Preferably, the polymerization is carried out using a mixture of different polymerization initiators having different half-life periods so that the radical stream remains stable during the polymerization and during different polymerization temperatures. The stabilization of the batch is preferably achieved by means of an emulsifier and/or a protective colloid. This emulsion is preferably stabilized by an emulsifier to obtain a low dispersion viscosity. The total amount of the emulsifier is preferably from 0.1 to 15% by weight, preferably from 1 to 10% by weight and more preferably from 2 to 5% by weight, based on the total weight of the monomers used. According to a particular aspect of the invention, a portion of the emulsifier can be added during the polymerization reaction. In particular, suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, more particularly -36-201012836 - alkyl sulphates (preferably having from 8 to 18 carbon atoms in the alkyl group), alkyl groups having Alkyl and alkaryl ether sulfates of 8 to 18 carbon atoms and 1 to 50 ethylene oxide units; monosulfonate (alkyl sulfonate having an alkyl group having 8 to 18 carbon atoms is preferred) An alkylaryl sulfonate having an alkyl group of 8 to 18 carbon atoms, a diester and a monoester of an alkylphenol having a hydroxy succinic acid and a monohydric alcohol or an alkyl group having 4 to 15 carbon atoms; Suitably, these alcohols or φ alkylphenols are also ethoxylated via from 1 to 40 ethylene oxide units; - partial phosphate esters and their alkali metal and ammonium salts, having from 8 to 20 alkyl or alkaryl groups Preferred are alkyl and alkaryl phosphates having 1 to 5 ethylene oxide units; - alkyl polyglycol ethers having 8 to 20 carbon atoms and 8 to 40 epoxy groups in the alkyl group The ethane unit is preferred; - an alkaryl polyglycol ether, preferably having an alkyl or alkaryl group having 8 to 20 carbon atoms and 8 to 40 ethylene oxide units; Ethylene oxide / propylene oxide copolymer, preferably a block copolymer, having 8 to 40 ethylene oxide and / or propylene oxide units advantageously. More particularly, particularly preferred anionic emulsifiers include fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C1 5-alkane sulfonates, which are usually alkali metal salts, particularly It is used in the form of a sodium salt. These compounds are commercially available, more specifically, under the trade names Disponil® FES 32, A er os ο 1 ® OT 7 5, T ex ap ο η ® K 1 2 9 6 and Statexan® Kl, sold by Cognis GmbH, Cytec Industries, Ine. and Bayer AG 〇-37· 201012836 wisely, nonionic emulsifiers include a third octylphenol ethoxylate having 30 ethylene oxide units and an alkyl group having 8 to 20 carbon atoms and 8 to 40 ethylene oxide units are preferred fatty alcohol polyglycol ethers. These emulsifiers are available from the market under the trade names Triton® X 305 ( Fluka ) and Tergitol® 15-S-7 ( Sigma-Aldrich Co.).

Marlipal® 1618/25 (Sasol Germany) and Marlipal® 0 1 3/400 (Sasol Germany) ° Preferably, a mixture of an anionic emulsifier and a nonionic emulsifier can be used. The weight ratio of the anionic emulsifier to the nonionic emulsifier may be judiciously in the range of 20:1 to 1:20, preferably 2:1 to 1:10 and more preferably 1:1 to 1:5. Particularly suitable mixtures which have proven to be anionic emulsifiers comprise sulphates (more particularly fatty alcohol ether sulphates, lauryl sulphates or sulphonates, more particularly diisooctyl sulfosuccinate) or alkane sulphonates. The acid ester, nonionic emulsifier is an alkylphenol ethoxylate or a fatty alcohol polyglycol ether, each of which has 8 to 20 carbon atoms and 8 to 40 epoxy groups in the alkyl group. Ethane unit. Suitably, the emulsifier can also be used in the form of a mixture of protective colloids. Suitable protective colloids include partially hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, carboxymethyl, methyl, hydroxyethyl and hydroxypropyl-cellulose, starch, protein, poly(meth)acrylic acid, poly (Meth) acrylamide, polyvinyl sulfonic acid, melamine-formaldehyde sulfonate, naphthalene-formaldehyde sulfonate, styrene-maleic acid and vinyl ether-maleic acid copolymer. If a colloid for protection is used, preferably, they are used in an amount of from 〇1 to 1.0% by weight based on the total amount of the monomers. The protective colloid may be included in the initial charge before the start of the polymerization in 201012836 or referred to therein. The initiator may be included in the initial charge or metered into it. In addition, it is also possible to include a portion of the initiator in the initial charge or in the metering allowance. This polymerization is preferably carried out by heating the batch to the polymerization temperature and weighing the initiator (preferably in an aqueous solution). The metering of the emulsifier and the monomer can be carried out separately or in a mixture. In the case where a mixture of the emulsifier and the monomer is metered in, the emulsifier and the monomer are mixed in advance in the upstream of the mixer of the polymerization Φ reactor. Preferably, after the start of the polymerization, the remaining emulsifiers and monomers not included in the initial charge are weighed separately from one another. Preferably, the feed can be weighed starting at 10 to 35 minutes after the start of the polymerization. Emulsified polymers having a high proportion of insoluble polymer can be obtained in the foregoing manner, and reaction parameters for obtaining high molecular weight are known. Therefore, more specifically, the use of the molecular weight modifier is omitted here. One way to influence the adjustment of the particle radius is via the emulsifier ratio. The higher the ratio of φ, more particularly at the beginning of the polymerization, the smaller the particles obtained, the polymer which is obtained according to the aforementioned method, in particular the preferably obtained emulsified polymer, representing the other standard of the invention. . The emulsified polymer may preferably be 2 to 6 重量% by weight based on the weight of the emulsified polymer, more preferably 10 to 50% by weight, and most preferably 20 to 40% by weight, which may be dissolved at 20 ° C. In tetrahydrofuran (THF). To determine the soluble fraction, the polymer sample which had been dried without oxygen was stored in a solvent of 20 ° C in an amount of 200 times the weight of the sample for 4 hours. To ensure that no oxygen is present -39- 201012836, for example, the sample can be dried under nitrogen or under reduced pressure. Thereafter, by filtration, the insoluble fraction is separated from the solution. After the solvent was evaporated, the residue weight was measured. For example, 0.5 g of an emulsion polymer sample dried under reduced pressure can be stored in 150 ml of THF for 4 hours. According to a preferred modification of the invention, the emulsified polymer can swell at least 1000%, preferably at least 1400% and at least 1600%, in tetrahydrofuran (THF) at 20 °C. For its part, the upper limit of swelling is not specified, but the swelling is preferably not more than 5,000%, more preferably not more than 3,000%, and not more than 2,500%. To determine swelling, the emulsified polymer which had been dried under anaerobic conditions was stored in 200 times the amount of 20 ° C THF for 4 hours. As a result, the sample swollen. The swollen sample was separated from the supernatant liquid solvent. After that, the solvent is removed from the sample. For example, most of the solvent can be evaporated at room temperature (20 ° C). The residual solvent can be removed in a dry oven (140 ° C), which is usually 1 hour. The swelling ratio is obtained from the weight of the solvent absorbed by the sample and the weight of the anhydrous sample. Further, the difference between the weight of the sample before the swelling test and the weight of the dried sample after the swelling test gave a soluble ratio of the emulsified polymer. The particle radius of the emulsified polymer can be in a wide range. Therefore, in particular, an emulsified polymer having a particle radius in the range of 1 to 100 nm (preferably in the range of 5 to 59 nm) can be used. According to another feature of the invention, suitable particle radii range from 60 nanometers to 500 nanometers, more preferably from 70 to 150 nanometers and from 75 to 100 nanometers. The particle radius can be determined by PCS (photon correlation spectroscopy) and the data provided is for d50 (50% of the particles are smaller and 50% larger). This can be done by using, for example, the Beckman Coulter N5 Submicron Particle Size Analyzer. -40- 201012836 Emulsified polymers with high swelling factors are particularly surprisingly advantageous. Preferred emulsifying polymers have a swelling factor of at least 2, more particularly at least 4, particularly preferably at least 6 and more particularly preferably at least 8. The swelling factor was measured by the method described above by first measuring the particle radius (r*) of the emulsified polymer in water. The emulsified polymer was then swollen in a solvent/water mixture (THF / water = 90:1) and the particle size (microgel) (rigm) was determined using a Coulter Nanosizer N5. For this purpose, a corresponding amount of φ tetrahydrofuran (THF) is added to the dispersion to set the volume ratio of thF / water in the dispersion to 90:10. The dispersion was swollen for 5 minutes after addition of a solvent (THF) as measured at 20 °C. The quotient of the particle volume calculated from the obtained particle radius (Γigaί and r water) is defined as the swelling factor (QF): QF = I^1 Hydrophobic The emulsified polymer with a low initial cross-linking exhibits a high swelling factor. Here, the preliminary cross-linking of 〇 means that the emulsified polymer is undesirably cross-linked before it is applied to the particles to be coated. Accordingly, an emulsifier compound obtained from a monomer mixture having a ratio of a compound having two or more (meth) acrylate groups has a high swelling factor. Preferably, the above-described alcohol-derived fatty acid ester having 1 to 4 carbon atoms, particularly fatty acid methyl ester (FAME), is reacted to produce a polymer having these properties. The glass transition temperature of the polymer of the present invention is preferably in the range of -30 ° C to 70 ° C, more preferably in the range of -20 ° C to 40 ° C and in the range of 〇 ° c to 25 -41 - 201012836 Excellent in the range of °c. This glass transition temperature may be affected by the nature and proportion of the monomers used to make the polymer. The glass transition temperature 'Tg of the polymer can be determined in a known manner by differential scanning card (DSC). In addition, the glass transition temperature Tg can also be calculated in advance by Fox. According to Fox T. G., Bull. Am. Physics Soc. 1,3,p · 1 2 3 (1 9 6 5 ) ’ which is 丄=five + 3_ + ... + 3_

Tg Tgl Tg2 Tgn

Wherein Xn represents the mass fraction (% by weight / 100) of the monomer n and Tgn represents the glass transition temperature (unit: K) of the homopolymer of the monomer η. Further useful information can be found by the skilled artisan in Polymer Handbook, 2nd Edition, J. Wiley & Sons, New York (1975), which provides Tg値 for most common homopolymers. The polymer herein may have one or more different glass transition temperatures. Therefore, these numbers are used for the segments obtainable by polymerizing the monomer mixture of the present invention.

Used in many applications and properties, the construction of the polymer is not strictly limited. Accordingly, the polymer (particularly an emulsifying polymer) may comprise a random copolymer, a tapered copolymer, a block copolymer and/or a graft copolymer. The block copolymers and tapered copolymers can be obtained, for example, by discontinuously changing the monomer composition during chain propagation. According to a preferred aspect of the invention, the emulsion polymer comprises a random copolymer in which the monomer composition at the time of polymerization is substantially fixed. However, since the monomers may have different copolymerization parameters, the exact composition of the polymer chain of the polymer may vary. This polymer may constitute a homogeneous polymer which, for example, forms particles having a fixed composition in an aqueous dispersion. In this case, the polymer (preferably emulsified - 42 - 201012836 polymer) may be composed of one or more segments which can be obtained by polymerizing the monomer mixture of the present invention. According to another system, the emulsified polymer may constitute a core-shell polymer which may have one, two, three or more shells. In this case, the segment obtained by polymerizing the monomer mixture of the present invention may preferably form the outermost shell of the core-shell polymer. This shell can be attached to the core or inner shell by covalent bonds. In addition, the shell can also be polymerized on the core or inner shell. In this system, in many cases Φ, the segments which can be obtained by polymerizing the monomer mixture of the present invention can be separated and separated from the core by a suitable solvent. The weight ratio of the segment to the core which can be obtained by polymerizing the monomer mixture of the present invention may preferably be in the range of 2:1 to 1:6, more preferably 1:1 to 1:3. The core is formed of a polymer comprising from 50% by weight to 100% by weight, more preferably from 60% by weight to 90% by weight, based on the unit derived from (meth) acrylate. Here, preferably, the alcohol moiety of the (meth) acrylate preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 to 10 carbon atoms. More particularly, it includes (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylate Isopropyl ester, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate and hexyl (meth)acrylate. According to a particular system of the invention, the core can be made using a mixture comprising a methacrylate and an acrylate. Thus, more particularly, a mixture of methyl methacrylate and an acrylate having 2 to 6 carbon atoms (-43-201012836 such as ethyl acrylate, butyl acrylate and hexyl acrylate) is used. Further, the core polymer may include the aforementioned comonomer. According to a better modification, the core can be cross-linked. This crosslinking can be achieved by using a monomer having two, three or more radically polymerizable double bonds. The shell of the emulsifying polymer of the present invention which can be obtained by polymerizing the monomer mixture of the present invention preferably comprises 15 to 50% by weight of a monomer derived from the formula (I) wherein the R1 group has at least one double bond Unit of A. According to a particular aspect, the core has a glass transition temperature in the range of from -30 ° C to 200 ° C, more preferably in the range of from - 20 ° C to 150 t. The emulsified polymer shell of the present invention, which is preferably obtained by polymerizing the monomer mixture of the present invention, preferably has a glass transition temperature in the range of -30 ° C to 70 ° C at -20 ° C. It is more preferably in the range of 40 ° C and in the range of 0 ° C to 25 ° C. According to a particular aspect of the invention, the core glass transition temperature can be greater than the glass transition temperature of the shell. Sensically, the core glass transition temperature is at least 1 (TC, at least 20 ° C better than the glass transition temperature of the shell). The iodine number of the polymer of the invention is in the range of 1 to 150 grams of iodine per 100 grams of polymer. Preferably, it is preferably in the range of 2 to 100 g of iodine per 100 g of polymer, and preferably in the range of 5 to 40 g of iodine per 100 g of polymer, which is determined according to DIN 5324 1 - 1. More particularly, it can be determined on the basis of the dispersion of the invention. Smartly, the acid number of the polymer is in the range from 0.1 to 40 mg KOH / gram, preferably from 1 to 20 mg KOH / gram and from 2 to Excellent in the range of 10 mg KOH / g. This acid number can be measured from the dispersion according to DIN EN ISO 2114 -44 - 201012836. The hydroxyl number of this polymer is in the range of 〇 to 2 〇〇 mg K 〇 H / gram. Preferably, it is preferably from 1 to 100 mg KOH/g and is preferably in the range of from 3 to 5 mg KOH/g. This hydroxyl number can be measured from the dispersion according to DIN EN ISO 4629. The polymer obtained by the monomer mixture. According to a special system of the present invention, the dispersion obtained by the emulsion polymerization reaction can be The form is used as a coating. Accordingly, the aqueous dispersion is a further standard of the invention. The solid content of the aqueous dispersion is preferably in the range of 10 to 70% by weight, more preferably 20 to 60% by weight. The dynamic viscosity of the body is in the range of 〇丨 to 180 mPas, preferably from 1 to 80 inpas and from 1 〇 to 50 mpas. This is measured according to DIN EN ISO 25 5 5 at 25 ° C ( Brookfield). The aqueous dispersion may be supplied with additives 其他 or other components in a known manner such that the properties of the coating meet specific requirements. These additional materials include, more particularly, drying aids (referred to as desiccants) and flow improvers, pigments and Preferably, the coating of the invention has a minimum film forming temperature of not more than 50 ° C, preferably not more than 35 ° C and not more than 25 ° C, which can be determined according to DIN ISO 21 1 5 . The coating does not require a desiccant, but the additive may include optional components as a composition. Particularly preferably, a desiccant may be added to the aqueous dispersion. More particularly, these desiccants include organometallic compounds. For example, -45-201012836, metal soaps of transition metals (such as cobalt, manganese, lead and zirconium), alkali metals or alkaline earth metals (such as lithium, potassium and calcium). Examples which may be mentioned include cobalt naphthalate and acetic acid. Cobalt. The desiccant may be used singly or in a mixture, particularly preferably comprising a mixture of a cobalt salt, a cerium salt and a lithium salt. The aqueous dispersion of the invention may more particularly act as a coating or as an auxiliary agent thereof. Materials include, more particularly, paints and varnishes, doping compositions, adhesives, and/or primer systems. Particularly preferably, the aqueous dispersion can be used to make paint, varnish or doping compositions for wood and/or metal. The coatings obtainable from the coatings of the present invention have high solvent resistance; more specifically, only a small portion of the coating is dissolved by the solvent. Preferably, the coating is highly resistant and, more particularly, highly resistant to methyl isobutyl ketone (MIBK). Therefore, the weight loss after the treatment with MIBK is not more than 50% by weight, and more preferably not more than 35% by weight. The MIBK absorption is preferably not more than 300% by weight, and not more than 250% by weight, based on the weight of the coating used. These tethers were measured at a temperature of about 25 ° C and an exposure time of at least 4 hours, and the coating to be measured was a completely dried coating. This drying is carried out, for example, in the presence of oxygen, air, for crosslinking. The coating obtained from the coating of the present invention exhibits high mechanical stability. The pendulum hardness is preferably at least 15 seconds, preferably at least 25 seconds, as determined by DIN ISO 1522. In addition to the emulsified polymer, the dispersion of the present invention also contains other components. These include, in particular, alkyd resins. The term "alkyd resin" has been known for a long time. Generally, it is a resin obtained by condensing a polybasic carboxylic acid and a polyhydric alcohol to obtain a compound of -46-201012836, for example, usually a long-chain alcohol (fatty alcohol), a fatty acid. Or a compound containing a fatty acid (such as 'fat or oil) modified (din 55945; 1968). Alkyd resins are described, for example, by Ullmann’s

Encyclopedia of Industrial Chemistry, 5th edition, CD-ROM version. In addition to these conventional alkyd resins, resins having similar properties can also be used. For example, these resins similarly have a high amount of groups derived from the aforementioned long chain alcohols (fatty alcohols), fatty acids and/or fatty acid containing compounds (e.g., fats or oils). However, these derivatives do not necessarily have to contain a high base carboxylic acid, but can be obtained, for example, from the reaction of a polyhydric alcohol with an isocyanate. The alkyd resin is preferably diluted or mixed with water. For example, it is preferred to use an alkyd resin which can be modified by a polymer obtained by radical polymerization. Such resins are disclosed in the announcement, including US 5,53 8,760, US 6,3 6 9,1 3 5 and D E -A -1 9 9 5 7 1 6 1 . The resin proposed in US 5,538,760 (22.05.95 filed in the U.S. Patent Office (USPTO), application number 446,1 30) is included for the purposes of this application. The resin set forth in Announcement 1 186, 3 69, 13581 (13.08.96 filed in the United States Patent Office (USPTO), application Serial No. 08/696,36 1) is incorporated herein by reference. The resin proposed in the publication DE-A-199 57 161 (27.11.99 filed in the German Patent and Registered Trademark Office (DPMA), application number DE 1 9957 1 6 1.9) is included for the purpose of this application. . According to the publications US 5,538,760 and US 6,369,135, the modified alkyd resin can be obtained by a method comprising a polymerization reaction of a monomer mixture in the presence of an alkyd resin. Here, the weight ratio of the monomer mixture to the alkyd resin is preferably from -47 to 201012836 in the range of from 100:1 to 1:4, more preferably from 5:1 to 1:1. Particularly sensibly, the acrylate-modified alkyd resin described in DE-A-1 99 57 161 is included. These alkyd resins contain a group obtained by polymerizing a (meth) acrylate in addition to an alkyd core. An alkyd resin obtainable according to the publication US 5,096,959 is preferred. These alkyd tree-modified cycloaliphatic polycarboxylic acids, cyclohexanedicarboxylic acid, and cyclohexanedicarboxylic acid are particularly suitable for this modification. For disclosure purposes, US 5,096,959 B1 (30.10.90 filed in the US Patent Office (USPTO), application number 609,024) is incorporated herein by reference. Further, an alkyd resin modified with polyethylene glycol can be used. Many patents describe the preparation of water-emulsifiable alkyd resins modified with polyethylene glycol (PEG). In most processes, about 10% to 30% of the PEG is directly incorporated into the alkyd resin by esterification or transesterification (see, in particular, U.S. Patent Nos. 2,634,245; 2,853,459; 3,133,032; 3,223,659; 3, 379, 548; 3, 437, 615; 3, 437, 618; 10 3, 442, 835; 3, 4 57, 2 06; 3, 639, 315; and German published specification 14 95 032; or British Patent Nos. 1,038, 696 and 1, 044, 821. Preferred polyethylene glycol modified alkyd resins include self-announcement EP-A-0 029 145 is known. For disclosure purposes, the publication ΕΡ-Α-0 029 145 (filed at the European Patent Office at 30.10.80, application number ΕΡ 80106672·1) is incorporated into this application. According to the announcement, polyethylene glycol can be first reacted with an epoxy group-containing carboxylic acid. The resulting reaction product is then used in a reaction mixture for preparing an alkyd resin. The number average molecular weight of the diol is, for example, 500 to 5000 g/m 201012836. Particularly preferred polyethylene glycol modified alkyd resin may be additionally copolymerized (eg, by methacrylic acid, unsaturated fatty acid) And ethylene And/or by polymerization of a vinylidene compound.) According to a feature of the invention, these alkyds can also be modified by copolymers obtainable by the monomer mixtures of the invention. Also, judiciously, alkyds are subjected to uric acid. Ester-based modification. This type of ester © alkyd resin is described, inter alia, in WO 2006/092211 and EP-A-1 533 342 for disclosure purposes, publication EP-A-1 533 342 (09.11.04 in the European Patent Office) The application, application number EP 040265 1 1 .8) is incorporated herein by reference for its disclosure. Preferably, it can be used by polyhydric alcohol A', modified fatty acid B', fatty acid C' and more A carbamate alkyd resin obtained by reacting a functional isocyanate D'. The modified fatty acid B' can be obtained by reacting an unsaturated fatty acid with an unsaturated carboxylic acid B2'. Alkyd resins are known from WO 2006/0922 1 1 for the purpose of disclosure, publication WO 200 6/0 92211 (20.02.06 filed in the European Patent Office, application number PCT/EP2006/00 1 503) The resin proposed in the present application is included in the present application. The fatty acid B is preferably at least 80 mg/g, particularly preferably, the acid number increased by grafting is in the range of 80 mg/g to 250 mg/g, at 100 mg/g. It is particularly preferred in the range of 150 mg/g, which is determined according to DIN EN ISO 2114. The iodine number of the fatty acid C' used to prepare the carbamate alkyd resin is preferably from -49 to 201012836, preferably less than 80 g / 100 g and more preferably at least 120 g / 100 g. The preparation of a carbamate alkyd resin is described in WO 2006/09221 1 'Generally, the components A', B' and C' are reacted first, and the hydroxy functionality of the condensate is preferably at least 1.9, at least 2 is better. . This condensate may further contain a group derived from a polybasic carboxylic acid (particularly the aforementioned dicarboxylic acid and tricarboxylic acid). This condensate is then reacted with a polyfunctional isocyanate. Preferred polyfunctional isocyanates include, in particular, toluene 2,4 and 2,6-diisocyanate and their industrial mixtures, bis(4-isocyanatophenyl)methane, isophorone diisocyanate Esters, bis(4-isocyanatocyclohexyl)methane and 1,6-diisocyanatohexane and biurets, carbamates and isofluranes derived therefrom. In addition to the aforementioned alkyd resins which are conventionally used and generally used in the preparation of polybasic carboxylic acids, other resins may be used, as described above. These include, in particular, urethane based alkyds. These more particularly include the carbamate alkyd resins obtainable by reacting another polyhydric alcohol with a polyfunctional isocyanate. Preferred urethane resins are known, for example, from E P - A - 1 1 2 9 1 4 7 . For example, they can be obtained by reacting a guanamine ester diol with a polyol and a polyfunctional isocyanate. The guanamine ester diol used in accordance with EP-A-1 1 29 1 47 can be obtained by reacting a vegetable oil with an N,N-dialkylolamine. Further, the monomer mixture of the present invention can also be used to modify an alkyd resin. The examples and comparative examples of the present invention are described below, but the invention is not intended to be limited by the examples. Example of the invention la (manufacture of a mixture of methacryloxy-2-ethyl fatty acid decylamine) -50- 201012836 equipped with a sabre stirrer with a stirring sleeve and a stirring motor, a nitrogen inlet, a liquid phase thermometer and a distillation bridge A four-necked round bottom flask was charged with 206.3 grams (0.70 moles) of a mixture of fatty acid methyl esters, 42.8 grams (0.70 moles) of ethanolamine, and 0.27 grams (0.26%) of LiOH. The fatty acid methyl ester mixture comprises 6 wt% saturated C12 to C16 fatty acid methyl ester, 2.5% by weight saturated C17 to C20 fatty acid methyl ester, 52% by weight monounsaturated C18 fatty acid methyl ester, 1-5 wt% monounsaturated C20 To C24 fatty acid methyl ester, 36% by weight of polyunsaturated C18 fatty acid methyl ester and 2% by weight of polyunsaturated C20 to C24 fatty acid methyl ester. This reaction mixture was heated to 150 °C. 19.5 ml of methanol was removed by distillation over 2 hours. The obtained reaction product contained 86.5 % of a fatty acid ethanolamine. The resulting reaction mixture was further processed without purification. After cooling, 1919 g (19.2 mol) of methyl methacrylate, 3.1 g of LiOH, and an inhibitor mixture consisting of 500 ppm of hydroquinone monomethyl ether and 500 ppm of phenothiazine were added. The reaction apparatus was purged with nitrogen for 10 minutes. The reaction mixture is then heated to boiling. The methyl methacrylate/methanol azeotrope was separated and then the temperature of the distillation head was gradually increased to 1 Torr (TC. After the end of the reaction, the reaction mixture was cooled to about 70 ° C and filtered. Separation of excess methyl groups on a rotary evaporator Methyl acrylate. This gave 370 g of product. Example 1 b of the invention was introduced in a four-neck round bottom bottle equipped with a sabre mixer with a stirring sleeve and a stirring motor, a nitrogen inlet -51 - 201012836, a liquid thermometer and a distillation bridge 206.3 g (0.70 mol) of a mixture of fatty acid methyl esters, 42.8 g (0.70 mol) of ethanolamine and 0.27 g (0.26%) of LiOH. The fatty acid methyl ester mixture contains 6 wt% of unsaturated C12 to C16 fatty acid methyl esters. 2.5% by weight of saturated C1 7 to C20 fatty acid methyl ester, 52% by weight of monounsaturated C18 fatty acid methyl ester, 1.5% by weight of monounsaturated C20 to C24 fatty acid methyl ester, 36% by weight of polyunsaturated C18 fatty acid A Ester and 2% by weight of polyunsaturated C20 to C24 fatty acid methyl ester. The reaction mixture was heated to 150 ° C. 19.5 ml of methanol was removed by distillation over 2 hours. The resulting reaction product contained 86.5 % ethanol. The resulting reaction mixture was further processed without purification. After the addition of an inhibitor mixture consisting of 500 ppm hydroquinone monomethyl ether and 500 ppm phenothiazine, 108 g (0.70 mol) of methacrylic anhydride was slowly The solution was weighed at a liquidus temperature of 8 (TC. The reaction mixture was heated to 90 ° C and stirred at this temperature for 6 hours. The formed methacrylic acid was separated on a thin film evaporator. This gave a brown liquid product. Example 2 A polymer dispersion was prepared using a monomer mixture obtained according to Example 1 of the present invention and comprising different methacryloxy-2-ethyl fatty acid decylamine. First, in a 2 liter PE beaker, 180 grams of acrylic acid Butyl ester (BA), 156 g of methyl methacrylate (MMA) '60 g of methacryloxy-2-ethyl fatty acid decylamine mixture, 4 g of methacrylic acid (mas), 1.2 Grams of peroxydiammonium disulfate (APS), 12_0 grams of -52- 201012836 〇13?〇11丨1?£8 32 (30% form) and 359.18 grams of water use 1;1"&-

The Turrax was emulsified for 3 minutes at 40 00 rpm. A 2 liter glass reactor equipped with a water bath heating device and equipped with a paddle stirrer was introduced with 230 grams of water and 0.3 grams of Disponil FES 32 (30% form) and the initial introduction was heated to 80 ° C with 0.3 grams of peroxygen Ammonium disulfate (APS) (in a solution of 10 grams of water) is blended. After 5 minutes of APS addition, it was weighed into the pre-manufactured emulsion in 2 40 minutes (interval: 3 minutes of feeding, 4 minutes of pause, • 23 7 minutes of the remaining material). After the end of the feeding, the batch was stirred at 80 ° C for 1 hour. Then, it was cooled to room temperature and the dispersion was filtered through a VA sieve fabric having a mesh size of 0.09 mm. The resulting emulsion had a solids content of 40 ± 1%, a pH of 5 · 6, a viscosity of 37 mPas and an rN5 70 of 70-75 nm. The properties of the resulting coatings were investigated in several ways. Here, experiments on solvent resistance, water absorption, and hardness were carried out on the dried film. The solvent resistance was carried out using methyl isobutyl ketone (MIBK), and the sample φ was swollen at room temperature for 4 hours with MIBK. After the sample was taken out from the solvent and excess solvent was removed. Thereafter, the solvent was dried at about 1 40 ° C for 1 hour. The proportion of sample removed from the solvent was calculated from the weight loss. The weight loss reported in Table 1 in ethanol was measured in a manner similar to that described in the previous experiments, but using ethanol as the solvent. The water absorption was measured using an untreated solid pine sample (size: 45-50 mm X45-5 0 mm x 17 mm). This sample was coated and placed in water at room temperature with only the coated area in contact with water. The water absorption is calculated from the weight of the sample. -53- Ο 201012836 The results are shown in Table 1. The results of the obtained coatings in DIN 6886 1 - 1 are shown in Table 2. Comparative Examples 1 and 2 For comparison purposes, a commercially available alkyd resin was investigated, and the comparative example 1 was a commercially available alkyd resin (Worl0e 'named El 50W ) and the sensitivity of Comparative Example 2 was Xyladecor sold by ICI. The results are shown in Table 1. Comparative Example 3 First, in a 2 liter PE beaker, 206.8 g of butyl acrylate (BA), 165.2 g of methyl methacrylate (MMA), 4 g of methacrylic acid (MAS), 24 g. Ethylacetate ethyl methacrylate (AAEMA), 1.2 g of ammonium peroxydisulfate (APS), 12.0 g of 〇18卩〇11丨1 [£8 32 (30% form) and 359.18 g of water are used "3-Turrax is emulsified for 3 minutes at 4000 rpm. 230 liters of water and 0.3 gram of 〇8 〇11丨1?£8 32 (30% form) are introduced into a 2 liter glass reactor with a water bath heating device and a paddle stirrer. And the initial feed was heated to 80 ° C and blended with 〇.3 g of ammonium peroxydisulfate (APS) in 1 gram of water. After 5 minutes of adding APS, the emulsion was prepared. Weighed in 240 minutes (interval: 3 minutes of feeding) 4 minutes pause, 237 minutes of remaining material. After the end of the feeding, the batch was stirred at 8 ° C for 1 hour. After that, it was cooled to room temperature and dispersed. Body furnace 〇.〇 9mm mesh size VA mesh fabric -54- ( 201012836 This dispersion is in the form of a molar to 6 wt% AAEMA' Diterpenes (human 0; 9) cross-linking. This was achieved by adding 6.54 g of a 15% strength AD Η solution to 100 g of dispersion during stirring and stirring was continued for 30 minutes. On the dried film In the above, experiments relating to solvent resistance, water absorption and scratch resistance were carried out. Table 1: Results of the study of the properties Example 2 of the present invention Comparative Example 1 Comparative Example 2 Comparative Example 3 Pendulum hardness [sec] 36.4 13.3 12.6 21.7 Pencil Hardness 3H < 6B B - Weight loss in MIBK [%] 9.7 47.7 23.5 13.6 Weight loss in ethanol [%] 11.0 - 24.0 14.2 Water absorption after 24 hours 9.7% 45.5% 25.2% 17.2% Table 2: DIN 6886 1 - 1 倶 test Example 2 of the invention Comparative example 3 倶 test NH3 (10%) 1 hour 3 1 16 hours 3 1 Furniture test EtOH (48%) 1 hour 5 2 16 hours 4 1 Furniture test HOAc ( 15%) 1 hour 5 5 16 hours 4 1 DIN 68861-1 furniture test shows that the dispersion of the invention gives the coating a high stability for a variety of different solvents. Conversely, the stability of the uncrosslinked polymer for ethanol is extremely high. Low, the coating according to the invention is based on a base, an acid and a polar-55-201012836 solvent Stability. -56

Claims (1)

201012836 VII. Patent application scope: 1. A monomer mixture comprising at least one monomer of the formula (I) (I). wherein R is hydrogen or methyl, and X1 and X2 are independently oxygen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), but the group X1 and At least one of X2 is a group of the formula NR' (wherein R is hydrogen or a group having 1 to 6 carbon atoms), z is a linking group, and R1 is an unsaturated having 9 to 25 carbon atoms a group, and at least one monomer B of the formula (II) Wherein R is hydrogen or methyl 'X1 and X2 are independently oxygen or a group of formula NR' (wherein R' is hydrogen or a hydrazine having from 1 to 6 carbon atoms), but at least one of the groups Χι and X2 One is a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), hydrazine is a linking group, and R2 is a saturated group having 9 to 25 carbon atoms. 2. The monomer mixture of claim 1 wherein the weight ratio of the monomer to the monomer is in the range of from 100:1 to 1:1. 3. The monomer mixture of claim 1 or 2, wherein the monomer A of the formula (I) has an iodine number in the range of 50 to 300 g iodine/gram. -57-201012836 4. The monomer mixture of claim 1 or 2, wherein the monomer mixture comprises at least one monomer A of formula (III) (III). ❹ wherein R is hydrogen or methyl, X1 is oxygen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), Z is a linking group, and R' is Hydrogen or a group having 1 to 6 carbon atoms and R1 is an unsaturated group having 9 to 25 carbon atoms, and at least one monomer B of the formula (IV) (IV), wherein R is hydrogen or methyl, X1 is oxygen or a group of the formula NR' (wherein R' is hydrogen or a group having 1 to 6 carbon atoms), Z is a linking group, and R' is hydrogen Or a group having 1 to 6 carbon atoms and R2 is a saturated group having 9 to 25 carbon atoms. 5. The monomer mixture of claim 1 or 2, wherein at least some of the unsaturated groups R1 of monomer A of formula (I) contain exactly one double bond. 6. The monomer mixture of claim 1 or 2, wherein at least some of the unsaturated groups R1 of monomer A of formula (I) contain two or more double bonds. 7. The monomer mixture of claim 1 or 2, wherein the monomer A of the formula (I) having exactly one double bond in the unsaturated group R1 is -58- 201012836, and the unsaturated group R1 contains two The weight ratio of the monomer A of the formula (1) of the multiple or more double bonds is in the range of 10:1 to 1:5. 8. The monomer mixture as claimed in claim 1 or 2 wherein the monomer mixture contains at least 5% by weight of monomer A having 17 to 21 carbon atoms in the unsaturated group R1. 9. The monomer mixture as claimed in claim 1 or 2 wherein the monomer mixture contains at least 1% by weight of monomer B having 11 Φ to 17 carbon atoms in the saturated group R2. 10. The monomer mixture of claim 1 or 2, wherein the monomer mixture contains monomer A and/or monomer B having at least one hydroxyl group in the linking group Z. 11. The monomer mixture of claim 1 or 2, wherein the monomer mixture is obtained by reacting a fatty acid methyl ester with an amine. 12. The monomer mixture of claim 1 or 2, wherein the monomer mixture contains a monomer copolymerizable with the monomers ruthenium and osmium. Φ 13. The monomer mixture of claim 12, wherein the monomer mixture contains at least one monomer having an acid group. I4. The monomer mixture of claim 12, wherein the monomer mixture contains a monomer C comprising an ester group and different from the monomer of formula I or II. A monomer mixture according to claim 14 wherein the monomer mixture comprises (meth) acrylate, fumarate, cis-butenediate and/or vinyl acetate. 16. The monomer mixture of claim 1, wherein the -59-201012836 monomer mixture contains styrene monomer. 17. The monomer mixture of claim 1 or 2, wherein the monomer mixture comprises 0.1 to 50% by weight of monomer A, 0.1 to 50% by weight of monomer B, and 30 to 95% by weight of ester-containing ester. The monomer C of the group is 〇 to 10% by weight of the monomer having an acid group, 〇 to 50% by weight of the styrene monomer, and 〇 to 50% by weight of the other comonomer. 18. The monomer mixture of claim 1 or 2, wherein the monomer mixture comprises 0.5 to 30% by weight of monomer A, 0.5 to 30% by weight of monomer B, and 40 to 90% by weight of ester-containing ester. The monomer C of the group, 1 to 8% by weight of the monomer having an acid group, 〇 to 50% by weight of the styrene monomer, and 〇 to 50% by weight of the other comonomer. 19. The monomer mixture of claim 1 or 2, wherein the proportion of the compound having two or more (meth) acrylate groups in the monomer mixture is limited to not more than 2% by weight. 20. A polymer comprising a repeating unit derived from a monomer mixture of at least one of claims 1 to 19. 21. The polymer of claim 20, wherein the polymer has a glass transition temperature in the range of from -20 to 40 °C. The polymer of claim 20 or 21, wherein the polymer is an emulsion polymer. 23. The polymer of claim 20 or 21 wherein the polymer has a swelling factor of at least 2 as measured by a tetrahydrofuran/water mixture at 20 °C. A composition for producing a coating, characterized in that the composition comprises the polymer of at least one of claims 20 to 23. Φ 25· A composition for producing a coating characterized in that the composition contains an alkyd resin. 26. A method of preparing a monomer mixture of at least one of claims 1 to 19, characterized in that the fatty acid ester mixture is reacted with an amine and then the resulting decylamine and (meth) acrylate are / or (meth)acrylic acid reaction. 27. The method of claim 26, wherein the fatty acid methyl ester is used as the ester of the fatty acid ester mixture. The method of claim 26, wherein the intermediate obtained is reacted without purification to form monomer A of formula (I). 29. The method of claim 26, wherein the reaction of the obtained decylamine with (meth) acrylate is carried out in the presence of a base. 30. A method of preparing a monomer mixture of at least one of claims 1 to 19, characterized in that a mixture of fatty acid esters is reacted with an amine, and then the resulting decylamine is reacted with (meth)acrylic anhydride . 3. A method as claimed in claim 30, wherein methyl ester of fatty acid is used as the ester in the mixture of fatty acid esters. -61 - 201012836 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none