JPH0442427B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermosetting binder mixtures based on organic resins containing hydroxyl groups. Many chemical reactions have been proposed and used for crosslinking curing of binders in coatings. The chemical bonds formed during the crosslinking reaction are often not sufficient for all the demands made on the coating. In two-component systems, one of the reactive groups often has to be shielded to suppress rapid reactions. Furthermore, the compounds liberated during baking, especially in the case of amines or phenols, pollute the environment. In recent years, electrodeposition coating has been widely used for undercoating conductive substrates. Conventionally, anodic electrodeposition undercoating was the main method. The resin binders used for this purpose are resins containing carboxyl groups, such as maleated oils, maleated epoxy resins, alkyd resins,
It belongs to acrylic resins and especially maleated polybutadiene. This resin is rendered water-soluble, preferably by salt formation with an amine, and deposited by means of an electric current on the anode in an electrodeposition bath. However, anodic electrodeposition priming has significant drawbacks. During electrical deposition, oxygen is evolved at the anode, which oxygen can significantly adversely change the resin deposited on the anode.
Furthermore, metal ions are dissolved in solution at the anode, and these ions are included as interfering points in the baked film.
Metal ions can lead to discoloration and stain formation. Metal ions cause quality defects, especially due to salt formation and a consequent reduction in waterproofing and corrosion protection. Since the above-mentioned drawbacks are largely avoided, anodic processes are increasingly being replaced by cathodic electrodeposition priming processes, which have been commercially developed in recent years. In this way, at the cathode, where the coating is deposited, hydrogen is separated which does not affect the resin binder during the deposition process. Since the cathode is deposited in a relatively neutral pH range, metal ions are hardly soluble. Binders suitable for cathodic deposition have primarily amino groups, which are neutralized with acids to make them soluble in water. European Patent No. 12463 discloses a binder which crosslinks by transesterifying a crosslinking agent containing a β-hydroxyalkyl ester group with a resin-like compound containing a hydroxyl group. However, this transesterification requires large amounts of heavy metal salts as curing catalysts. The object of the present invention is to avoid the disadvantages of the known technology and to create a binder mixture for producing coating materials whose components exhibit an increased reactivity. The binder mixtures according to the invention should reduce environmental pollution when applying the corresponding paints. Furthermore, coatings based on the binder mixture according to the invention must be suitable for all application methods, i.e. they can be used both for conventionally applied baking coatings and for powder coatings and aqueous powder slurries. It's good to be able to do that. By incorporating solubilizing groups, this binder mixture should be suitable for electrocoating processes. The task is to provide binder mixtures of the type mentioned at the outset, which binder mixtures contain: A) at least 0.2 equivalents of hydroxyl groups in 100 g resin and have a molecular weight of at least 850;
B) a crosslinking agent based on an organic compound having at least two carbalkoxymethyl ester groups per molecule. In addition to components A and B, this binder mixture advantageously also contains as component C pigments, fillers, crosslinking catalysts, corrosion inhibitors and other coating aids. The amount of component A is 50-95% by weight and the amount of component B is 5% by weight.
~50% by weight, with component A
The sum of and B is 100%. During the baking step, the carbalkoxymethyl ester groups of component B react with the hydroxyl groups of component A with the formation of an ester. The crosslinking mechanism is basically illustrated by the following reaction steps: The eliminated hydroxyacetate preferably exhibits a boiling point such that it acts as a leveling aid during the baking process. The ester bonds that occur during baking have a very advantageous effect on the adhesion of the coating, especially on metal substrates. This likewise increases the elasticity of the coating. This crosslinking mechanism results in a high stability of the coating against solvents, alkaline substances and salt spray. On steel plates without pretreatment, this film forms a very resistant coating even without corrosion inhibitors. Component A of the binder mixture preferably has a number average molecular weight
Showing 850-20000, advantageously 1000-10000. Especially when using binder mixtures for electrocoating methods,
In addition to hydroxyl groups, component A additionally contains primary and/or secondary amino groups. Optionally, both tertiary amino groups and quaternary ammonium groups may additionally be present. The presence of primary or secondary amino groups in addition to hydroxyl groups in component A has important implications in addition to the solubility of the resin in the aqueous electrodeposition bath. The primary and secondary amino groups also contribute to crosslinking, ie, during baking, these amines react with the carbalkoxymethyl ester groups of component B to form amide compounds. A highly effective crosslinking is thereby achieved and the resulting coating provides excellent corrosion protection.
The storage stability and the stability of electrodeposition baths made with this binder are improved. Binder mixtures in which component A contains, in addition to hydroxy groups, at the same time primary and/or secondary amino groups are particularly preferred embodiments of the invention. The introduction of primary and/or secondary amino groups into organic resins for the production of component A involves the use of resins having at least one, preferably two, epoxide or isocyanate groups per molecule and polyamines and/or
Alternatively, it is carried out by reaction with ketimine containing an amino group and/or a hydroxyl group. Component A can also be added by other addition reactions, e.g.
They can also be obtained by esterification or amidation with compounds having primary and/or secondary amino groups with resins having groups suitable for this purpose. Epoxide group-containing resins selected from the group of polyglycidyl ethers, polyglycidyl esters and polyglycidyl amines, preferably with terminal epoxide groups, have proven particularly suitable for the preparation of component A. Other suitable epoxide group-containing resins are acrylic acid and/or methacrylic acid glycidyl ether or other olefinically unsaturated polymerizable compounds having glycidyl groups and alkyl and/or hydroxyalkyl esters of acrylic and/or methacrylic acid. , and/or copolymers with vinyl compounds such as styrene, vinyltoluol, or vinylcarbazole. Other advantageously suitable resins are partially epoxidized polybutadiene oils. Within the scope of the present invention, polyglycidyl ether is defined by the general formula is a polyglycidyl ether, where R ₁ =H or C _o H _2o+1 R ² =(CR ¹ ₂ ) _o R ³ =R ¹ , halogen and preferably H n =0-5. The polyglycidyl ethers of the general formula described have number average molecular weights of about 340-5000 and therefore epoxide equivalent weights of 170-2500. The epoxide resin can be used even if it is hydrogenated or partially hydrogenated. Some of the reactive groups of the epoxide resin can be reacted with other compounds to adjust the membrane properties. For this purpose, the following are used: a) Compounds containing carboxyl groups, such as saturated or unsaturated monocarboxylic acids (e.g. benzoic acid, linseed oil fatty acids, 2-ethylhexanoic acid, Versatica), various aliphatic, cyclic and/or aromatic dicarboxylic acids (e.g. adipic acid, sebacic acid, isophthalic acid or dimeric fatty acids), hydroxyalkyl carboxylic acids (e.g. lactic acid, dimethylolpropionic acid) and carboxyl group-containing polyesters or b) Compounds containing amino groups, such as diethylamine or ethylhexylamine or diamines with secondary amino groups, such as N,N'-dialkylalkylene diamines such as dimethylethylenediamine, N,N'-dimethyl-polyoxypropylene diamines, etc. N,N-dialkyl-polyoxyalkylene amines, polyaminoamides, e.g. fersamides or monoglycidyl esters with 2 mol of monoglycidyl ether, in particular glycidyl esters of branched chain fatty acids such as ferzatectic acid, or c) compounds containing hydroxyl groups , such as neopentyl glycol, bisethoxylated neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, hexanediol-1,6, hexanediol-2,5,1,4
-bis-(hydroxymethyl)-cyclohexane, 1,1-isopropylidene-bis-(p-
phenoxy)-2-propanol, trimethylolpropane, pentaerythritol or amino alcohols such as triethanolamine, methyldiethanolamine or hydroxyl-containing alkylketimines such as aminomethylpropanediol-1,3-methyl-isobutylketimine and various functionalities and Molecular weight polyglycol ether, polyester polyol, polyether polyol, polycaprolactone polyol. Instead of polyglycidyl ethers based on bisphenol A, it is also possible to use polyglycidyl ethers based on other base components, such as triglycidyl isocyanurates, heterocyclic diclycidyl compounds or diglycidyl hydantoins. Suitable polyglycidyl esters are, for example, reaction products of bisglycidyl terephthalate or bisglycidyl isophthalate with, for example, bisphenol A. The epoxide equivalent weight of this product is between 200 and 2500. In order to adjust the membrane properties, a portion of the remaining reactive glycidyl groups can also be reacted with other compounds. For this purpose, the compounds listed above under a, b and c are used. Polyglycidylamine is a glycidyl group-containing resin obtained by introducing glycidyl groups into an NH ₂ functional resin, for example via epichlorohydrin. A copolymer of acrylic and/or methacrylic acid glycidyl ester or other olefinic unsaturated polymerizable compound having a glycidyl group with an acrylic and/or methacrylic acid ester and a polymerizable vinyl compound, with a number average molecular weight of 700 or more. 10,000 and epoxide equivalent weights of 600 to 3,000 are also suitable. Preference is given to acrylic esters with C ₂ -C ₈ -alcohols and methacrylic esters with C ₁ -C ₄ -alcohols. This copolymer may contain other monomers such as hydroxyalkyl (meth)acrylates or (meth)acrylamides. The copolymerization is carried out in known manner by solution, suspension or emulsion polymerization, with the addition of radical initiators, such as peroxides, hydrogen peroxide, peresters or thermally decomposable azo compounds, and optionally molecular weight regulators. Partially epoxidized polybutadiene oil refers to the reaction product obtained by reacting commercially available polybutadiene oil with a peracid or an organic acid/H ₂ O ₂ mixture. The manufacturing method is described, for example, in Chemiker-Zeitung, Vol. 95, p. 857 (1971). For the production of a water-dispersible binder, an epoxide group-containing resin and a polyamine and/or an amino group and/or
Alternatively, it is reacted with ketimine containing a hydroxyl group. If the addition of compounds having primary and secondary amino groups is carried out in the form of their ketimines, the reaction conditions must be such that no substances that decompose the ketimines remain in the reaction product. Preferred ketimines are reaction products of ketones with alkylamines or alkyldiamines having hydroxy groups or secondary amino groups having the general formula R-NH-R-NH ₂ or HO-R-NH ₂ . Ketimine, for example, has the following structure: [In the formula: X=-( _CR2 ) _{o -} R=-H _{, -R '}

[Formula] -X-OH, -R' or Z==CO, -X n=1-6 m=1-12] The ketone used for the reaction with the primary amino group is generally an aliphatic ketone, such as methyl ethyl ketone,
Diethyl ketone, methyl isobutyl ketone, ethyl-n-propyl ketone and cycloaliphatic ketones such as cyclopentanone and cyclohexanone. Preferred aminoalkylamines and alkanolamines are mainly diethylenetriamine, N-methyl-ethylenediamine, N-methyl-propylenediamine, N-aminoethyl-piperazine, 2
-Aminoethanol, 1-aminopropanol-
2,1-aminopropanol-3,2-amino-
2-methyl-propanol-1,3-amino-
2,2-dimethyl-propanol-1,1,5-
Diamino-pentanol-3 or N-(2-aminoethyl)-N-(2-hydroxyethyl)-ethylenediamine. The exothermic addition of the aminoketimine to the epoxide groups of the base resin of binder component A is generally carried out at room temperature. For complete conversion, the reaction is often terminated at a temperature of 50-125°C. The addition of hydroxyketimine to the epoxide groups of the base resin of binder component A is generally carried out in the same temperature range, but with a basic catalyst such as N,N-dimethylbenzylamine or a Friedel catalyst such as tin chloride (). It is also advisable to use a Krafts catalyst. Introduction of reactive hydroxyl groups is greatly facilitated by the use of secondary alkanolamines such as methylethanolamine, diethanolamine, diisopropanolamine, butylethanolamine, cyclohexylethanolamine, and the like. As the base resin for the binder component A, a base resin having at least two isocyanate groups can be used. Preferred resins containing isocyanate groups are highly functional polyisocyanates prepared by trimerization or oligomerization from diisocyanates or polyisocyanates and polyfunctional compounds containing OH- or NH groups. Typical isocyanates are toluylene diisocyanate, hexamethylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6
-diisocyanate-2,2,4-trimethylhexane and 1-isocyanate-methyl-3-isocyanate-1,5,5-trimethylcyclohexane. Furthermore, polyglycol ether,
Isocyanate-containing prepolymers based on polyester polyols, polyether polyols, polycaprolactone polyols, polycaprolactam polyols or polyaminoamides can advantageously be used. Binder component B, which is a crosslinking agent, is a compound having at least two carbalkoxymethyl ester groups. Crosslinking agents are low-molecular compounds or correspondingly substituted resins. For the esterification, monoalcohols such as methyl alcohol, for example methyl alcohol,
When using ethyl alcohol or butyl alcohol, the transesterification reaction proceeds very slowly. In this case the crosslinking rate is too low and the baked film is not sufficiently stable to solvents. This disadvantage is avoided according to the invention when carbalkoxymethyl esters are used for the transesterification reaction. The compound forming the crosslinking agent is preferably a polyester resin, but other compounds containing free carboxyl groups and capable of being used for esterification can also be used. Preference is given to using polycarbalkoxymethyl esters of polycarboxylic acids as transesterification components. These include bis-(carbalkoxymethyl)-azelate, bis-(carbalkoxymethyl)-sebacate, bis-(carbalkoxymethyl)-adipate, bis-(carbalkoxymethyl)-succinate, bis-(carbalkoxymethyl)-terephthalate, etc. belong to Polyfunctional crosslinkers can advantageously be prepared as follows. First, dicarboxylic anhydride (phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, succinic anhydride) and polyol (glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol) are mixed in equivalent amounts. The reaction is carried out at a temperature below 145°C. The resulting acidic intermediate product is then reacted into the final product. For this purpose, for example, the acidic intermediate is converted into an ammonium salt, which is then reacted with monochloroacetic acid ester. Component B is preferably a polyacrylate resin consisting of the following monomers: a) alkyl acrylates with 1 to 18 carbon atoms in the alkyl group and/or alkyl methacrylates with 2 to 18 carbon atoms in the alkyl group Ester 10-50% by weight b) Methacrylic acid methyl ester 0-60% by weight c) Styrol, α-methylstyrene, o-
and/or p-chlorstyrol, p-tert-
Butylstyrene, vinyltoluol and/or vinylcarbazole 0 to 35% by weight d) Olefinic unsaturated polymerizable material containing acrylic acid carbalkoxymethyl ester and/or methacrylic acid carbalkoxymethyl ester or other carbalkoxymethyl ester groups Compound 2-65% by weight, where the sum of components a, b, c and d is
It is 100%. The binder mixture according to the invention is present as a solid fine powder or dissolved in an organic solvent. For electrocoating, it is necessary that the binder mixture be protonated with an acid and in the form of an aqueous solution or suspension. Primary, secondary and/or tertiary binder components and/or crosslinker components that have water solubility
It is produced by neutralizing the primary amino group with acid. Suitable acids are in particular organic acids, but it is also possible to use, for example, hydrochloric acid or phosphoric acid. It is advantageous to neutralize the amino groups with formic acid, acetic acid, malonic acid, lactic acid or citric acid. Said acids can also be used when the introduction of solubilizing groups for the binder component and/or crosslinker component is carried out by adding ammonium groups or salts of sulfide/acid or phosphine/acid mixtures to the binder or crosslinker. can be used. The degree of neutralization of the solubilizing group is from 0.2 to 1.0 acid with respect to this group.
equivalents and preferably from 0.25 to 0.6 equivalents. Neutralization can also be carried out as follows. The acid is dissolved in water, optionally together with dispersing aids, and the resin solution is incorporated into the water at room temperature or optionally at elevated temperature. However, it is also possible to add the acid directly to the resin solution. This neutralized resin solution can be mixed into water, and in some cases, water can also be slowly mixed into the resin solution. The dispersion may contain up to 20% organic solvent to adjust its viscosity, electrolytic pressure and malleability. If the formulation contains large amounts of solvent that impair its properties due to the selected manufacturing method, this solvent is distilled off from the resin solution or from the aqueous suspension before dispersion. Taking all properties into account, it is advantageous to use as little organic solvent as possible. The solid content of the precipitation bath containing the dispersion of the present invention is 7 to 35
parts by weight, preferably 12 to 25 parts by weight. PH of the brewing bath
The value is between 4 and 8, preferably between 5 and 7.5. A non-corrosive steel anode or a graphite anode is used as the anode of the precipitation bath. The temperature of the bath formulation should be between 15 and 35°C, preferably between 20 and 30°C. The deposition time and electrolytic pressure are selected in such a way that the desired layer thickness is achieved. After deposition, the coated object is washed and is ready for baking. Regardless of the method of application of the paints produced on the basis of the binder mixture according to the invention, the crosslinking of the paint film is
Baking is carried out at temperatures of 130-200° C. for 10-60 minutes, preferably 15-180° C. for 15-30 minutes. The crosslinking reaction is further promoted by suitable catalysts.
For this, ammonium compounds such as benzyltrimethylammonium hydroxide, benzyltrimethylammonium chloride, trimethylcetylammonium bromide or tetramethylammonium iodide and organotin compounds such as dibutyltin dilaurate and iron acetylacetonate (), zinc acetate are used. ,
Particularly preferred are zinc-2-aminohexoate, cobalt naphthenate, lead acetate, lead octoate or butyl titanate. Due to the high reactivity of the binder component, acceleration of the crosslinking reaction can be achieved even with small amounts of catalyst. Pigment coloring is carried out by known methods. Pigments and other additives, such as fillers, corrosion inhibitors and defoamers (component C), are hereby ground together with one of the two binder components. As the grinding device, for example, a sand mill, a ball mill or a three-roller mill is used.
The completion of the paint is carried out in a generally known manner. It is also possible to mix the individual components A and B and optionally component C in the form of their concentrated solutions and disperse them together. Dispersing components A and B individually,
It is also possible to mix dispersions of the individual components in the required ratio, with the pigment being rubbed into A or B. Furthermore, the present invention relates to a method for producing coatings by depositing on a substrate by baking a paint containing a binder mixture, which binder mixture comprises the following components: A) containing at least 0.2 equivalents of hydroxy groups in 100 g resin; and has a molecular weight of at least 850
B) a crosslinking agent based on an organic compound having at least two carbalkoxymethyl ester groups per molecule. An advantageous embodiment of the process according to the invention is that the paint is a solid fine powder and the loading of the paint is carried out by means of an electrostatic powder spraying device, or the binder mixture is dissolved in an organic solvent and the loading of the paint is carried out by spraying or dipping. , by flow coating, roller, knife application, etc., or by immersing the electrically conductive substrate in a water bath of a paint at least partially neutralized with an acid, optionally additionally containing an organic solvent, and connected as a cathode. The film is then deposited on the substrate with direct current, the substrate is removed from the bath, and the film is cured by baking. Furthermore, the invention relates to the use of a binder mixture for the production of coatings, wherein this mixture comprises the following components: A) containing at least 0.2 equivalents of hydroxyl groups in 100 g resin and having a molecular weight of at least 850
B) a crosslinking agent based on an organic compound having at least two carbalkoxymethyl ester groups per molecule. An advantageous embodiment of the use according to the invention is that the binder mixture is a solid fine powder and the binder is used in powder coatings, or that the binder mixture is dissolved in an organic solvent and is used in baking coatings. or The binder mixture is protonated with acid and used in the form of an aqueous solution or suspension for cathodic electrodeposition coating. Next, the present invention will be described in detail with reference to Examples. Example 1 Production method of tetrafunctional crosslinking agent (crosslinking agent) 109g of pentaerythritol and 474g of phthalic anhydride
are mixed in a 4-necked flask equipped with a reflux condenser, stirrer, internal thermometer and gas line and heated to 140° C. under nitrogen atmosphere. The reaction then proceeds exothermically and is kept at 160° C. by cooling. Acid value 305
Then, cool this mixture to room temperature and add 300 g of acetone.
Add. Thereafter, 81 g of triethylamine was added, and 98 g of chloroacetic acid ethyl ester was added dropwise thereto. Then heat to reflux temperature. This temperature is maintained for 4 hours, after which the formulation is cooled. After 12 hours, the triethylammonium chloride formed is filtered off. Acetone is distilled off from this filtrate using a rotary evaporator. Example 2 Preparation of polyfunctional crosslinking agent (crosslinking agent) 142 g of trimethylolpropane, 23 g of caprolactone and 600 g of methyl isobutyl ketone are placed in a reaction vessel and heated to reflux temperature. After 6 hours, 609 g of trimellitic anhydride are added. Acid value
When the temperature reaches 228, cool to 50°C, add 600g of methyl isobutyl ketone, and slowly add 641g of triethylamine dropwise. Temperature 60 by cooling
Keep at ℃. Then 685 g of chloroacetic acid methyl ester are added. The reaction is carried out at 60°C for 4 hours. Further, it is cooled to room temperature and the formed salts are filtered off. The solids of the crosslinker resin is 70%. Example 3 Preparation of a polyfunctional crosslinker (crosslinker) based on polyacrylate resins 560 g of methyl butyl ketone (MIBK) are charged into the reactor 5 under a nitrogen atmosphere and heated to reflux temperature. Methyl methacrylate over 4.5 hours
1400g, carbethoxy methacrylate 560g,
A monomer mixture consisting of 840 g of ethylhexyl methacrylate and 14 g of dodecyl mercaptan is added dropwise. At the same time, 140 g of tert-butyl peroctoate in 200 g of MIBK are added. Postpolymerization is then carried out until a constant viscosity of 4.0 dPa.s (50% in MIBK) is reached. Then adjust to 70% solids with MIBK. The number average molecular weight (determined by gel permeation chromatography against polystyrene standards) is
It was 2100. Example 4 Preparation of Binder Dispersion Equivalent epoxide in a 4-reactor equipped with a stirrer, nitrogen line, heater, thermometer and reflux condenser.
1301 parts of commercially available epoxide resin based on 188 bisphenol A, perhydrobisphenol
Charge 623 parts and 95 parts of xylol. 9 parts of dimethylbenzylamine are added to this for the catalytic reaction and the mixture is heated to 160°C. Hold at this temperature until the epoxide equivalent weight reaches 1050. It is then cooled to 110° C. and 519 parts of the crosslinking agent described in Example 1 and 182 parts of diethanolamine are added. after that,
This formulation is held at 110°C for 1 hour. During this time a dispersion bath consisting of 2634 parts of deionized water, 52 parts of glacial acetic acid and 53 parts of a commercially available emulsifier solution is prepared.
A resin solution is dispersed in this. 1 1/2 hours later,
Add another 1012 parts of deionized water and mix for 15 minutes. This dispersion exhibits a solids content of 37.5%. Example 5 Preparation of a binder dispersion 1132 parts of a commercially available epoxide resin based on bisphenol A with an epoxide equivalent weight of 188, molecular weight 750, in a 4-reaction vessel equipped with a stirrer, a nitrogen line, a heater, a thermometer and a reflux condenser. 564 parts of polypropylene glycol, 343 parts of bisphenol A, 133 parts of xylol and 3 parts of dimethylbenzylamine are charged. Increase the temperature to 160°C and maintain this temperature until the epoxide equivalent weight reaches 670. Thereafter, it is cooled to 135° C., an additional 6 parts of dimethylbendiamine are added, and this temperature is maintained until the epoxide equivalent weight is 1250. Furthermore, it was cooled to 110°C, and Example 2
Also add 615 parts of the crosslinker solution described in 1. and 158 parts of diethanolamine. The addition reaction was carried out for 1.5 hours,
Add 171 parts of phenyl glycol and mix for 15 minutes. Meanwhile, 2248 parts deionized water, commercially available emulsifier solution
Prepare a dispersion bath consisting of 52 parts and 45 parts of glacial acetic acid.
A resin solution is stirred into this dispersion bath. After 1 hour, add an additional 1532 parts of deionized water and mix. The amount of solids in the dispersion was 37.5%. Example 6 Preparation of binder dispersion The formulation of Example 5 is repeated, but the crosslinker solution of Example 3 is
Added 615 copies. This dispersion was prepared as in Example 5, but in the second addition of deionized water, 3282 parts of deionized water was added so that the solids content in the dispersion was 30%.
Make it so that A low boiling point solvent is extracted from this dispersion.
Removed by distillation in vacuum at 80°C. A total of 1250 parts of aqueous and organic phase are distilled off. This dispersion has a solids content of 35%. Example 7 Preparation of a gray pigment paste 800 parts of butyl glycol are added to 953 parts of a commercially available epoxide resin based on bisphenol A with an epoxide equivalent weight of 890. Heat this mixture to 80°C. The resin solution contained 221 parts of a reaction product consisting of 101 parts of diethanolamine and 120 parts of an 80% aqueous lactic acid solution.
Add part. This reaction continues until the acid value drops below 1.
Perform at 80℃. 1800 parts of this product were precharged with 2447 parts of deionized water, 2460 parts of TiO ₂ , 590 parts of extender based on aluminum silicate, lead silicate.
135 parts, carbon black 37 parts and lead octoate
Mix 25 parts. This mixture is ground in a grinding device to a Hegman particle size of 5 to 7. Then add 1255 parts of deionized water to achieve the desired paste consistency. This gray paste is very storage stable. Example 8 Preparation of electrodeposition bath and deposition 500 parts by weight of binder dispersant are mixed with 196 parts of the pigment paste described in Example 6 and adjusted to 20% solids in the bath with deionized water. Deposition of the coating takes place on a zinc phosphate-treated board for 2 minutes. The bath temperature is 27°C.
Bake this film at 180°C for 20 minutes.

[Table] Example 9 Preparation of a polyfunctional crosslinking agent (crosslinking agent) based on acrylate resins First, the following monomers are prepared. acrylic acid 580
g with 500 g of acetone. 810 g of triethylamine are added dropwise to this mixture. At this time, the temperature rises to 50°C. Cool to room temperature and then add dropwise 870 g of chloroacetic acid methyl ester. First of all,
2 g of potassium iodide are added as a catalyst to the ammonium salt solution. After the addition is complete, heat to reflux temperature and maintain this temperature for 2 hours. Thereafter, it is cooled and left to stand overnight, and the resulting precipitate is filtered off. 480 g of the listed monomers were added to 120 g of methacrylate, 120 g of butyl acrylate and methyl isobutyl ketone.
Mix with 300g. The monomer mixture is mixed with 19.2 g of t-butyl peroctoate and heated to 80°C. Polymerization is carried out at this temperature for 6 hours. The solvent is then distilled off in vacuo and the solids content is adjusted to 70% with ethyl glycol. Example 10 Preparation of binder dispersion 75% in 5-reactor equipped as required
Charge 1058 g of epoxide resin solution (EEW = 490) and use polyester diol consisting of neopentyl glycol and adipic acid (OH-value 210).
Mix with 214g and heat. Add 2.4 g of dimethylbenzylamine and maintain the temperature at 135° C. until the epoxide equivalent weight reaches 1130. It is then cooled to 90 DEG C. and a mixture consisting of 47 g of methylethanolamine and 59 g of a 72% solution of diethylenetriamine-bismethylisobutylketimine in methylisobutylketone is added. At this time, an exothermic reaction occurs. Increase temperature to 118°C and hold for 1 hour.
Next, 90g of phenyl glycol and crosslinking agent
Add 540g and mix for 15 minutes. Meanwhile, a dispersion bath consisting of 1728 g of deionized water, 23 g of glacial acetic acid and 40 g of an emulsifier mixture is prepared. The resin is dispersed in this. After 1 hour, deionized water
Add another 950 g, stir for 15 minutes and filter the dispersion. Data for the dispersion Solids content: 36.3% (150 °C, 30 min) Density: 1.043 PH-value: 6.9 MEQ acid: 0.27 MEQ base: 0.62 Example 11 Preparation of binder dispersion Proceed as in Example 10, but cross-linked 772 g of crosslinking agent V is added as an agent. The dispersion bath was initially charged with the following: 1498 g of deionized water, 23 g of glacial ethyl acetate and 40 g of an emulsifier mixture. After adding the resin proceed as described above. Data for the dispersion - solids content: 36.7% (150 °C, 30 min) Density: 1.049 PH value: 7.1 MEQ - acid: 0.26 MEQ - base: 0.65 Example 12 Preparation of binder dispersion 5 - equipped as required 1378 g of a commercially available epoxide resin based on bisphenol A (EEW188) and neopentyl glycol were added to the reactor.
Charge 305g. Heat to 130°C and add 3g of dimethylbenzylamine. After the exothermic reaction has subsided, the temperature is increased until an epoxide equivalent weight of 1100 is reached.
Hold at 130℃. Cool to 90° C. and add 123 g of diethanolamine and 108 g of a 72.5% solution of diethylenetriamine bismethyl isobutyl ketimine in methyl isobutyl ketone. At this time, the temperature rises again. The temperature is maintained at 115° C. for 1 hour and 123 g of phenyl glycol and 565 g of crosslinker are added. Mix for 15 minutes. During this time a dispersion bath consisting of 2842 g of deionized water, 42 g of glacial acetic acid and 49 g of emulsifier solution is prepared. The acid value of this bath is 13.8. The resin is dispersed in this. After 1 hour, add 1555 g of deionized water, stir for 15 minutes and filter the resulting dispersion. Data for dispersion Solids content: 35.9% (150 °C, 30 min) Density: 1.050 PH value: 7.0 MEQ acid: 0.28 MEQ base: 0.67 Example 13 Preparation of binder dispersant Proceed as in Example 12 and crosslink as crosslinker agent
Use 807g. Prepare the following mixture as a dispersion bath. 2600 g deionized water, 42 g glacial acetic acid and 49 g emulsifier solution. After dispersing the resin, proceed as in Example 12. Dispersion Data Solids Content: 36.3% (150°C, 30 min) Density: 1.044 PH-Value: 6.9 MEQ-Acid: 6.9 MEQ-Base Example 14 Electrodeposition Bath and Method of Deposition 500 parts by weight of binder dispersion ~ is mixed with 196 parts of the pigment paste described in Example 7 and adjusted to a bath solids content of 20% with deionized water. Deposition of the coating is carried out for 2 minutes on a zinc phosphate treated plate. The bath temperature is 27°C. Bake this film at 180°C for 20 minutes.

[Table] Good Good

Claims (1)

[Scope of Claims] 1 Ingredients: A) Contains at least 0.2 equivalents of hydroxyl groups in 100g resin and has a molecular weight of at least 850
and B) a crosslinking agent based on an organic compound having at least two carbalkoxymethyl ester groups per molecule. . 2 In addition to components A and B, a pigment as component C;
A binder mixture according to claim 1 containing fillers, crosslinking catalysts, corrosion inhibitors and other coating aids. 3 The amount of component A is 50 to 95% by weight and the amount of component B is 5 to 50% by weight, in which case the total amount of components A and B is
A binder mixture according to claim 1 or claim 2 which is 100%. 4. The binder mixture according to any one of claims 1 to 3, wherein component A has a number average molecular weight of 1,000 to 20,000. 5. A binder mixture according to any one of claims 1 to 4, wherein component A additionally contains amino groups or ammonium groups in addition to hydroxyl groups. 6. The binder mixture according to any one of claims 1 to 5, wherein component B has a number average molecular weight of 200 to 10,000. 7 Component B is the following monomer: a) 10 to 50% by weight of an acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl group and/or a methacrylic acid alkyl ester having 2 to 18 carbon atoms in the alkyl group b) Methacrylic acid methyl ester 0-60% by weight c) Styrene, α-methylstyrene, o-
and/or p-chlorstyrol, p-tirt-
Butylstyrene, vinyltoluol and/or vinylcarbazole 0 to 35% by weight d) Olefinic unsaturated polymerizable material containing acrylic acid carbalkoxymethyl ester and/or methacrylic acid carbalkoxymethyl ester or other carbalkoxymethyl ester groups Compound 2-65% by weight, where the sum of components a, b, c and d is
7. A binder mixture according to any one of claims 1 to 6, which is 100% polyacrylic resin. 8. A binder mixture according to any one of claims 1 to 7, which is a finely divided solid. 9 Claim 1 dissolved in an organic solvent
The binder mixture according to any one of paragraphs 1 to 7. 10 In the form of an aqueous solution or in the form of an aqueous dispersion by protonation with an acid, claim 5
The binder mixture according to any one of paragraphs 1 to 7.