DE102006040471A1 - se of an epoxy-functional adduct prepared from triglycidyl iscyanurate or triglycidyl trimellitate as a crosslinker or hardener for carboxy-functional polyesters suitable for producing powder coatings - Google Patents

Abstract

Solid adduct produced by reacting triglycidyl iscyanurate or triglycidyl trimellitate with a fluorinated cyclic monocarboxylic acid or with a monoester prepared by reacting a dicarboxylic anhydride with a fluorinated alcohol, hydroxybenzotrifluoride or a silanol (I) or silyl-substituted alcohol is used as a crosslinker or hardener for carboxy-functional polyesters suitable for producing powder coatings. The adduct has more than 2 epoxy groups per average molecular weight. Solid adduct produced by reacting triglycidyl iscyanurate or triglycidyl trimellitate with a fluorinated cyclic monocarboxylic acid or with a monoester prepared by reacting a dicarboxylic anhydride with a fluorinated alcohol, hydroxybenzotrifluoride or a silanol RnSi(OH)4-n (I) or silyl-substituted alcohol is used as a crosslinker or hardener for carboxy-functional polyesters suitable for producing powder coatings. The adduct has more than 2 epoxy groups per average molecular weight. R : an aliphatic, aromatic, alicyclic or heterocyclic group; n : 2 or 3. An independent claim is also included for the use of a liquid, semisolid or solid adduct having at least 0.3 epoxy groups per average molecular weight as an additive for coatings, where the adduct is produced by reacting an epoxide having at least two epoxy groups with a fluorinated carboxylic acid or anhydride or with a monoester prepared by reacting a dicarboxylic acid or anhydride with a fluorinated alcohol or hydroxybenzotrifluoride or with a perfluorocarboxylic acid F(CF2)mCOOH or with a monoester prepared by reacting a dicarboxylic anhydride or a silanol (I) or silyl-substituted alcohol. m : 5-21.

Description

The The invention relates to the use of a solid at room temperature Epoixdaddukts with more than two, but less than three epoxide groups per average molecular weight and pendant fluorohydrates and / or Silicon-organic groups, in particular based on the modification of liquid triglycidyl trimellitate, as a crosslinking agent or hardener for powder coatings on the basis of carboxyl-containing polyesters according to the following versions and the claims 1 and 2 and 5 to 7.

Further the invention relates to the use of a fluid at room temperature, semi-solid or solid epoxy adduct (D) with less than one, however, at least 0.3 epoxide groups per average molecular weight and attached Fluorine-containing and / or silicon-organic groups, preferably having a fluorine and / or silicon content of at least 5% by weight, as an additive for solvent-free, solvent-based, dilutable or in the form of aqueous Dispersions present coating or for powdery coating compositions or for modifying binders or binder components according to the following and the claims 3 to 8.

The Production and application of powder coatings based on carboxyl-containing polyester and epoxy group-containing crosslinking agents or hardeners known state of the art; as well as the production of carboxyl-containing polyester, the for Powder coatings are suitable, and the preparation of crosslinking agents, For example, solid epoxy resins having more than one epoxy group per Average molecular weight and / or solid crosslinking agents with more than two, but less than three or three epoxide groups per average molecular weight.

This prior art is extensive in standard works of the technical literature including the references cited therein, for example, (L1) Zeno W. Wicks, Jr., Frank N. Jones, S.Peter Pappas, Organic Coatings, Science and Technology, Volume 2, Applications, Properties, and Performance, published 1994 by John Wiley & Sons, Inc., New York Chichester Brisbane Toronto Singapore, Page 230-252 ; (L2) Stoye / Freitag, Lackharze, Carl Hanser Verlag Munich Vienna 1996, pages 57, 59-60, and 275-276 ; (L3) Dieter Stoye, Werner Freitag (Editors), Paints, Coatings and Solvents, Wiley-VCH Verlag GmbH, D-69469 Weinheim 1998, pages 115-118, 123-124, and 184-193 ; (L4) Volume IV, Waterborne & Solvent Based Saturated Polyesters and their End User Applications, edited by Dr Don Sanders PhD, published in 1999 by John Wiley & Sons Ltd in association with SITA Technology Limited, London UK, pages 443-502, especially page 446- 447, 454-455 and 466-468 , (L5) Ulrich Poth, Polyester and Alkyd Resins, Vincentz Network GmbH & Co. KG, Hannover 2005, page 150-161 , as well as other patent publications, for example EP 0 720 997 A2 . WO 95/01407 respectively. EP 0 706 546 . DE 19 548 491 A1 . WO 95/16753 . EP 0 536 085 B1 , described.

When typical crosslinking agent for the production of good weather-resistant powder coatings based on carboxyl-containing polyester has triglycidyl isocyanurate (TGIC) proven.

Under health aspects has been triglycidyl isocyanurate (TGIC) meanwhile usually by solid crosslinking agents, for example, from a eutectic mixture of room-temperature solid dicarboxylic acid diglycidyl esters, preferably aromatic dicarboxylic acid diglycidyl esters, such as phthalic acid diglycidyl ester, isophthalate and / or terephthalic acid diglycidyl ester, especially the latter, and at room temperature liquid polyglycidyl compounds, preferably trimellitic triglycidyl ester, exist, replaced.

When example for a commercial product is "Araldite PT 910 "(registered Trade name of Ciba Specialty Chemicals, Polymers Division).

Reference is made to the above literature (L4), pages 454-455, and the extensive claims and embodiments in the EP 0 536 085 B1 and the references therein, in particular U.S. Patent 3,859,314 , pointed out. For example, in the EP 0 536 085 B1 , Page 3, lines 18-20, also triglycidyl isocyanurate (TGIC), and in line 44-45 (in connection with line 34) also called hexahydrophthalic diglycidyl ester.

In my DE 39 33 890 A1 , Col. 1, lines 64-68 and et seq. Column 2, lines 1-4, is used for the introduction of carboxyl end groups, for example for the use of polyesters for the preparation of powdered coating compositions (use with triglycidyl isocyanurate or epoxy resins) or for the achievement of water dilutability ( after neutralization with bases, preferably amines) on the reaction of the hydroxyl groups of polyester (cf., column 1, lines 53-63) with polycarboxylic acids or their derivatives, eg. For example, isophthalic acid, trimellitic anhydride, hexahydrophthalic indicated.

According to claim 7 and column 9, lines 24-33, in the preparation of the modified polyester preferably epoxidized oils, for. epoxidized linseed oil or soya oil, or defined glycidyl esters of tertiary synthetic fatty acids such as "Cardura E" (registered trade name of Shell).

The reaction of carboxyl-containing polyesters with versatic acid glycidyl esters such as "Cardura E 10" (registered trade name of Shell) is described, for example, in US Pat DE 33 39 230 C2 , Page 7, reference example 2.

The reaction of carboxyl-containing polyesters with epoxidized linseed oil is for example in EP-A-0 512 523 (Priority DE-OS 41 15 042 ), Example 2, Component B.

The preparation of carboxy-functional, epoxide group-containing polymers based on polyester using epoxidized linseed oil is described for example in Examples 7 and 8 of WO 95/228429 respectively. PCT / EP 95/01411 respectively. EP 0 703 935 , described.

In the WO 95/21208 are powder coatings based on polymers having epoxide groups reactive groups, preferably carboxyl groups containing polyester, and defined aliphatic crosslinking agents, preferably epoxidized soybean oil or epoxidized linseed oil, and defined catalysts described ((description and claims, especially page 15, line 11-12, and page 24, examples I and II).

Special production methods for powder coatings, among others on the WO 95/21208 Reference is made in the WO 95/20017 described.

In my DE 196 34 721 C2 , Column 4 [0022] are reacted with carboxyl-containing polyester reaction products having at least one free epoxide group which, by reacting epoxide compounds with at least two epoxide groups, according to lines 15-21, in particular commercial diepoxides such as liquid at room temperature epoxy resins based on bisphenol A, aliphatic or cycloaliphatic epoxy resins, in particular based on cyclohexanedimethanol, Hexahydrophthalsäurediglycidylester, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and triglycidyl isocyanurate (TGIC), and defined fluorine compounds (lines 34-47), and optionally used fluorine-free compounds (Line 47-58).

Out Column 7, Preparation of the reaction product R [0040] is for the expert can be seen that on an epoxy group theoretically (technical products) about 0.07 equivalents of perfluorooctanoic acid as technical product "Fluorad acid FC 26" (registered trade name from 3M Company) and from column 9, preparation of the reaction product R 4 under [0047] that on an epoxide group 0.2 equivalents of the half-ester were used, so that it is practically modified Epoxy resins with more than one epoxide group per average molecular weight is.

Furthermore R4 is almost as a clear slightly yellowish at room temperature completely tack-free solid resin having a fluorine content of about 6.74 wt .-% described.

Next it is noticed that the DE 196 34 721 C2 See claim 1 as well as column 1 [0001], column 3 [0017], column 5 [0024], row 16 (reaction in the melt), and column 6 [0030], row 12-14, - also comprises pulverulent coating agents.

From my DE 199 01 118 C2 and additives are solid at room temperature, modified cycloaliphatic epoxy resins, processes for their preparation and their use and also known that the said modified cycloaliphatic epoxy resins have a fluorine content of 0.01 to 2 wt .-% (claim 2, etc.) and / or a Silicon content of 0.01 to 15% by weight, preferably 0.01 to 2% by weight of fluorine and 0.1 to 7% by weight of silicon ( DE 100 00 190 A1 , Claims 1-16 and 18-19).

With respect to the use of said modified cycloaliphatic epoxy resins is described in the DE 100 00 190 A1 , Column 9, lines 8-10, generally referred to the embodiments in the parent application.

In the DE 199 01 118 C2 , Columns 15-17 to [0115] is carried out in detail for the preparation of pigmented or transparent powder coatings, in particular with respect to the combination of said modified cycloaliphatic epoxy resins with carboxyl group-containing polyester and the possibility of using suitable curing agents, e.g. Triglycidyl isocyanurate (TGIC), modified triglycidyl isocyanurate, β-hydroxyalkamides.

To Column 16 [0114], et seq. Column 17, lines 1-7, may be the said modified ones cycloaliphatic epoxy resins in conventional coating compositions as Binder component in a smaller amount, z. B. less than 10 wt .-%, based on binder, be included.

In my article in COLOR & LACK 9/1999, page 106-109, "High Gloss, Weather Resistant Powder Coatings" is on page 109 under "Other binder components are easily modified" with reference to [3] DE 196 34 721 A1 stated below, that in particular the fluorinated, preferably trifluoromethyl and / or perfluoroalkyl, modified cycloaliphatic epoxy resins contained also for the modification of Bin Of course, it is also possible for the reaction to be carried out in the coating (note: coating) [3], and it is of course also possible for the reaction to take place in the coating with functional groups, preferably carboxyl groups, which react with epoxide groups [3].

In the DE 196 34 721 C2 , Col. 4 (0022), lines 21-24, is also the use of epoxy resins having more than one epoxide group per average molecular weight, e.g. B. at room temperature solid epoxy resins based on bisphenol A, described for the preparation of the claimed reaction products with at least one epoxy group, and the reaction product R 4 by column 9 (0047) is as stated above, a solid resin with a fluorine content of about 6, 74% by weight.

From the DE 199 01 118 C2 and the DE 100 00 190 A1 are, as stated above, powder coatings based on carboxyl-containing polyesters and solid modified cycloaliphatic epoxy resins having a fluorine content of 0.01 to 2 wt .-% ( DE 199 01 118 C2 , Claim 2 etc.) and / or a silicon content of 0.01 to 15 wt .-%, preferably 0.01 to 2 wt .-% fluorine and 0.1 to 7 wt .-% silicon, known ( DE 100 00 190 A1 , Claims 1-16 and 18-19).

In Considering the above statements It is therefore state of the art or at least for the skilled person readily Useful, for the production of powder coatings on the base of carboxyl-containing polyesters and solid epoxy resins a) Fluorine-containing bisphenol-based solid epoxy resins A and / or b) solid modified cycloaliphatic epoxy resins with a higher one Fluorine content than 2 wt .-% and / or a silicon content to use.

From the DE 196 34 721 C2 is further, as already stated above, known to use triglycidyl isocyanurate for the preparation of fluorine-containing reaction products.

A Use of in the claims 1 and 2 and 5-7 specified and prepared solid epoxide adducts (C) with more than two but less than three epoxide groups per Average molecular weight and pendant fluorine-containing and / or Silicum-organic groups, especially based on the basis from liquid triglycidyl trimellitate (Component A2), with respect to triglycidyl isocyanurate (TGIC) expressis verbis not described, and in relation to trimellitic acid glycidyl ester not obvious.

The EP 0 536 085 B1 relates to defined solid compositions consisting of solid mixed phases of liquid polyglycidyl compounds, preferably trimellitic triglycidylester (claim 8, page 8, lines 31-35), and solid polyglycidyl compounds, preferably terephthalic acid diglycidylester (claim 18, examples 6-9).

The powder coating crosslinking agent used as the equivalent of triglycidyl isocyanurate is in accordance with EP 0 536 085 B1 , Lines 34-35, according to the aforementioned literature (L 4), page 455, a solid mixture of the co-production of 25 wt .-% trimellitic triglycidyl (liquid) and 75 wt .-% terephthalic acid diglycidyl ester (solid) and the registered Trademark "Araldite PT 910" (Ciba Specialty Chemicals, Poylmers Division).

Provided for the preparation of Epoxidaddukten (C) according to claim 1 at all Triglycidylisocyanurat is used, it is convenient modified triglycidyl isocyanurate of defined composition and manufacture.

Preferably Triglycidyl isocyanurate (component A1) only in mixture with triglycidyl trimellitate (Component A2) used, wherein the mixture (component A) to more than 50% by weight, preferably more than 70% by weight, of trimellitic triglycidyl ester (A2).

Component (A2) is triglycidyl trimellitic acid liquid, the preparation of which is described in US Pat EP 0 536 085 B2 , Page 10, lines 12-14, attracted DE-A-16 43 777 Example 15, published June 8, 1972, is known.

The reaction of trimellitic triglycidyl ester (component A2) and fluorine and / or organosilicon compounds (component B) for the preparation and use of epoxide adducts (C) according to claim 1, the skilled person from the EP 0 536 085 B1 do not remove or deduce, since it is in the EP 0 536 085 B1 are not chemical reactions of trimellitic triglycidyl ester, but are solid mixed phases consisting partly of trimellitic triglycidyl ester.

epoxy adducts (C) according to claim 1, in particular on the basis of (A2) Trimellitsäuretriglycidylester built up.

The Average molecular weight is generally below 1500 and is not just the type and amount of epoxy adducts that you need (C) used component (B), but also of process engineering Production conditions dependent, as in the production of epoxy adducts bekantlich unavoidable Side reactions, especially etherification reactions, occur.

The fluorine and / or silicon content is at least 1% by weight, preferably more than 2 % By weight of fluorine and more than 1% by weight of silicon, very particularly preferably more than 5% by weight of fluorine and / or silicon.

Of the Melting point is in the range of about 35 ° C to 100 ° C, preferably 70 to 90 ° C, and preferably For example, epoxide adducts (C) contain more than 2.2 epoxide groups per average molecular weight.

Provided in the preparation of epoxide adducts (C) triglycidyl isocyanurate (A1), this is practically modified triglycidyl isocyanurate.

Preferably Triglycidyl isocyanurate (TGIC) is only mixed with trimellitic triglycidyl ester (A2) used as component (A) according to claim 1, wherein the mixture to more than 50% by weight, preferably to more than 70% by weight, of trimellitic triglycidyl ester (A2).

Examples for the Component (B1) according to claim 1 are 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 3- (trifluoromethyl) benzoic acid, 4- (trifluoromethyl) benzoic acid and / or 2,3,4,5,6-pentafluorobenzoic acid.

Preferably are mixtures of these compounds containing the latter, in particular in a mixture with 4-fluorobenzoic acid or 3- (trifluoromethyl-benzoic acid and / or benzoic acid 4- (trifluoromethyl), used.

To Examples of the components (B2) and (B3) will be explained below concerning half esters for the preparation of epoxide adducts (C) and (D) pointed.

Under the aspect of the melting point of the epoxide adduct (C) may also be substituted the fluorine-containing cyclic monocarboxylic acids having a melting point above 40 ° C in subordinate Quantities, based on the equivalent weight the component (B), perfluorooctanoic acid (melting point 45-50 ° C) or technical Products with lower melting point, to be used, especially in Use of a component (B2) and / or (B3), if for the production said half ester phthalic anhydride. or mixtures of dicarboxylic acid anhydrides containing phthalic anhydride be used.

The Epoxide adducts (C) can be adjusted depending on their melting point analogously known methods / methods of the known prior art for the production of powder coatings based on carboxyl groups Polyesters, for example, the above-mentioned publications use.

Of course, epoxide adducts (C) may also be used in admixture with other crosslinking agents, for example, commercial crosslinking agents such as "Araldite PT 910" (registered trade name of Ciba Specialty Chemicals, Polymers Division), or epoxidized soybean oil and / or epoxidized linseed oil according to U.S. Pat WO 95/21208 and / or the WO 95/20017 or solid modified cycloaliphatic epoxy resins according to mine DE 199 01 118 C2 , in particular with fluorine content, are used.

In this connection, it is noted that the use of epoxide adducts (C) because of aromatic structural units in their structure for the preparation of transparent powder coatings, in particular powder clearcoat, for example based on cycloaliphatic carboxyl-containing polyesters, in view of high weather resistance can not be recommended, and this will be on the DE 199 01 118 C2 , Column 15, and ff. Column 16, lines 1-62.

In this context, further to the above remarks to mine DE 196 34 721 C2 and DE 199 01 118 C2 with respect to the production of powder coatings based on carboxyl-containing polyesters and solid epoxy resins having a fluorine content higher than 2 wt .-% and / or a silicon content.

to Production of powder coatings based on carboxyl groups Polyesters are many suitable polyesters available commercially and mentioned in the literature, and / or described in detail in technical data sheets of the manufacturer.

To The epoxide adducts according to claims 3-8 are the following versions made.

The after the DE 196 34 721 C2 prepared fluorine-containing reaction products contain at least one free epoxy group (claim 1 and description) are practically preferably modified epoxy resins having more than one epoxide group per average molecular weight (examples for the preparation of the reaction products R, R 3 and R 4).

Moreover These reaction products are not as such, but for the production one defined by a "product-by-process" claim Polyester, the 0.01 to 10 wt .-% of fluorine, especially 0.2 to 10 Wt .-% of fluorine, and carboxyl and / or hydroxyl groups and its Fluorine content is based on groups located at the end of the chain, and the in coating compositions in x-arbitrary amount is used.

In contrast, epoxy adducts (D) according to the claims contain less than one epoxide group pe, but at least 0.3, preferably 0.5 to 0.8 epoxy groups per average molecular weight and are used as such as additives for coating agents.

Moreover is used in terms of composition and manufacture Epoxide adducts (D) a selection has been made.

Of the The term additive in the sense of the invention also encompasses the terms "additives" and "modifiers" for binders. The additives are virtually non-volatile and can also be present in the coating in the form of inclusion compounds with the binder be.

The Modification of Binders Reactive to Epoxide Groups, for example Carbamate groups, hydroxyl groups, in particular carboxyl groups, may already be made in the preparation of these binders be used, for example in the extruder in powder coating, however, preferably takes place by reaction in the coating, for example, by the effect of temperature at higher temperatures, for example 60 to 200 ° C.

The preparation and use of epoxide compounds having at least two epoxide groups are extensively described in the literature, including publications, for example in US Pat DE 196 34 721 C2 and DE 199 01 118 C2 and the references cited therein and the literature and patent publications referred to above.

Examples for aliphatic Epoxy compounds are aliphatic diglycidyl ethers, for example butanediol diglycidyl ethers, or diglycidyl esters of aliphatic dicarboxylic acids, for example, adipic acid diglycidyl ester, or epoxidized fatty oils, for example, epoxidized soybean or linseed oil.

Examples for aromatic Epoxy compounds are liquid Epoxy resins based on bisphenol A and / or bisphenol F or liquid Polyglycidyl esters, for example trimellitic triglycidyl esters.

Preferably, diglycidyl esters of aromatic and / or cycloaliphatic dicarboxylic acids or their anhydrides, for example of phthalic anhydride and / or isophthalic acid and / or hexahydrophthalic anhydride and / or tetrahydrophthalic anhydride and / or 5-norbornene-2,3-dicarboxylic anhydride and / or diglycidyl ester according to mine DE 100 54 504 A1 and or DE 102 18 038 A1 and or DE 102 03 685 A1 and / or cycloaliphatic Diepoxidverbindungen based on cycloolefins or cycloalkenes used. Particular preference is given to epoxide compounds according to claim 4 and / or digylcidyl esters DE 100 54 504 A1 . DE 102 18 038 A1 and DE 102 03 685 A1 used.

Of the Term includes epoxy compounds having at least two epoxide groups in the context of the invention also epoxy compounds, which are technically conditioned only approximate contain two epoxy groups and / or production-related in mixture are present with other epoxy compounds or are commercially available, for example liquid Epoxy resins based on bisphenol A and / or bisphenol F.

The Choice of epoxy compounds depends on whether solid, semi-solid or liquid Epoxy adducts (D) are produced, and also by type and Amount of for reaction with the epoxy compounds for the preparation of the epoxide adduct (D) used fluorine- and / or silicon-containing carboxyl group-containing Compounds such as fluorine-containing monocarboxylic acids or their anhydrides and / or perfluorocarboxylic the given general formula, preferably perfluorooctanoic acid, and / or the said half esters as described and claims.

A appropriate selection of epoxy compounds and the above Carboxylic compounds prepares the expert in consideration the above statements no significant difficulties.

Preferably are used to make solid or semi-solid epoxide adducts (D) Epoxy compounds according to claim 4 used.

When aromatic dicarboxylic acid diglycidyl esters are preferably solid dicarboxylic acid glycidyl esters, in particular Phthalic acid diglycidyl ester, and / or isophthalate and / or terephthalic acid diglycidyl ester, used.

For the preparation of liquid epoxide adducts (D) are preferably cycloaliphatic epoxy compounds, most preferably cycloaliphatic Dicarbonsäurediglycidylester, in particular Hexahydrophthalsäurediglycidylester and / or Tetrahydrophthalsäurediglycidylester and / or Norbonendicarbonsäuredigylcidylester and / or Diglycidylester after DE 102 03 685 A1 , Claim 22, wherein optionally in minor amounts, preferably less than 50%, in particular 2-20%, based on the equivalent weight of all epoxide compounds used (= 100%), aliphatic diglycidyl ethers, for example Butandioldiglycidylether, can be used.

Examples of fluorine-containing carboxylic acids or their anhydrides are Trifluoressigsäureany hdrid, which is converted to trifluoroacetic acid "in situ" by addition of the calculated amount of water in the preparation of the epoxide adduct (D), and / or 2,2,3,3,3-pentafluoropropionic acid and / or 3-fluorobenzoic acid and / or 3 - (Trifluoromethyl) benzoic acid and / or 4- (trifluoromethyl) benzoic acid and / or 2,3,4,5,6-pentafluorobenzoic acid. For the preparation of solid or semisolid Epoxidaddukten (D) preferably fluorine-containing cyclic monocarboxylic acids are used, preferably those which are mentioned in the description as component (B1) to claim 1.

As perfluorocarboxylic acid of the general formula F- (CF ₂ ) n -COOH, where n is an integer from 5 to 21, perfluorooctanoic acid is preferably used.

The preparation of half esters by reaction (addition reaction) of dicarboxylic anhydride and monohydric or polyhydric alcohols has long been known in the art and, for example, in US Pat EP 0 316 873 B1 described. To accelerate the addition reaction and known esterification catalysts, for example toluene-4-sulfonic acid monohydrate, conveniently as a solution in butyl glycol, wherein the additional amount, calculated as toluene-4-sulfonic acid monohydrate and on the reactants, for example 0.1 to 0.2 Wt .-% is used.

to Preparation of in the claims 1-3 as well as 6 and 6 defined half esters become saturated and / or unsaturated Dicarboxylic acid anhydrides or Mixtures of dicarboxylic anhydrides, preferably dicarboxylic which are used or suitable for the production of polyesters especially succinic anhydride, dodecenyl succinic anhydride, glutaric, citraconic, Itaconic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride or 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (nadic anhydride), or mixtures of these dicarboxylic anhydrides used. acid anhydrides used.

Especially preferred are succinic anhydride and / or maleic anhydride and / or phthalic anhydride and / or tetrahydrophthalic anhydride and / or hexahydrophthalic anhydride and / or Nadic anhydride, in particular eutectic mixtures of these dicarboxylic acid anhydrides, preferably containing phthalic anhydride and / or hexahydrophthalic anhydride, with a mixed melting point below 100 ° C.

The production of eutectic mixtures can be determined by relatively simple experiments. For example, it will open AM Paquin, epoxy compounds and epoxy resins, Springer-Verlag Berlin / Göttingen / Heidelberg 1958 , Page 484, last paragraph and the attached FP 1114888, and page 485 with table.

Suitable fluorine-containing monohydric alcohols for the preparation of the half-esters are the literature, for example the one in my DE 199 01 118 C2 , Column 13, lines 38-41, and subsequent enumeration in column 13, lines 41-50.

Preferably are 2,2,2-trifluoroethanol and / or heptafluoro-1-butanol and / or 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and / or 1H, 1H-perfluoro-1-octanol and / or 2,3,4,5,6-pentafluorobenzyl alcohol used.

The preparation of half esters, hereinafter referred to as "silicone half-ester", by reacting dicarboxylic acids or their anhydrides, especially the latter (addition reaction), and organosilanols having one to three hydroxyl groups, in particular one or two hydroxyl groups, and / or mono- or dihydric alcohols , especially monohydric alcohols containing at least one silyl group, has been my since publication DE 100 00 190 A1 (08.02.2001) Prior art, and it is pointed to column 7, line 26-60, and column 8, lines 8-37, and claims 2 and 11 to 13, and examples 1,2 and 8.

To suitable for preparing the "silicone half-ester" and preferably used dicarboxylic anhydrides or mixtures thereof is based on the above directed.

Examples for the preparation of the "silicone half-ester" suitable organosilanols, which correspond to the general formula according to claim 1, are trimethylsilanol and / or triphenylsilanol and / or dimethylheenylsilanol and / or Diphenylmethylsilanol and / or dimethylsilanediol and / or diphenylsilanediol and / or methylphenylsilanediol.

Examples for monovalent Alcohols containing at least one trimethylsilyl group or another silyl group, for example, a tertiary Butyldimethylgruppe contain, are 2- (trimethylsilyl) ethanol and Trimethylsilylbenzylalkohol.

Preferably, in the preparation of the "silicone half-esters", organosilanols having one or two hydroxyl groups known as silicone resin precursors and having the general formula of claim 1, wherein R is preferably an alkyl, aryl, aralkyl and / or a Alkylaryl radical, and / or organosilanols which are useful or known as chain scavengers For example, trimethylsilanol used.

The term silicon-organic compounds, which include organosilanols, is for example on Römpps Chemie-Lexikon Bd. 5, PI-SB revised and expanded edition, Franckh'sche Verlagshandlung, W. Keller & Co., Stuttgart 1987, page 3853-3854 with further references.

The there versions explain also the term organosilanols and page 3857 contains a production scheme the Wacker Silicone (especially the methyl silicones), where trimethylsilanol called chain stopper or to adjust the chain length is.

Of course you can too Half esters used on the reaction of dicarboxylic anhydride (s) and sharing the described and claimed Fluorine-containing monohydric alcohols and / or described and claimed organosilanols and / or the described and claimed Alcohols containing at least one silyl group, based.

The term half ester in the context of the invention also includes half esters in their preparation - for whatever reason - fluorine- and / or silicon-free compounds, in particular with hydroxyl group (s), for example mono- or polyhydric alcohols, polyglycol ethers, glycol monoalkyl ethers, for example butyl glycol , be used, and this is on the DE 100 00 190 A1 , Column 8, lines 22-37, and column 11, example 8.

The preparation of the epoxide adducts (C) or (D) used according to claims 1 or 3 is carried out according to prior art preparation processes known per se. For example, it will open Volume II, Waterborne & Solvent Based Epoxies and their End User Applications, edited by dr. P Oldring PhD BA, published 1996 by SITA Technology Limited, London, especially pages 55-67 , the DE 196 34 721 C2 , Column 4, lines 59-68, and ff. Column 5, lines 1-11, and the DE 199 01 118 C2 , Column 12, line 38-60, and the DE 102 03 685 A1 , Column 12, lines 14-30.

It is also known prior art that for the preparation of epoxy adducts the optimal equivalent ratios the reactants in the epoxy / carboxy addition reaction can not be calculated exactly in advance, but due to unavoidable Side reactions, especially etherification reactions, by empirical Attempts in dependence from the process conditions, in particular the temperature profile and the type and amount of catalysts must be determined.

procedural Features for the preparation of the epoxide adducts (C) or (D) are already in the claims 1 or 3 included.

The Therefore, the invention can also be understood to refer to a method for producing the in claims 1 or 3 by their properties and their preparation characterized epoxy adducts (C) or (D) with claimed use, and the method of their preparation characterized in that according to the manufacturing characteristics the claims 1 or 3 is moved.

Preferably is used in the preparation of the epoxide adducts (C) for use according to claim 1 or the epoxide adducts (D) for use according to claim 3, that submitted to claim 1 or 3 claimed epoxy compounds be and at elevated Temperature, for example 60-90 ° C, with solid epoxide compounds well above their melting point, in substance or in the presence of organic inert solvents, for example, xylene, and / or catalysts for the epoxy / carboxy addition reaction, for example, lithium hydroxide monohydrate, lithium stearate, zirconium compounds, for example, zirconium octoate, zirconium acetylacetonate, tetraethylammonium bromide, Benzyltriethylammonium chloride, and / or polymerization inhibitors, For example, hydroquinone monomethyl ether, by gradually taking place discontinuous or continuous addition of those in claims 1 or 3 defined fluorine and / or organosilicon compounds under consideration the exothermic reaction and increase in the Temperature, for example 95-130 ° C, be reacted until the acid number under 40, in particular under 20, has fallen or even further Temperature increase. for example 140-160 ° C, optionally after adding relatively small amounts of the epoxy compounds, further reacted becomes until the acid number to the desired Value, for example, below 20, has fallen or the reaction by a thermal aftertreatment should be completed, the proportions the epoxy compounds and the fluorochemicals defined in claims 1 or 3 and / or silicon-organic Connections chosen be that they claim for the preparation of the epoxide adducts (C) 1 given epoxy / carboxy equivalent ratios and for the preparation of the epoxide adducts (D) specified in claim 3 Epoxy / carboxy equivalent ratios correspond.

As already stated above, the preparation of the epoxide adducts (C) or (D) can also be completed so that the production process comprises a final stage, in which the addition reaction by a temperature treatment at a higher temperature, preferably 130-200 °, outside the batch separately, for example, in a small layer thickness, for example 3-5mm, or is completed in special heatable mixers or in extruders, preferably in the production of solid epoxy adducts (C) or (D). For this purpose, for example, on the DE 199 01 118 C2 , Column 18, Examples 5 and 6, and the DE 100 00 190 A1 , Examples 2-10.

to ring opening the epoxide group can also small amounts of phosphoric acid, for example, an 85% or 89% aqueous ortho-phosphoric acid solution used become.

To Claim 7 are compounds selected for improved ring opening of the epoxide group used. As the fluorine-containing cyclic amino compound is preferably 2-aminobenzotrifluoride, and as a fluorine-free aliphatic aminoalcohol with secondary Amino group preferably used diethanolamine.

The fatty alcohol polyglycol ethers recited in claim 8 are commercially available as nonionic surfactants and are described in the literature, for example Tensid-Taschenbuch, ed. by Helmut Stache and Kurt Kosswig, 3rd Edition, Carl Hanser Verlag Munich Vienna, 1990. The perfluoroalcohol polyglycol ethers used are preferably those which correspond to the general formula given in claim 8 for fatty alcohol polyglycol ethers, but where R is a perfluoroalcohol radical R _f and which are also commercially available as solvent-free fluorosurfactants.

Preferably contain the epoxide adducts (D) according to claim 3 per average molecular weight 0.5 to 0.8 epoxide groups. Of course, the epoxide adducts contain (D) also secondary Hydroxyl groups from the epoxy / carboxy addition reaction, optionally can be further implemented, for example, with polyisocyanates or dicarboxylic anhydrides, and preferably have an acid number under 20.

The Average molecular weight of epoxide adducts (D) is generally in the range of 500 to 1500; among others, depending on whether liquid, semi-solid or solid epoxide adducts (D). The fluorine and / or Silicon content can vary within wide limits and is preferably more than 5 wt .-% fluorine and / or silicon. Very particularly preferred For example, the epoxide adducts (D) contain both fluorine and silicon.

To the term used in claim 3 additive in the sense of The invention, which also includes the terms "additives" and "binder modifiers", has already been developed outlined above.

From my DE 196 34 721 C2 , Column 6, lines 61-66, it is known that coating agents said modified polyester (Note: fluorine content 0.01 to 10 wt.%) Even in minor amounts, eg. B. less than 10 wt .-%, based on binder, may contain, in order to effect especially a trouble-free Ausbidlung of coating compositions per se known composition after the order.

In Column 5, lines 54-64, is executed, inter alia, at line 59-62 Coating agent in addition to said modified polyesters among others also as other resins acrylic copolymers, preferably with hydroxyl and / or epoxy groups, optionally also in the form of its solution, emulsion or dispersion in water, e.g. B. aqueous Polyurethane dispersions, may contain.

For a content of fluorine-containing solid modified cycloaliphatic epoxy resins and for modifying Bindernelnn is already discussed above to my remarks DE 199 01 118 C2 and my article in color & lacquer 9/1999, page 106-109 referenced.

The Use of "additives" for coating agents is familiar to the expert. The necessary paint technical compatibility tests with Coating agents and the binders contained therein as well The selection and the amount of additives in relation to their intended effectiveness depending on type and purpose the coating agents are daily Routine tasks of the expert. It is also known, if appropriate solubilizers or "cosolvent", preferably butylglycol, use. Of course can the coating agents also other auxiliaries and additives, for example volatile Fluorine and / or Silicone additives, rheology aids included.

Liquid epoxide adducts (D) are preferably used in substance as additive / additive for solvent-free Coating agents, for example 2-component systems based on liquid Epoxy resins based on bisphenol A and / or bisphenol F and polyamines and / or polyaminoamides as curing agents. Liquid or Semi-solid epoxy adducts (D) are preferably used in bulk or in solution as an additive for solvent-based coating compositions, in particular based on polyesters, including alkyd resins and / or polyester urethane resins and / or polyurethane resins and / or Acrylic (co) polymers, in particular with carboxyl groups used.

Epoxy adducts (D), the hydrophilic polyoxyethylene units according to claim 7 in their structure are preferably used as additive / additive for water-dilutable or in the form of aqueous dispersions present coating compositions, in particular based on polyesters including air-odr oven-drying alkyd resins and / or acrylic copolymers and / or polyurethane resins, for example acrylate and / or polyurethane dispersions , used.

firm Epoxy adducts (D) are preferably used as additives for powder coatings, for example on the basis of carboxyl-containing polyesters and crosslinking agents.

in the In general, the coating compositions, based on binder, 1 to 10 wt .-% additive added.

The Coating may also heated be, for example, at 40 to 80 ° C, a Prereaktion with the To cause binders. For powder coatings, the pre-reaction as an epoxy / carboxy addition reaction also before or during the Production in the extruder at higher Temperatures, for example 120 ° C or higher, for example 150 ° C, dependent on of the composition and the residence time in the extruder.

The Epoxide adducts (C) used according to the invention do not count to the state of the art and allow simultaneous crosslinking and introduction of fluorine-containing and / or Silicon-organic groups in the curing of powder coatings on the Base of carboxyl-containing polyesters in the coating by the effect of temperature, for example 150-200 ° C, after the Application to a substrate (substrate), such as zinc phosphated or galvanized and / or primed steel sheet, or aluminum.

The as an additive for Coating agent or as a modifier for binders used epoxide adducts (D) count also not state of the art and distinguish themselves among others a relatively high fluorine and / or silicon content, preferably because of synergistic effect by fluorine and silicon content.

Claims (8)

Use of a solid at room temperature Epoxidaddukt having more than two, but less than three epoxy groups per average molecular weight and pendant fluorine-containing and / or silicon-organic groups (C), prepared by addition reaction of a component (A) consisting of (A1) triglycidyl isocyanurate and or (A2) trimellitic triglycidyl ester, having a component (B) consisting of (B1) cyclic fluorine-containing monocarboxylic acids having a melting point above 40 ° C., in particular above 100 ° C., and / or (B2) semiesters from the reaction of dicarboxylic anhydride or a mixture of dicarboxylic acid anhydrides and monovalent fluorine-containing alcohols and / or hydroxybenzotrifluoride, and / or (B3) half-esters from the reaction of dicarboxylic anhydride or a mixture of dicarboxylic acid anhydrides and organosilanols having one or two hydroxyl groups corresponding to the general formula R _{n n} SiX _4-n , wherein R aliphatic, aromatic, cycloaliphatic e or heterocyclic radicals and X is OH, and / or monohydric alcohols containing at least one silyl group, at elevated temperature in the absence or in the presence of organic solvents and / or catalysts for the epoxy / carboxy addition reaction and / or polymerization inhibitors and or in an inert atmosphere, wherein only one epoxide group (1 epoxy equivalent) of component (A) is reacted with less than one, in particular less than 0.8, carboxy equivalent of component (B) in such a way that the resulting epoxide adduct ( C) has more than two, in particular more than 2.2, epoxide groups per average molecular weight, as a crosslinking agent or hardener for carboxyl-containing polyesters suitable for the preparation of powder coatings. Use of an epoxide adduct (C) according to claim 1 that both fluorine-containing and silicon-organic groups prepared by addition reaction component (A) both with component (B1) and / or (B2) and the component (B3). Use of a liquid at room temperature, semisolid or solid epoxy adduct with less than one, but at least 0.3 epoxide groups per average molecular weight and pendant fluorine-containing and / or silicon-organic groups (D), prepared by addition reaction of epoxide compounds having at least two epoxide groups, and Fluorine-containing carboxylic acids or their anhydrides and / or half-esters from the reaction of fluorine-containing monohydric alcohols and / or hydroxybenzotrifluoride, and dicarboxylic acids or their anhydrides, especially the latter (addition reaction), and / or perfluorocarboxylic acids of the general formula F- (CF ₂ ) n- COOH, where n is an integer from 5 to 21, and / or half esters from the reaction of dicarboxylic anhydride or a mixture of dicarboxylic anhydrides and organosilanols having one or two hydroxyl groups corresponding to the general formula R _n SiX _4-n , where R is aliphatic, aromatic , cycloaliphatic or heterocyclic radicals and X is OH, and / or monohydric alcohols which contain at least one silyl group, at elevated temperature, in substance or in the presence of organic solvents and / or catalysts for the epoxy / carboxy addition reaction and / or polymerization inhibitors and / or in an inert atmosphere, wherein the proportions of the epoxy compounds and the above carboxy, based to the epoxy / carboxy equivalent ratio, such that the resulting epoxide adduct (D) has less than one but at least 0.3 epoxide groups per average molecular weight as additives to solventless, solventborne, waterborne or aqueous dispersant coating compositions or for powdered coating compositions or powder coatings; in particular for coating compositions which contain binders or binder components with groups which are reactive toward epoxide groups, in particular carboxyl groups, or for the modification of these binders or binder components. Use of an epoxide adduct (D) according to claim 3, characterized in that for its preparation aromatic and / or cycloaliphatic Dicarbonsäuredigylcidylester and / or 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate (ECC) and / or bis (3,4-epoxycyclohexylmethyl adipate used become. Use of an epoxide adduct (C) according to claims 1 and 2 or an epoxide adduct (D) according to claims 3 and 4, characterized that for their preparation half ester from the reaction of a mixture of dicarboxylic acid anhydrides and a mixture of fluorine-containing monohydric alcohols and organosilanols having one or two hydroxyl groups and / or monohydric alcohols containing at least one silyl group, be used. Use according to claim 5, characterized that for the preparation of the half-ester a eutectic mixture of dicarboxylic containing phthalic anhydride and / or hexahydrophthalic is used. Use of an epoxide adduct (C) according to claims 1 and 2 and 5 and 6, or an epoxide adduct (D) according to claims 3 to 6, characterized in that for their preparation for improved ring opening the epoxy groups and based on one epoxide group (1 epoxy equivalent), 0.01 to 0.2 equivalents Perfluoroctansäureamid or polyglycol ether-modified aminosilane, or 0.01 to 0.03 equivalents 4-hydroxybenzoic acid or 4-aminobenzoic acid or a fluorine-containing cyclic amino compound or fluorine-free aliphatic amino alcohols used with secondary amino group become. Use of an epoxide adduct (D) according to claims 3 to 7 and with polyoxyethylene units in its structure, characterized in that for its preparation in a minor amount, based on the total carboxy equivalent weight of all carboxy compounds used, half esters from the reaction of dicarboxylic anhydride or a mixture of dicarboxylic anhydrides and fatty alcohol polyglycol ethers of the general formula RO- (CH ₂ -CH ₂ O) _n H, where n is an integer from 4 to 12 and R is a saturated and unbranched fatty alcohol radical, in particular having 12 to 18 C atoms , and / or polyethylene glycol monoalkyl ethers having a hydroxyl number of at least 100, and / or Perfluoralkoholpolyglycolethern having a hydroxyl value of at least 50, and / or triethylene glycol and / or tetraethylene glycol and / or polyethylene glycols having a hydroxyl value of at least 100, are used.