DE2626845A1 - Aqueous coating - Google Patents

Description

The invention relates to coating compositions that have a component high molecular weight and a low molecular weight component and are applied from aqueous media to the surfaces to be coated. These masses are particularly suitable for high speed direct application using roller devices, for example for coating metals. Lower speed direct applications using Aufwalzvorrxchtungen and applications using Reversing rollers and other devices for applying coatings also make use of these Masses in question. The coating compounds have excellent flow properties and flow properties and can be used without Difficulties transferred from the rollers to the substrates -

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8000 MUNICH 80 FOB 800780 KXBSI .: MUEBOPAT TEL. (OSD) 471079 TELEX 0-

An important use of these masses is in the production of lubricant feed trains, especially for steel. Lubricant coatings are alkali-removable coatings for metals such as copper, Brass, aluminum, magnesium and various types and types of steel, such as stainless steel. These coatings serve to improve when processing the metal, they also serve to protect against corrosion and other harmful influences. Direct application using roller equipment is the preferred method of applying the lubricant coating, other application methods such as reverse roll application, wiping, or application squeegee, dipping, or electrodeposition can also be used. A second use for these masses consists in a use as thermoplastic air-drying lacquers, which by spraying, dipping, dipping or other methods, either pigmented or non-pigmented, which is convenient all hard surfaces come into question. If these masses are pigmented, they are suitable as base coats for hardboard or tiles. If they contain a high concentration of pigment, they are used as sealing materials with a sanding effect suitable for these materials. If they contain corrosion-inhibiting pigments, they are excellent air-drying ones Primer paints for steel and other metals.

Metals are deformed and prepared, among other things, for shipment to factories, where they are rolled in such a way that they are sent through a roller mill to transform them into the desired shape. A lubricant is required between the rollers and *, the metal workpiece in order to reduce friction and keep the energy required to deform the metal to a minimum. The cold rolling of metals means that the temperature on the metal surface that is in contact with the rolls is up to 100 to 200 ^° C.

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increases, although there is no external heat acting. Desired characteristics of a lubricant coating are high film strength, lubricity, Corrosion resistance, non-staining and removability.

The lubricity, the flow and the protective properties A coating require a variety of properties that are difficult to achieve in a suitable coating. The coating the metal must resist corrosion, rusting and the formation of deposits during handling and shipping and storage and still be easily removable. He must have a suitable lubricity "and a suitable one." Possess coefficients of friction so that the metal in complex Metal feeding, rolling, cutting machines and similar devices can be processed. The coatings according to the invention can easily be formulated in such a way that they exactly correspond to the conditions that are used from device to device or can fluctuate from system to system so that they meet the various requirements of the manufacturer. A simple one Modifying the coating after application for change its friction and lubricity properties is easily possible with aqueous solutions. Basic aqueous systems are used to completely remove the metal coating. One of the conventional lubricant coatings consists of a two-coat system, one being resinous coating and a so-called release oil or a so-called resin activator be used. Combinations of this type are described in U.S. Patent 3,568,486 which polyacrylates are useful Resins for the system mentioned among other resins.

Compositions according to the invention used as lubricant coatings Not only can they be easily applied by roller devices operating at high speeds, they are also omitted also the need to use a triggering oil

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The compositions of the invention are also good temporary coatings for metals such as iron and steel, brass, aluminum and galvanized steel. Coating hardboard is another area in which these masses are of great use are. A hardboard sand often requires that a waterproofing coat be applied prior to sanding, as some hardboard does have a tendency to fray under the action of the cutting action of abrasive materials. Are the inventive masses with pigmented at a high pigment volume concentration, they serve excellently as a sealing agent for sanding. They also serve as base coats for hardboard or tiles when they are pigmented in the normal range. Man can also produce pigmented coatings that are suitable on metals, especially if the pigment is a corrosion-inhibiting one Pigment is. In this case, excellent air-dried primers for metals are obtained.

Have coatings produced from the compositions according to the invention a multitude of other valuable properties, some of which more specifically, if the compositions have been "tailored" for a particular use, coated metal sheets can be stacked or stored for different periods of time, sometimes even at moderately elevated temperatures. It is essential that the coatings not stick to one another when facing side by side during storage, and also do not stick to the metal if they come into contact with metal. It is advantageous to have a coating material available that can be applied from an aqueous medium to avoid air pollution, fire hazards and other problems that occur in the case of systems containing organic solvents contain. Direct roller application at a high speed is economically very advantageous at However, such an application method has to accept other restrictions with regard to the coating mass, such

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Systems often tend to dry on the roller application system, cause difficulty in cleaning, or bubble up with forced drying. In the case of final coatings, they often lack desired properties such as moisture resistance, Durability and hardness. Characteristically, water-based systems are very difficult to achieve rheological Formulate properties suitable for high speed direct roller application. Through the invention Masses made available, which no longer adhere to these disadvantages.

The invention also relates to thermosetting coating compositions, which are likewise applied from aqueous media to the surfaces to be coated be applied. In addition to the high and low molecular weight components, these compositions also contain a third crosslinking component and are suitable for direct application using a roll-on device with high Speed works, for example for the decoration of metals, furthermore for direct coating as well as for reverse coating with low-speed rollers and other application devices. Own the coating compounds excellent flow properties, leveling properties and can be easily transferred from the rollers to the substrate transfer and result in coatings with high gloss, resistance to corrosion, resistance to piling up when hot and resistance to deterioration or extraction under sterilization conditions «

Under "metal decoration" is to be understood that a metal sheet is coated with a suitable coating compound, whereupon the Sheet metal is subjected to various mechanical deformation processes. Examples of metal decorated items that are commonly used are beer cans, beverage cans, vegetable cans, screw

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closures for glasses and aerosol containers. The covers for such Articles must withstand a variety of manufacturing treatments without cracking or peeling off the coating. These manufacturing treatments can range from very mild treatments (for example, in the manufacture of can bodies) can fluctuate up to extremely harsh conditions (for example in the manufacture of aerosol domes}. Of course, the masses can can also be applied to previously deformed objects, for example on by means of a thorn \ jyerfQ., consisting of two parts Can bodies, toothpaste tubes etc.

In performing a typical process for forming a coated decorated metal article, one will use a pigmented white basecoat is rolled onto a metal substrate and the coated substrate is baked. A decorative one Pressure is then applied to the white backing cover. While the ink is still wet, one becomes clearer Overprint varnish rolled onto the printing ink to protect it. The coated metal sheet is then used to develop its final hardness burned. The finished coated metal sheets can then be used for various periods of time prior to processing End product to be stacked or stored. It is essential that the coating has good stacking resistance in a hot state so that the metal sheets are prevented from sticking to each other, as this will damage the coatings caused. The coated sheets then become different Finished forms. The. Processing requirements depend on the particular end use of the material, for example whether the material is to be processed into cans, lids, screw caps, etc. The coatings don't just have to withstand various manufacturing operations performed on the metal, also requiring many end uses processing or sterilization at high temperatures

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appear. In such cases, the coating must withstand exposure to elevated temperatures.

So that the coatings have maximum properties when stacking in if its state is to be bestowed, it is expedient to use a thermosetting To use coating compound, which requires a high degree of crosslinking during curing. However, the cured coatings must also have sufficient flexibility to perform processing treatments, to which they are subjected. If the coated metal is subjected to severe manufacturing operations, then a "soft" thermosetting resin should be used. In contrast, the coated metal is relatively mild manufacturing conditions then a "hard" thermosetting resin can be used.

So far, coatings have been applied to decorate metals, possibly containing anti-corrosive pigments in non-aqueous Binders based on a dry oil, such as linseed oil, on the basis of a quick-drying varnish made from natural resins, a mixture of natural and synthetic resins or an alkyd base modified with a urea, melamine or phenol / formaldehyde resin. Such coating compositions are usually supplied in high boiling solvents so the films applied with roller coating flow well. and run. The solvents are often flammable and often give off noxious fumes during the coating process. To the fire and health hazards often require solvent recovery systems are provided. In addition, with a view to preventing air pollution, efforts are made to reduce or eliminate the emission of organic solvents into the atmosphere.

There has long been a need for thermosetting coating compounds, from an aqueous medium to avoid air pollution,

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- ο -

Fire hazards and other problems associated with the use of coating compositions based on organic solvents occur, can be applied. Aqueous coating systems known to date, as described in US Pat. Nos. 2,760,886, 2,918,391, 3,033 and 3,845,066 have not been found to be entirely satisfactory in coating metals containing the According to the invention specified purposes are supplied, can be used by direct rolling devices. Lots of systems tend to dry on the roller, causing difficulty cleaning, or throwing bubbles when the damp Products are placed directly in an oven. Furthermore, many systems lack desired end properties, such as a moisture resistance and durability. In addition, they are not suitable for post-deformation operations a fragility or suitable for further handling due to their softness, pie greatest difficulty in the case of systems water-based is the setting of rheological properties necessary for high-speed roll-on application of the Systems are suitable.

It is often found that there are ribs in the form of standing waves in the coating composition layer on the rolls of lay-up rolling machines form. These ribs often cause the transfer of a pattern to the substrate, so that there is no surface smoothness is achieved, rather, so-called "internal flow lines" occur in the coating on the substrate. You know that there Forces are in play that act on the coating mass, for example the surface tension, the wetting of the rollers and the substrate as well as the flow under high shear forces during the application, in addition, low shear forces occur during the course after application. These factors play a role a role in achieving well-coated and attractive products. The flow of the mass under these conditions is influenced by elastic and time-dependent phenomena that have not yet been clarified. For practical

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Purposes is a mass required that has such flow and leveling properties that when they are used a directly working roller device is applied, a uniform and smooth surface that is free of. Schlieren is, forms. It is known that aqueous emulsions have poor flow and leveling properties when coating Own metals (see Paint and Varnish Production, February 1964, pages 28-33), The flow and the running of pigmented Primer coatings are most critical because pigmentation markedly degrades the flow of aqueous systems ,

Other binder systems, such as water-thinnable polyesters, acrylic compounds and alkyd compounds, are difficult to achieve acceptable flow and leveling properties, and it is difficult to comply with the solvent restrictions of California Rule 66 of Los Angeles County, according to which less than 20% by volume of organic solvent may be present. Storage stability problems also arise in the case of these binders as a result of hydrolysis of the binder. Colloidal dispersion polymers, colloidal solution polymers as well Polymer emulsions often flow poorly and dry quickly on the reels. It is difficult to control the viscosity of the systems. Often their use is on at low speed working roller application systems limited. The invention eliminates these disadvantages Masses are comparatively easy to paint formulate, either in clear or pigmented form, with excellent properties achieved and adaptation to high-speed direct roll application systems is possible.

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In lubricating oil technology it is known that there are noticeable improvements The rheological properties are achieved when high molecular weight materials are used with materials are mixed with low molecular weight. Since there are no theoretical explanations for the factors involved in If coating play a role in terms of transferring from the rollers as well as flowing and leveling, it is difficult to make a prediction as to whether there is an analogy between these lubricating oil systems and the invention. In any case, it can be seen that the mixture of binding agent components with high molecular weight and low molecular weight according to the present invention an exceptional one Conditional improvement of the desired rheological properties. One can assume that the critical level for the flow occurs when the most volatile components have left the film and the flow through the extent of the Controlled flow of the binder system before drying is complete This flow depends noticeably on the molecular weight distribution of the binder.

According to the invention, masses are made available which consist of consist of a stable aqueous alkaline mixture of the following components:

A) an addition copolymer of (1) 3 to 30% by weight of one olefinically unsaturated monomers which contain a carboxyl group, (2) at least one ester of acrylic acid and / or methacrylic acid and optionally (3) one or more other olefinically unsaturated monomers, the total amount of (1), (2) and (3) is 10Q%, and where the weight average the molecular weight of the copolymer varies between 10,000 and 500 QOQ and it is in the form of a solution or a colloidal Solution is present in an aqueous phase, and

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B) at least one oligomeric addition copolymer from (1) an ester of acrylic acid or methacrylic acid, (2) about 9 to about 50% of an olefinically unsaturated monomer with at least one carboxyl group and optionally (3) other olefinically unsaturated monomers, the total amount of (1), (2) and (3) is 100%, and where the weight average the molecular weight of the copolymer is between about 400 and about 6000 and the molecular weight distribution is such, that the heterogeneity index is 3.0 or less.

The scope of the invention also includes thermosetting compositions which are suitable for direct roller coating of substrates wherein the component (A) is dissolved or dispersed in the form of a salt of a volatile amine or ammonia. These In addition to components (A) and (B), compounds contain

C) a crosslinking agent selected from the group consisting of the following Constituents;

a) an alcohol-modified aminoplast resin, which consists of the Condensation product of an aldehyde with a compound selected from ureas, polyamides and triazines will,

b) a polyepoxide containing at least two adjacent epoxy groups, the epoxy oxygen atom with adjacent carbon atoms is linked,

c) a polyaziridine which has at least two aziridinyl groups contains, and

d) a ß-hydroxyalkylamide of the formula:

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R ³ R ² OOR ² R ³

[ _Η 0 — CC — Ν — C—] -ZCCNCC-OH] -,

UIIL IU ⁿ

CCΝC] ZC],

U Ip Ii ⁿ ■ L I2 U ⁿ

R ³ R ² R ¹ -R ¹ R ² R ³

which contains at least two β-hydroxyalkylamide groups, where Z a bond, Vhydrogen, a monovalent or polyvalent one organic radical which can be traced back to a saturated or unsaturated alkyl having 1 to 60 carbon atoms, aryl, tri-lower-alkylamino or an unsaturated radical, R is hydrogen, low-

2 3 denotes alkyl or hydroxyalkyl, R and R are identical or different and are made up of hydrogen or straight-chain or branched

2 3 whose alkyl consist, where one of the radicals R or R can be bonded to the carbon atoms to which they are linked to form a cycloalkyl, η is an integer of or 2, and η is an integer from 0 to 2 Where, when η is 0 and η has a value of more than 1, a polymer or copolymer of β-hydroxylalkylamide is present when Z is an unsaturated radical, the agent being present in the form of a dispersion or solution in the aqueous mixture in which, on a solids basis, C) is 5 to 50% by weight, A) plus B) is 95 to 50% by weight, where A) in an amount of 95 to 25% and B) in an amount of 5 to 75% by weight of the total amount of A) -, plus B) is present, and wherein the mixture has a volatile aqueous phase of 70 to 95% by volume of water and 5 to 30% by volume of a volatile organic solvent and the mass has a solids content between 15 and 70% by weight, a viscosity between hen 25 and 150 seconds, measured in the Ford cup no. 4 at 25 ⁰ C, has.

By "lower alkyl" is alkyl of 1 to 8 carbon atoms, in particular 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, to understand.

609882/1 OA 1

Such compounds can be referred to as "3-component compounds".

In the "2-component masses" contains, based on solids, the mixed binder 90% A) and 10% B) to 10% A) and 90% B), based on weight. The mixture preferably has a volatile aqueous phase composed of 70 to 95% by volume of water and 5 to 30% by volume of volatile organic solvents. the The coating compound preferably has a solids content between 15 and 70% by weight and has a viscosity between 25 and 150 seconds, measured in a # 4 Ford cup at 25 ° C, the pH being between about 8.0 and 9.8. In each A) and B) make the esters of acrylic acid or methacrylic acid preferably at least 10% and in particular at least 50% % By weight of the copolymer. Component A) is preferably in the form of a salt of a volatile amine or of ammonia.

The binder according to the invention consists of two components: A) a high molecular weight addition copolymer which Carboxyl groups and acrylate and / or methacrylate mers in the form of a solution or a colloidal solution in an aqueous phase contains, and B) an acid-containing oligomer with a narrow Molecular weight distribution containing acrylate and / or methacrylate mers in the aqueous phase. The coating mass is stable and has the hard-to-achieve rheological properties required for high speed direct roller application required are. The dry coating shows a high gloss, corrosion resistance, resistance to damage, resistance to stacking when hot, resistance to decomposition and when used as a metal lubricant, does not require an activator or trigger oil to achieve proper lubricity as well as a suitable coefficient of friction.

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The following describes the high molecular weight component. The high molecular weight copolymer component A) is a solution or colloidal solution of a salt, usually of a volatile amine or of ammonia, which is composed of copolymers, which is about 3 to about 30% by weight of an addition-polymerizable Ethylenically unsaturated carboxylic acid, in particular selected from acrylic acid, methacrylic acid and itaconic acid, and at least one ester of such an addition-polymerizable acid, in particular acrylic acid and / or methacrylic acid and optionally other olefinically unsaturated monomers is prepared. The salt is made by adding the Amine or ammonia to the polymer prepared in an aqueous medium, which is also a cosolvent, as described below is defined in more detail, may contain. In some cases a limited amount of permanent base can be used, up to 1/4 of the amine or ammonia content are used in the manufacture of the salt. The salts obtained often seem colloidal Form aggregates or micelles in aqueous solution. A typical salt obtained according to the invention forms micelles with a diameter of 500 S (determined by light scattering and sedimentation measurements) when it is dissolved in water. The solutions of the copolymer salts are therefore in conveniently referred to as "colloidal solutions". The number average molecular weight of this component, measured by calibrated gel permeation chromatography, is 10,000 to 5Q0 00Q, with the range of 20,000 between 75 is preferred.

The colloidal nature of the dissolved polymer in a colloidal one The solution is clearly based on a determination of the self-crowding constant (self-crowding constant) K for the polymer in the solution according to A. Mercurio ("Rheology of Acrylic Paint Resins ", Canadian Paint and Varnish, September 1964). In Spheres suspended in a liquid change viscosity

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according to the Mooney equation:

in '} - ^ ⁰

where In = natural logarithm,
A rel = viscosity of the system divided by that of the

pure liquid,

0 = volume fraction of beads and K = the self-crowding constant.

Mercurio modified the Mooney equation as follows:

₌ __ _ ^ln \ rel ^BC 2.5

where the new symbols are as follows:

B = an experimental constant and

C = the concentration of the polymer in the liquid. K is calculated by extrapolating plots from ₁

over 1 up to ^ _ _{= Q extrapo} ii _e rt. This leads to the finding that dispersions of beads such as polymer emulsions have K values in the region of 1.9, colloidal solutions of about 1.0, and simple solutions of about 0. Therefore, the self-crowding constant of about 1.0 serves as another way of characterizing the colloidal solutions.

The esters of acrylic acid or methacrylic acid which are used to prepare the copolymer of component A) can be by the formula:

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R ¹ O I. Il H ₂ C = C- -C- -OR

represent where R is H or methyl and R is an alkyl group, preferably with 1 to 24 carbon atoms, in particular with 1 to 12 carbon atoms and in particular with 1 to 4 carbon atoms, an alkenyl group, preferably with 2 to 4 carbon atoms, an aminoalkyl group, preferably with 2 to 8 carbon atoms, an alkylaminoalkyl group, preferably with up to 6 carbon atoms, a dialkylaminoalkyl group, preferably with up to 6 carbon atoms, an isocyanate alkyl group, preferably with 2 to 8 carbon atoms in the alkyl part, a hydroxyalkyl group, preferably with 2 to 8 carbon atoms, a 3 - (1,3-Oxazolidinyl) -alkyl group, preferably with 2 to 4 carbon atoms in the alkyl part and optionally with up to 2 (C -CJ-alkyl substituents on the oxazolidinyl ring, an allyloxyalkyl group, preferably with up to 12 carbon atoms, an alkoxyalkyl group, preferably with up to 12 carbon atoms, an aryloxyalkyl or aralkoxyal kyl group, preferably with up to 12 carbon atoms, in particular a phenoxyalkyl group, benzyloxyalkyl group, substituted phenoxyalkyl group or substituted benzyloxyalkyl group, an aralkyl group, preferably with up to 10 carbon atoms and in particular a benzyl group or substituted benzyl group or an acryloyloxyalkyl or methacryloyloxyalkyl group, preferably with up to 4 carbon atoms in the alkyl portion, or a group of the formula: -A ¹ N (R ^{3 is} JCXNR ¹ R ² , wherein

R is selected from the group consisting of H, alkyl groups with 1. to 4 carbon atoms, hydroxyalkyl groups with 1 to 4 carbon atoms and alkoxymethyl groups with 2 to 5 carbon atoms consists,

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A is an alkylene group with 2 to 8 carbon atoms, R,

if not directly connected to R, for H, phenyl, methylbenzyl, Benzyl, cyclohexyl, alkyl of 1 to 6 carbon atoms, hydroxyalkyl with 1 to 6 carbon atoms or N-alkoxyalkyl with 2

2 1

to 6 carbon atoms, R, if not directly with R connected, is H, phenyl, methylbenzyl, benzyl, cyclohexyl or alkyl having 1 to 6 carbon atoms, the substituents R

2
and R, if they are directly linked to one another, form the morpholino radical - C ₂ H ₄ OC ₂ H. -, the piperidino radical - (CH ₂ J ₅ - or the pyrrolidino radical - (CH ₂ J ₄ -) and X is selected from the group , which consists of oxygen and sulfur, polymerizable monoethylenically unsaturated molecules that have a cyclic ureido group of the formula:

Il

where A is an alkylene group having 2 to 3 carbon atoms, R is selected from the group consisting of H, -CH ₃ OH and -CH ₃ OCH ₃ , and X is oxygen or sulfur.

Examples of these acrylic and methacrylic acid ester monomers are the following: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, Isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, Lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, Dimethylamxnoethyl methacrylate, tert-.i- ^ tylamine »äthylinethacrylät, * 2-Hydroxyäthylmethacrylat, Ethyl 2-hydroxymethyl acrylate, 2-hydroxypropyl methacrylate, Oxazolidinylethyl methacrylate, allyloxyethyl methacrylate, Allyl methacrylate, allyloxyethoxyethyl methacrylate, isopropyl

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oxazolidinylethyl methacrylate, isopropylideneglyceryl methacrylate, T'-ketiminopropyl methacrylate, methyl acrylate, ethyl acrylate, propyl, isopropyl and cyclopropyl acrylates, isobutyl, tert-butyl, butyl and cyclobutyl, acrylates, pentyl and cyclohexyl acrylates and cyclohexyl and cyclohexyl acrylates, and cyclohexyl and cyclohexyl acrylates, and cyclohexyl and cyclohexyl acrylates, and cyclohexyl and cyclohexyl acrylates Cycloheptylacrylate, octyl acrylates, including 2-ethylhexyl acrylate, decyl acrylates Nonylacrylate _r, ündecylacrylate, lauryl, myristyl, cetyl, stearyl acrylate, Phenyläthylacrylat, Phenylpropylacrylate, allyl acrylates, dimethylaminoethyl acrylate, tert-Butylaminoäthylacrylat, Dimethylaminobutylacrylate, Diäthylaminoäthylacrylat, Morpholinoalkylacrylate, Oxazolidinylalkylacrylate, Piperidinoalkylacrylate, Ketiminoalkylacrylate, Methoxyäthylacrylat, Ethoxyethyl acrylate, butoxyethyl acrylate, hexyloxypropyl acrylate, jithoxypropyl acrylate, propoxybutyl acrylate, hexyloxyhexyl acrylate, phenoxyethyl acrylate, benzyloxyethyl acrylate, allyloxyethyl acrylate, allyloxyethoxyethyl acrylate , Allyloxypropyl acrylate, ß-thioureidoethyl methacrylate, N-methyl-N'-ß-methacryloxyethyl urea, N- (ß-methacryloxypropyl) -N-iuethylol-Ν, Ν ¹ propylene urea, ß-ureidoethyl acrylate, N-methylol-N ¹ -methylol ß-acryloxyethyl urea, N- (ß-acryloxyethyl) -N-N'-ethyleneurea, N- (ß-acryloxyethyl) -N-methoxymethyl-Ν, Ν ¹ -ethylene urea, N- (ß-acryloxyethyl) -N-methylol- Ν, Ν ¹ -ethylene thiourea, N- (3-acryloxypropyl) -N, N'-trimethyleneurea, N- [ß- (oC- acryloxyacetamide) -äthylj -N, N'-ethylene urea, N- [ß- (ß- Acryloxyacetamido) -äthylJ -N-methylol-N, N ¹ -äthylenurstof f, N- [ß- & G-Methacryloxyacetamido) -ethyl] -N, N'-Ethylenurea, N- [ß- (^ C - MethacryloxyacetamidoJ-äthylJ- N-methylol-NiN'-ethylthiourea, N- Cß ~ (οό-Methacryloxyac etamido) -propyl] -N, N'-propylene urea ff, N- [ß- (oC ~ acryloxyacetamido) -propyll-N, N ¹ * ■ trimethylene urea and N- [ß- (06-methacryloxyacetamido) ethyl} -N-methylol-N, N 'ethylene urea.

The preferred eaters are the C.-C.-2- alkyl esters / preferred the C ..- Cg-esters, the lower ones, namely the C.-C.-esters, are most preferred.

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Examples of olefinically unsaturated monomers that have a carboxyl group which are used in the copolymer component A), are the following: sorbic acid, cinnamic acid, vinylfurancarboxylic acid, ctf-chlorosorbic acid, p-vinylbenzoic acid, acrylic acid, methacrylic acid, Maleic acid, fumaric acid, aconitic acid, atropic acid, crotonic acid and itaconic acid or mixtures thereof, where itaconic acid and the 06, ß-unsaturated monocarboxylic acids, in particular methacrylic acid and acrylic acid, are preferred. Other polymerizable acid monomers are the alkyl half esters or partiesters of unsaturated polycarboxylic acids, such as itaconic acid, maleic acid and fumaric acid, or their partial amides. Preferred half esters are lower alkyl (C ..- Cg) esters, such as acidic methyl itaconate, acidic Butyl itaconate, acidic methyl fumarate, acidic butyl fumarate, acidic Methyl maleate and acid butyl maleate.

Other vinyl monomers that are present in the copolymer of component A) are used are monomers that contain at least one of the following groups:

Vinylidene CH ₀ = C ^ - vinyl CH ₂ = CH- and

Vinylene -CH = CH-.

Examples are the OC ß-ethylenically unsaturated monocarboxamides, <£, ß-ethylenically unsaturated aldehydes, οί-ß-ethylenically unsaturated Dicarboxylic acid esters, amides, half-esters and half-amides thereof, cC, ß-ethylenically unsaturated nitriles, hydrocarbons, such as vinylary compounds, vinyl halides, vinylacyloxy compounds (Esters of saturated carboxylic acids and ethylenically unsaturated alkanols), vinylamines and salts thereof, vinylureido monomers, Vinyl compounds with heterocyclic nitrogen-containing (HN <^) groups and halogen, hydroxyalkyl or aminoalkyl-substituted Derivatives thereof, regardless of whether they are homooligomers or cooligomers.

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Specific examples of vinyl monomers which can be used in component A) according to the present invention are the following: acrolein, methacrolein, ethylene, propylene, isobutene, butadiene, isoprene, chloroprene, styrene, C6-methyl styrene, vinyl toluene. Vinyl chloride, vinyl bromide, vinyl acetate, vinyl propionate, the vinyl pyridines, amino compounds such as ß-aminoethyl vinyl ether, aminopentyl vinyl ether, ureido monomers, such as acid ß- (N, N'-ethylenureido) -ethyl maleate, ß-ureidoethyl-N, N-vinyl ether, N-vinyl ethylene urea, N-vinyloxyethyl-NjN'-ethyleneurea, N-dimethylaminoethyl-N'-vinyl-N, N ¹ -ethyleneurea, N-hydroxyethyl acrylamide, N-methylolacrylamide and N- (dimethylamineethyl) acrylamide. Of these compounds, the vinyl aromatic monomers, especially styrene, 06- methylstyrene and vinyl toluene, are preferred.

The oligomer component is described below.

The oligomeric copolymer of component B) can according to various known methods are produced. The preferred production methods are an anionic polymerization, which is carried out by initiating an alkoxide ion catalyst in the presence of a chain regulating alcohol. These ways of working are described in DT-OS 22 62 588.

Other known methods of making polymers with low Molecular weight can also be used, for example using a large one. Amount of a free radical source Catalyst, maintaining a high polymerization temperature, the use of a chain transfer agent or the use of all of these measures. Of the chain transfer agents are carbon tetrabromide, allyl chloride, thio-ß-naphthol, Thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, Isopropyl mercaptan and tert-butyl mercaptan are mentioned. Become free

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If catalysts which give off radicals are used, then the concentration can be increased up to a point at which the molecular weight is considerably reduced, especially when high reaction temperatures are maintained. For example, the use of benzoyl peroxide or di-tert-butyl peroxide in amounts of 0.5 mol% to 5 mol%, based on the monomer, together with a solvent such as isopropyl benzene, and compliance with reaction temperatures of 110 up to 250 ⁰ C polymers with low molecular weight. The polymerization processes can be carried out in solution, in bulk or in emulsion, and a non-aqueous dispersion can also be used. In addition to the anionic polymerization and the polymerization proceeding via free radicals, a cationic polymerization can be carried out at high temperatures or in the presence of large amounts of initiator or chain transfer agent. Degrading processes can be used to produce the oligomers from high polymers, for example kneading, photochemically induced degradation, oxidation and bombardment with high-energy radiation such as X-rays, gamma rays and high-energy electrons. In those cases where the products have a broad molecular weight distribution, it may be necessary to achieve the preferred narrow molecular weight distribution, which corresponds to a weight average to number average molecular weight ratio of about 1.5 or less, by vacuum distillation, zone refining , selective precipitation, selective crystallization, solvent extraction or other known methods. It is of course preferable to employ a method which initially gives the narrow molecular weight distribution as described in the DT-OS mentioned above.

Most of the monomers used to make the oligomers of the Component B) are suitable are the same as in connection with the preparation of the copolymers of component A) with

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higher molecular weights have been described. The acidic groups in the copolymer are either using acidic monomers introduced or generated by hydrolysis of ester units in the oligomer, the latter method is preferred.

Component B) consists of (1) approximately 50 to 91% by weight of mer units that can be traced back to one or more monomers, which are preferably composed of styrene, ^ -Methylstyröl, acrylonitrile, Vinyl chloride, vinyl acetate, vinyl pyrrolidone, vinylidene chloride and monomers of the formula:

R 0

. · I I!

EC

are selected in which R is H or methyl and

Y amino, (C ₁ -C ₄ ) -alkylamino, di- (C ₁ -C ₄ ) -alkylamino, hydroxy- (Cj-C ₄ ) -alkylamino, bishydroxy- (C ₁ -C ₄ ) -alkylamino, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkylamino, bis ~ (C.-C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkylamino or a group of the formula -OR, in which

4th
R (C -C ₂₄ ) -Alkylf preferably (C - Cg) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₁ -C ₄ ) -aminoalkyl, alkylaminoalkyl with up to 6 carbon atoms, dialkylaminoalkyl with up to 6 carbon atoms, a group of the formula -A ¹ N (R ³ ) CXNR ¹ R ² , (C ₃ -Cg) -Isocyanatoalkyl, (C ₂ -Cg) -hydroxyalkyl, 1,3-oxazolidin-3-yl- (C ₂ -C ₄ ) -alkyl, optionally with up to two (C ^ CJ-alkyl substituents on the oxazolidinyl ring, allyloxyalkyl with up to 12 carbon atoms, alkoxyalkyl with up to 12 carbon atoms, aryloxyalkyl or aralkyloxy with up to 12 carbon atoms, aralkyl with up to 10 carbon atoms, acryloyloxy- (C ₁ -C ₄ I-alkyl, methacryloyloxy- (C ₁ -C ₄ ) -alkyl or a polymerizable monoethylenically unsaturated one

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Molecule that has a cyclic ureido group of the formula:

■■. i - ι

contains is where

R for H, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms or alkoxymethyl with 2 to 5 carbon atoms,

A is alkylene of 2 to 8 carbon atoms,

R ¹ , if not directly linked to R ² , is H, phenyl, methylbenzyl, benzyl, cyclohexyl, alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 1 to 6 carbon atoms or N-alkoxyalkyl with 2 to 6 carbon atoms,

2 1

R, if not directly connected to R, H, phenyl, methylbenzyl, Is benzyl, cyclohexyl or alkyl of 1 to 6 carbon atoms,

1 2

R and R, if directly connected to one another, form the morpholino radical -C ₂ H ₄ OC ₂ H ₄ -, the piperidino radical - (CH ₂ ) C * "or the pyrrolidino radical - (CH ₂ J ₄ -,

X consists of oxygen or sulfur, A is alkylene having 2 to 3 carbon atoms and

R is selected from the group consisting of H, -CH ₂ OH and -CH ₂ OCH ₃ and

(2) 9 to about 50% carboxylic acid mer units based on the

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Monomers acrylic acid, methacrylic acid or itaconic acid decrease. In each case in (1) and (2), the mer units can be derived from the given monomers by addition polymerization. However, the polymers need not be made from the monomers. According to a preferred embodiment of the invention For example, the acid mer units are made by hydrolysis of ester mer units in the polymer.

According to a more preferred embodiment, the component consists B) from a copolymer of esters or amides of acrylic acid or methacrylic acid or mixtures of these compounds with one another or with other vinyl monomers.

The weight average molecular weight as measured by calibrated Gel permeation chromatography, the oligomer component 400 to 6000, with a range of 500 to 2500 being preferred. The heterogeneity index, namely the ratio of the weight average molecular weight to the number average molecular weight, is 3 or less in the case of the lower range, with a value correspondingly less than 1.5 being particularly preferred will. Furthermore, a weight distribution is preferred which is so narrow that 80% by weight of the oligomer molecules have a molecular weight between about n / 3 to about 3.5 η, where η is the average number of mers in the polymer chain.

The crosslinking agent is described in more detail below «

Aqueous solutions or dispersions of the crosslinking agents of component C), which with the carboxyl groups of the polymer with high Molecular weight and the oligomer react to produce the highly crosslinked thermoset clear or pigmented coatings according to the invention used. The preferred crosslinking agent is an alcohol-modified aminoplast resin. Other crosslinking agents that can be used are polyepoxides with at least two

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adjacent epoxy groups, polyaziridines with at least two aziridinyl groups as well as poly (ß-hydroxyalkylamides) with at least two ß-hydroxyalkylamide groups, in particular ß-hydroxyethyl amide groups.

The alcohol-modified aminoplast resins, namely water-soluble, heat-convertible condensation products of a urea, a polyamide or a triazine (for example Melamine) with formaldehyde and / or their derivatives, which are obtained by reaction with ethanol or methanol, can according to one of the following methods can be prepared: (1) control of the reaction conditions in such a way that the degree of polymerization is kept very low, even up to the monomer stage, and (2) introduction of hydrophilic groups into the molecules of the polymeric condensates. That way they can get through careful control of the reaction conditions can be established (cf. Schildknecht "Polymer Processes", Volume X, p 295 ff. (Interscience Press, 1956}). Making another Class of compounds which are suitable for the invention, for example N, N'-bis (methoxymethyl) urea, is described in "Bull. Chem. Soc. Japan? Volume XI, No. 3,239 (1936). According to one The preferred embodiment of the invention is the crosslinking agent an essentially monomeric alcohol-modified one Condensation product of formaldehyde and melamine, being hexamethoxymethylmelamine and pentamethoxymethylmelamines are particularly preferred.

The polyepoxide crosslinking agent can be any of any water soluble or easily water-dispersible aliphatic Diglycidyl ethers of the following formula I consist, for example, of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether or trimethylene glycol diglycidyl ethers. Related water-soluble or easily water-dispersible glycidyl ethers, which are also can be used are the polyglycidyl ethers of

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polyhydric alcohols having 2 to 4 carbon atoms, such as ethylene glycol, glycerol / Trimethylengiy-Καΐ _f propylene glycol, butylene glycols, their dimers, trimers and higher polymers, in particular the water-soluble or water-dispersible glycidyl ethers according to one of the formulas I, II and III:

H ₂ C -CH CH ₂ 0 R 0 ^: CH ₂ . CH

0. '0

wherein where R is an alkylene group having 2 to 6 carbon atoms,

• ■ Ii '- ■■ · ■ .-

CHp-CHCH ₉ O (CH ₀ CH (OH) CH ₀ OlCH ₀ CH-CiI ₀

wherein χ is a number having an average value of 1 to 3 having,

III · - '■.

Hi _/ CHCH ₂ 0 (C _m H _{2 Ni} 0) ₂ CH ₂ CH- ^

o. O

where m is an integer from 2 to 4 and ζ means a number with an average value of 1 to 5. All of these polyepoxides contain at least two adjacent ones Epoxy groups in which the epoxy oxygen atom is bonded to neighboring carbon atoms

Since the polyepoxides can be obtained through reactions that cause condensation and elimination of water they are referred to as "condensates" and are characterized in this way in the present case for reasons of simplicity.

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Any epoxy condensate that is soluble in water or any water-dispersible epoxy condensate can be used. A dispersant such as octylphenoxypolyethoxyethanol can be used to promote dispersion of the latter type of condensate will. Their solubility in aqueous systems can be sufficiently increased by the addition of a lower alcohol, such as Ethanol, isopropanol or the like can be improved.

The water-insoluble copolymer is dispersed in the aqueous medium by a dispersant or a Held emulsifier, which generally has an anionic or non-ionic character.

Other polyepoxides that can be used are the condensates of bisphenol A

CH ₀

! ³

C-C

and epichlorohydrin, Cl-CH ₀ -CH-CH ₀ . A number of these condensates are listed in the following table.

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OT O CD OO OO NJ

Melting point,
⁰ C (Durans) Colour,
25 ⁰ C
(Gardner) Epoxy equivalent Average
Molecular weight Viscosity at
25 ° C, centipoise.
or Gardner-Holdt I. fluid 8 (max) 175-210 350-400 4,000-10,000 CO
1 fluid 12 (max) 175-210 350-400 5,000-15,000 fluid 10 (max) 225-290 450 A2-A1 40-50 8 (max) 300-375 700 A1-B 64-76 8 (max) 450-525 900-1000 C-G 95-105 6 (max) 870-1025 1400 Q-U 125-132 8 (max) 1650-2050 2900 Y-Z1 145-155 11 (max) 2400-4000 3800 Z2-Z5

In 40% butyl carbitol,

cn oo j> cn

Other polyepoxides that can be used are those produced by epoxidation are made from unsaturated fats and oils. Preferred compounds of this class are the soybean oil epoxies.

Polyaziridines which are suitable as crosslinking agents are the Trialkylenphosphoramxde and the tripropylenethiophosphoramides, such as tripropylenethiophosphoramide, tripropylenephosphoramide, the bis-iNfN'-diethylenephosphoramides), such as η-butyl, ally, cyclohexyl, Benzyl-, ethyl- and n-hexyliminobis- £ bis- (1-aziridinyl) -phosphine oxide, the diethylenimino and dipropyleniminophosphate esters small glycols, such as diethylene glycol, aziridine-saturated ones Polyglycols of the formula:

H ¹ . ". H ¹

J *

where η is an integer from 2 to 4,

m is a number between 1 and 50 and

1 2

R and R are hydrogen or (C ₁ -C ₄ ) -alkyl groups, such as, for example

N- (CH ₀ -CH ₀ -O) -

² I ^ N (CHCHO) CHCHNd I

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as well as compounds of the formula;

YCOZI-T

1 2
wherein R and R have the meanings given above, η is an integer from 2 to 6,
Z is a (C ^ -Cg) alkylene group,

B alkyl, aryl, aralkyl, a cycloaliphatic group, a heterocyclic group Is a group or a polyalkylene ether having 1 to 50 units, and

Y for oxygen, sulfur, nitrogen or an -NH group, how

0 CH ₃ -CH ₂ -G (CH ₂ -O-CCH ₂ CH ₂ N ^

-CH

'CE

stands.

Other water-soluble or water-dispersible polyaziridines are known. Mention should be made in this context of BE-PS 804 135.

The ß-hydroxyalkylamide cross-linking axels are in the DT-OS 25 09 237.

The coating compositions according to the invention can be used as clear coatings be used i.e. as non-pigmented clear top coatings, or as pigmented coatings. In the case of a pig

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The ratio of pigments to coating solids can change vary considerably, depending on the pigment used and the intended use in question. The relationship the pigment to coating solids can vary between 1:20 and 20: 1. The clear coatings according to the invention Compounds usually formulated with a solids content of 15 to 60% by weight. Pigmented formulations lie between 3Q and 70% by weight. The clear covers are suitable particularly as "upper coatings", i.e. so-called coatings over prints, which are used to protect decorative lower coatings without affecting the decorative Effect is lost. Since the clear coatings according to the invention have good clarity, high gloss, excellent Resistance to solvents as well as water and a high level of adhesion to a large number of surfaces, they are excellent as coatings over prints suitable.

Even if the coatings according to the invention are particularly suitable are for decorating metals, so they can still be applied to a variety of other substrates, the only limitation being the ability of the substrate to withstand the firing cycle that is essential to processing the 3-component coating compounds. Metals are particularly suitable, regardless of whether they have a primer coat exhibit or not.

The 2-component compounds are suitable as protective coatings, when a substrate is further processed after coating and the coating is then removed. The coating compositions according to the invention are particularly suitable as metal lubricants, in particular when the substrate is a metal sheet which is mechanically deformed or rolled after coating. Iron-, Steel, aluminum, copper, bronze or brass surfaces,

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particularly in sheet metal or wound form with thicknesses between 1.3 and 5.1 mm (0.05 to 0.20 inches) are particularly suitable Way as substrates for the coating compositions according to the invention. Ceramic surfaces as well as the surfaces of panels made of wood, including composite panels, the wood chips, wood sawdust or contain wood fibers, are also suitable as substrates. For roll coating a substrate with the inventive mass is used an amount that a finished dry layer with a thickness of 0.25 to 127 μ and preferably a thickness between 5.1 and 38.1 μ (0.01 to 5 mils or 0.2 to 1.5 mils).

You can use a variety of pigments in the invention Use masses. Typical pigments suitable according to the invention are titanium dioxide, iron oxide, potassium carbonate, barytes and numerous Clay types.

The coating compositions according to the invention are particularly suitable for an application using a direct application roller device, however, they can be applied in other ways, such as using a reverse roll coater or a spray gun.

Certain monomers are known to add toughness to the films. The monoolefinically unsaturated aromatic monomers, acidic monomers, monomers with hydroxyl and / or amide functionality may be mentioned here. The olefinically unsaturated monomers that contain a carboxyl group can consist of a simple monocarboxylic acid, it can also be a half-ester or a half-amide of an ÖC _r ß-unsaturated dicarboxylic acid and salts thereof with a volatile base such as ammonia or a volatile water-soluble amine, such as dimethylamine, dimethylethanolamine, triethylamine, triethanolamine, morpholine, n-methylmorpholine, picoline or the like act. Thieves-

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very even coating compounds can be used as lubricant coatings, clear top coatings or in pigmented form are used, a variety of pigments being usable. If the inventive lubricant coatings are used as coatings for Lubricating metals used, then no activators, such as release oils, or organic or aqueous oil solvent solutions necessary. For other coating purposes, they can contain materials called leveling agents, however, such materials are generally not necessary in the compositions according to the invention. Rheology modifiers can also be used in the masses or as part thereof, but they are also not necessary. It is known that the incorporation of leveling agents or rheology modifiers often results in a loss of certain properties Properties of the coatings or a reduction in these properties entails. One of the big advantages of the present invention is that these materials become obsolete. This requires a considerable Simplification of the composition as well as an improvement of the film properties by omitting materials that do not contribute to the functioning of the binder, but rather generally act as a diluent in the binder component works.

For a formulation of a coating made from a 2-component compound According to the present invention, a large number of compositions have proven to be suitable, depending on the desired ones Coating properties, For the production of very fluid systems with high Newton flow properties, up to about 90% of the oligomer selected. To achieve a high viscosity and to avoid Newton properties, a lower one is used Selected oligomer content of approximately 10%. The binder therefore varies between 90% oligomer and 10% of the colloid dissolved High molecular weight polymers, respectively

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expressed as weight% solids, and 10% of the oligomer and 90% of the colloidally dissolved polymer. A preferred range is between 80% oligomer and 20% of the colloidly dissolved Polymers and 30% of the oligomer and 70% of the colloidally dissolved polymer. The pH of the system is basic and usually lies between 8.0 and 9.8, being the preferred range moved between 8.7 and 9.5. The pH adjustments are made by adding basic materials such as ammonia, dimethylaminoethanol, Triethanolamine and morpholine to get both the ones you want To achieve rheological properties as well as the desired corrosion resistance. The viscosity of the system increases with an increase in pH in the usual pH range up to a pH of about 10. Within the same The corrosion effect on metal generally decreases in the area. The volatile components in a coating make 70 to 95% by volume water and 5 to 30% by volume organic Solvent, with the preferred range between 80 and 95% water and 5 to 20% organic solvents lies. In general, as the organic solvent content increases, the viscosity of a given binder increases. The viscosity using a # 4 Ford Cup according to the American Society for Testing Materials, Method D1200-58, of finished coating compositions according to the invention is between 25 and 150 seconds, with 40 to 100 seconds being preferred. The solvents used are those in general classified as "strong" solvents. These are lower alcohols such as propyl, butyl and pentyl alcohol, Ketones, such as methyl ethyl ketone, methyl butyl ketone, methyl propyl ketone and lower alkoxyethanol solvents such as propylethoxy and butoxyethanols.

Particularly suitable compositions are pigmented or non-pigmented Compounds that are suitable for direct roller coating of substrates and consist of a stable aqueous alkaline

609882/1041

Mixture with a binder composed essentially of the following ingredients: A) an addition copolymer of (1) about 20 to about 50% by weight of styrene, methyl methacrylate or both compounds, about 40 to about 60% butyl acrylate and about 10 to about 20% methacrylic acid, the weight average molecular weight of the copolymer fluctuating between 20 QOQ and 75,000, B) a partially hydrolyzed alkoxide-polymerized addition copolymer of methyl methacrylate and butyl methacrylate with an acid number between 100 and 200, the weight average molecular weight fluctuating between 500 and 2500 and the molecular weight distribution is such that the heterogeneity index is 1.5 or less, wherein in the mixture, on a solids basis, A) is between 70 and 20 and B) between 30 and 80% by weight and the mixture is a volatile aqueous phase of 70 Up to 95% by volume of water and 5 to 30% by volume are volatile Has organic solvents and, moreover, has a solids content between 15 and% by weight, the viscosity being between 25 and 150 seconds, measured in a Ford cup No. 4 at 25 ^° C. The pH value is between 8.7 and 9.5.

The 3-component coatings can be burned (250 to 350 ⁰ F) for a period of about 1/2 to 10 minutes at a temperature of about 120 to 180 ⁰ C. The firing or curing volatilizes the volatile material in the film including any remaining water, traces of monomers, leveling agents and tertiary amine. In aminoplast-crosslinked systems it is particularly important that the tertiary amine is volatilized as it inhibits the hardening of the aminoplast. The firing has a decomposition of the ammonium or amine salts of polymeric carboxylic acids de s result, although it appears that the acid form of the copolymer is released, which then reacts with the other components in such a way that they are insoluble. The firing has the consequence that the crosslinking agent with the oligomer and the poly

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meren with crosslinking as well as with insolubilization of the whole Films reacts.

An aminoplast is used in the preferred 3-component compound. Since aminoplasts are reactive under strongly acidic conditions, the mixture must not become too strongly acidic if they should have a significant shelf life. A volatile base such as ammonia or a tertiary amine, preferably dimethylaminoethanol, is used to make the system alkaline as tertiary amines do not react with the formaldehyde that is associated with is associated with the aminoplast. The tertiary amine also acts as a corrosion inhibitor when the coating composition is used for coating Metals should be used. The amine must be volatile to such an extent that essentially all of its amount is off the film is driven out during burning. However, it must not be so volatile that it evaporates from the film instantly or gasified if the coating is applied by spraying. Aminoplastsysterne made using ammonia brought to a high pH alone tend to have poor storage stability. However, become tertiary Amines used as predominant nitrogen bases then can small amounts of ammonia can be tolerated without adverse effects.

A component that may be used is a dispersant to disperse the pigment. In this case, too, it is a component that has adverse effects on the Properties of the finished film can exert, in particular water resistance. Another advantage of the invention is in that the use of a dispersant is not necessary in these systems.

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When formulating the 3-component systems according to the invention the type and amount of crosslinking agent selected are based on the coating properties desired. To achieve a high hardness and good stain resistance and opposed to solvents is a large amount of crosslinking agent expedient. A small amount is used for good flexibility. The appropriate amount of crosslinking agent varies between 5 and 50 percent of the binder solids on a weight basis, with a range of 15 to 40 percent preferred will. The remaining 50 to 95% of the binding agent consists of a mixture of the oligomer and the colloid solution High molecular weight polymers, the oligomer constituting 5 to 75% by weight of this remainder. 25 to 50% is preferred. The high molecular weight component accounts for 95 to 25 percent of this remainder, with 75 to 50 percent being preferred. The viscosity using a # 4 Ford Cup according to the American Society for Testing Materials, Method D-1200-58 The coating mass is between 25 and 150 seconds, 40 to 100 seconds being preferred. The volatile constituents in the coating compounds make up 70 to 95% by volume of water and 5 to 30% organic solvent, the preferred range being between 80 and 95% water and 5 to 20% organic solvent lies. The solvents used are generally those which are considered "strong" solvents. These are, for example, lower alcohols such as piropyl, butyl and pentyl alcohol, Ketones, such as methyl ethyl ketone, the methyl buty! Ketones and the methyl propyl ketones, and also to lower alkoxyethanol solution medium, such as propyl and butyl cellosoive (Union Carbide).

The following examples in which the parts and percentages are based on weight and viscosities using of the Brookfield viscometer, unless otherwise stated, illustrate the invention without restricting it.

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Examples of the high molecular weight component A) are
the following:

Example A1

a) Preparation of the acidic polymer in solution

A monomer mixture is made by combining the following materials manufactured:

Gram

Ethyl acrylate 215

Methyl methacrylate 215

ß-hydroxyethyl methacrylate 55

Methacrylic acid 15

2-ethoxyethanol 108

In a glass reaction vessel provided with a reflux condenser, a Teflon stirrer and a dropping funnel and a thermometer, are added 1,390 g of 2-ethoxyethanol. The contents of the flask are heated to a temperature of 75 ⁰ C using a water bath, after which 3.75 g of azobisisobutyronitrile (AIBN)
added to the 2-ethoxyethanol immediately before the addition of a quarter of the monomer mixture, the amount of which is added over a period of approximately 5 minutes. The batch temperature is kept at 75 ± 5 ^° C. while a second quarter of the monomer mixture is added after 30 minutes. A third quarter is added after 60 minutes and a fourth quarter after 90 minutes, the respective additions requiring approximately 5 minutes. The batch temperature is kept at 75 ^° C. for a further period of 3 to 15 hours, 1.9 g of AIBN being added 2 hours after the start of the monomer addition and 0.85 g of AIBN 2 hours later. The batch is cooled and through a
Cheesecloth sent to remove any insoluble residues that may be present

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Solids analysis determined which shows that the polymer is using Sales of 99% or more have been made.

b) Isolation of the solution polymer

The 25% concentrate of the polymer in 2-ethoxyethanol, the according to Example 1 a) has been obtained, is reduced to 12.5% (the exact dilution is not critical) with 2-ethoxyethanol or diluted methanol. A 19 liter jar will be approximately half filled with an equal mixture of water and ice, whereupon the mixture is stirred. The polymer solution will slowly added to the stirred ice / water mixture. A precipitate forms immediately. About 3.8 liters of the polymer solution can be precipitated this way. The ice / water mixture is allowed to warm to room temperature, whereupon the precipitated Polymer is removed by filtration through a Buchner funnel fitted with a coarse filter paper. Two to 4 successive washes with cold water remove all traces of solvent. The polymer is exposed to air dried.

c) solubilization of the isolated polymer

The polymer isolated according to b) is solubilized in the following way: The following components are placed in a suitable digestion flask:

Gram

Polymer 100 water 400 tert -butanol 25th D imethylaminoethanoI 4.6 (1.5 equivalents)

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This mixture is well mixed and digested at 70 to 80 ⁰ C over a period of several hours. The solution obtained is clear.

Example A2

a) Production of the acidic polymer as an aqueous latex

A monomer mixture is made from the following materials:

Gram

Ethyl acrylate 460

Methyl methacrylate 460

β-hydroxypropyl methacrylate 50 Methacrylic acid 30

CBrCl ₃ 2.5

In a glass reaction vessel equipped with a reflux condenser, a Teflon stirrer as well as an addition funnel and a thermometer, the following components are poured in:

Grams of water 1708

10% aqueous solution of dimethylaminoethanol solubilisier200 th polymers according to Example A1 c)

The batch in the flask is brought to 95 ° C using a steam bath heated, whereupon the monomer mixture is added uniformly over a period of 30 to 45 minutes while simultaneously and proportionally a solution of 1.88 g of ammonium persulfate is added in 100 ml of water from a Byrette. During the simultaneous addition of the monomer mixture and the initiator

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solution maintaining the batch temperature at a value above 90 ⁰ C, whereupon further stirred with a fairly fast speed (ie, 100 to 400 rpm). Heating is continued for 1/2 hour after the monomer addition is complete. the
The batch is then cooled to room temperature for storage or to 50 ^° C. if the solubilization is to be carried out immediately. The polymer latex (33% polymer) is a white, opaque, smooth product with a viscosity of 10 to 20 cps. It's very stable.

b) solubilization

Separate 90 g portions of the finished polymer latex from part a) are obtained by mixing the 90 g amount of the latex, obtained according to part a), with 1.0 g of Dimethylamxnoäthanön in χ grams of a mixture from water and cosolvent with a weight ratio of 100-y): y solubilized. The mixture is at 55 ° C for a Maintained a period of 2 hours. The cosolvent as well as χ and y are in the respective cases:

tert -butanol X y 1. n-butanol 125 6th 2. Isopropanol 125 3 3, Isophorone 50 20th 4th 2-ethylhexanol 100 10 5. 2- (butoxy). ethyl acetate 100 3 6th 2- (butoxyethoxy) ethyl acetate 110 5 7th Triethanolamine 80 5 8th. 2-butoxyethanol 100 3 9. 50 6th Example A3

As an example of another type of aqueous latex, a copolymer is made by emulsion polymerization of a mixture of

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Parts of butyl acrylate, 25 parts of methyl methacrylate, 10 parts of styrene and 15 parts of methacrylic acid. The initiator system consists of 1.5% hydrogen peroxide, 0.75 S hydroxylamine and 5 ppm iron (II) ions. The emulsifier consists of 0.5% sodium lauryl sulfate. The solids content of the latex is 35.0%. The emulsion has a viscosity of 120 cps, The copolymer has an Intrxnsicviskosität of 0.14 (in acetone at 3O ⁰ C) and a weight average molecular weight of 50 000 to. The solubilization is carried out as in Example A2, part b).

Example A4

A copolymer latex is made as in Example A2 using the following Monomer mixture produced:

Gram

Ethyl acrylate 510

Methyl methacrylate 440 methacrylic acid 50

CBrCl ₃ 2.5

Example A5

A copolymer latex is made as in Example A3 using the following Monomer mixture prepared: 25 parts of methyl methacrylate, 10 parts of styrene, 35 parts of butyl acrylate and 15 parts of methacrylic acid "

The following are examples of the oligomeric copolymer,, and although component B) is given;

Example B1

Stage A - Oligomeric methyl methacrylate / butyl methacrylate (75/25 by weight)

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60 g of toluene, 22.5 g of n-butanol, 29.4 g of a 25% solution of sodium methylate are placed under nitrogen in a 3 liter three-necked flask equipped with a condenser, paddle stirrer, thermometer, addition funnel and Y-tube in methanol and 12.7 g of a 30% solution of potassium methylate in methanol. 310 g of methyl methacrylate and 103 g of butyl methacrylate are added to this clear solution at 60 ^{° C. with stirring over a period of 30 minutes.} The pale yellow mixture is held at about 61 ⁰ C until the reaction mixture is exothermic (about 35'Minuten after the addition). ' The temperature is maintained at about 65 ⁰ C. After the exothermic reaction has ceased, 1067 g of methyl methacrylate, 355 g of butyl methacrylate and 414 g of toluene are added over a period of 1 hour, the reaction temperature being maintained at 60 to 63 ° C. while cooling with an ice bath. The product, which is obtained in a more than 98% conversion after a period of 1/2 hour following the second addition stage, consists of oligomeric methyl methacrylate (butyl methacrylate (75/25) with an M value of approx. 1450 and one M value of about 1300, so that the heterogeneity index, measured by calibrated gel permeation chromatography, is 1.1 This material is used to carry out the following step without further purification.

Stage B - hydrolysis of the oligomeric methyl methacrylate / butyl methacrylate to 25% methacrylic acid

1000 g (80.1% oligomer) of the oligomeric methyl methacrylate / butyl methacrylate from part A in a 3 l three-necked flask, which is provided with a bottom shut-off valve, a reflux condenser, a stirrer and a thermometer, are under a nitrogen atmosphere at 63 ^° C. 185 g (50.3%) of an aqueous sodium hydroxide are added. The reaction mixture is kept at 73 to 78 ^° C. for a period of 1 hour and then heated to reflux for a period of 4.5 hours. The titration results in this

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Time a conversion of 84%. The yellow viscous oil is cooled and diluted with 200 g of water and 200 g of toluene. 400 g of a heterogeneous distillate are removed over a period of 1 1/2 hours. The remaining clear yellow-orange solution is mixed with 200 g of toluene, whereupon the mixture is refluxed for a period of 5 1/2 hours. At this time, 200 g of toluene, 100 g of isobutanol and 710 g of water is cooled and the reaction mixture to 50 to 60 ⁰ C are added. Then 179 g (97%) sulfuric acid is added over a period of 15 minutes with cooling. The reaction mixture becomes a white, mobile two-phase mixture which is stirred for a further 14 to 20 minutes. After removal of the aqueous layer a further 700 g of water are added, is heated and then the reaction mixture to 60 to 7O ⁰ C under sufficient vacuum to remove the toluene. The pressure is adjusted to atmospheric pressure after collecting about 400 g of a distillate while the temperature is increased to 100 ^° C. The remaining white, consisting of two phases and soft gumartigen mixture are at 9O ⁰ C 222 g of dimethylaminoethanol and 464 g of butyl cellosolve was added. After two thirds of the dimethylaminoethanol (DMAE) have been added, solubilization takes place. The solution is cooled to 60-65 ° C and the remaining DMAE is added. The product solution is clear and light yellow (APHA color approx. <C 250). Solids: 60%, pH approx. 9.3, viscosity at 25 ° C. approx. 4000 cps, product acid number approx. 160 (at 10% solids), which indicates a copolymer which contains 25% methacrylic acid units.

In general, the oligomeric polymer can be in the acidic form can be left, it can also be neutralized with dimethylaminoethanoi as in this example or with another base. Other such bases are ammonia as well as various amines conventionally used in the formulation of coatings Water-based can be used.

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To determine the average molecular weights of the hydrolyze To calculate polymers, the final step is to find the average molecular weight (M.W.) of the Mers in the unhydrolyzed To obtain copolymers. This is 0.75 χ M.W. of methyl methacrylate plus 0.25 χ M.W. of butyl methacrylate, in numbers, 0.75 χ 100 + 0.25 χ 142 = 110.5. Since methacrylic acid has a molecular weight of 86, hydrolysis of 25% of the acid units have a new average molecular weight of about 0.25 86 + 0.75 110.5 = 104.5. For conversion the M and M values of the unhydrolyzed polymer to those of the hydrolyzed polymer, these are multiplied by the ratio 104.5 / 110.5. For the hydrolyzed polymer the M value is approx. 1370 and the M value approx. 1230.

Example B2

Stage A - Oligomeric methyl methacrylate

115 g of toluene, 2.4 g of methanol, 20.2 g of 30% strength methanolic potassium methylate and 216 g of methyl methacrylate are placed in a 2 liter three-necked flask equipped with a stirrer, thermometer and reflux condenser. The temperature of the reaction mixture rises to 27 ^° C. over a period of 25 minutes. The mixture is then ^{heated to 33 °} C. within 20 minutes. ^{The temperature reaches 42 °} C. within a further 20 minutes and requires cooling. After 40 minutes the reaction mixture is heated to maintain the temperature at about 40 ⁰ C. After 1 1/2 hours, the reaction temperature is increased to 6O ⁰ C. At this point a solution of 649 g of methyl methacrylate and 265 g of toluene is added while maintaining the temperature at 60 to 62 ° C. After a period of 45 minutes, the conversion exceeds 99%. An aliquot of the reaction mixture (300 μl) is treated with 1.05 g of concentrated sulfuric acid and 1.5 g of diatomaceous earth and filtered

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a clear light yellow oil with a solids content of 70.5% obtain. A molecular weight determination by gel permeation chromatography results in an M -value of 1700 and an M -value from 1350 to 14Q0 and thus a heterogeneity index of 1.2 to 1.3.

Stage B - Partially hydrolyzed oligomer of methyl methacrylate

161 g (50.9%) aqueous sodium hydroxide are added to 12Q0 g of oligomeric methyl methacrylate in a 2 liter Parrbome, which is provided with a sampling tube, a pressure indicator, a stirrer shaft, a pressure relief valve and a hose connection to a dry ice cooler. The bomb is heated to 130 to 135 ° C. in an oil bath with the vent valve open for a period of 1/2 hour. The vent valve is then closed, is set and then the temperature of the reaction mixture to 110 ⁰ C. The pressure is 0.98 atm. After 2 hours the heating is interrupted, whereupon 120 g of toluene and 24Q g of deionized water are added. After the temperature reached 8O ⁰ C and the pressure O, stirring is stopped, is opened and then the bomb. The contents are transferred to a 3 liter three-necked flask. Then 3Q6 g of toluene, 219 g of water and 67 g of n-butanol are added. The reaction mixture is held at 55 ° C while 219.7 g (90%) formic acid is added over a period of 15 minutes. The mixture is stirred for a further 20 minutes, after which the two phases separate. 9Q5 g of water, 164 g of butyl cellosolve and 210 g of DMAE are added to the organic phase in a 3 l flask. This mixture is heated to reflux to remove the organic distillate. The reaction mixture is cooled to 95 ° C. and treated with a further 100 g of DMAE. Stirring is continued for a period of 20 minutes after the solution has been cooled ^{to 60 ° C.} The product owns

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the following properties: It is essentially clear and colorless (APHA <1Q0) with a solids content of 48%. pH 9.3; Acid Number 115 (100% solids).

Examples B3 and B4

Using methods similar to those of Stage B of Example B1, the oligomeric methyl methacrylate / Butyl methacrylate copolymers according to B1, level A, hydrolyzed, where 7% methacrylic acid units in the copolymer (Example B3) and 15% methacrylic acid units in the copolymer (Example B4) can be obtained.

Example B5

By essentially the same method as described in Example B1, an equal weight of the copolymer is obtained made from methyl methacrylate and butyl methacrylate which have a weight average molecular weight of 1,100 and a number average of the molecular weight of 950, so that the heterogeneity index is 1.16. The copolymer is used to produce 54% Methacrylic acid units hydrolyzed in the product.

Examples B6 and B7

According to the method described in Example 2, an oligomeric homopolymer of methyl methacrylate with a weight average of Molecular weight of 110Q and a heterogeneity index of 1.2 manufactured. A portion of the. Qligomer is hydrolyzed, whereby 27% methacrylic acid units (example B6J are obtained. Another portion becomes 36% methacrylic acid units (example B7) hydrolyzed.

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Example B8

According to the method described in Example 2, an oligomeric Homopolymer of butyl methacrylate with a weight average molecular weight of 1110 and a heterogeneity index of 1.16 manufactured. It is then hydrolyzed to obtain a product with 34% methacrylic acid units.

Example B9

Free radical initiated oligomer

341.8 g of butyl cellosolve and 4.7 g of tert-butyl peracetate, 75% in white spirit, given. The initiator is gradually added to this flask over a period of 6 hours. A monomer mixture is fed in in a separate stream, the flask temperature being kept between 145 and 149 ^° C. The gradual addition of the initiator consists of 88.8 g of tert-butyl peracetate (75% in white spirit) and 1.2 g of butyl cellosolve. The monomer mixture is composed as follows;

Gram

n-butyl methacrylate 280

Methyl methacrylate 770

Methacrylic acid 350

2 -hydroxy a thy Inter kaptan 21

After the end of the polymerization, the remaining monomer is removed by the use of a trapping catalyst? pressed to a minimum. 510 grams of Butyl CelIosolve are added to reduce the solids to a calculated 65% by weight. The solids content is 66%.

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The final viscosity of the system is above 100,000 centipoise at 25 ⁰ C. The weight average molecular weight of about 2000 and the heterogeneity index is about 2.8.

Example B10

Free radical initiated polymer

The method and the device used are similar to the method and the device according to Example B9. The polymerization is carried out for a period of 3 hours, maintaining the temperature between 14Q and 150 ⁰ C is maintained. The flask charge consists of 341.8 g of butyl cellosolve, while the initiator stream consists of 65.4 g of tert-butyl peracetate, 75% in white spirit. The monomer flow is composed as follows:

Gram

n-butyl acrylate 439.6

n-butyl methacrylate 103.6

Methyl methacrylate 506.8

Styrene 88.2

Methacrylic acid 261.8

After the 3 hour polymerization is complete, a scavenger is used to reduce the amount of unreacted monomer. 240 g of butyl cellosolve are added. The final solids content is 71.8% by weight. The viscosity is above 10 000 centipoise at 25 ⁰ C. The weight average molecular weight is about 25,000 and the heterogeneity index about 2 _f. 5

Example B11

The method and apparatus are similar to the method and the pre

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direction according to example B9. The polymerization is carried out over a period of 6 hours, with the temperature is kept between 146 and 154 ° C. The flask charge consists of 415 g of butyl cellosolve and 10 g of 2-hydroxyethyl mercaptan. The initiator stream consists of 53.3 g of tert-butyl peracetate (75% in white spirit). The monomer flow is composed as follows:

Gram

n-butyl methacrylate 230

Methyl methacrylate 52Q

Methacrylic acid 250

After the completion of the 6 hour polymerization, a scavenger is used to decrease the amount of unreacted monomer. The solids content is 71% by weight (calculated and found). The M value is 8420 and the M value is 3140 and the Heterogeneity index 2.7. 259.4 g of dimethylaminoethanol are used for Neutralization of the acid added, the solids content increasing 60% is reduced. Water is added, whereby the solids content is reduced to 50% by weight. The viscosity is 20,000 centipoise at 25 ° C.

Example B12

Ethoxylation of hydrolyzed oligomer

The following ingredients are placed in an autoclave:

a. The hydrolyzed product of Example B5 (450 g) at 6.27 Milliequivalents of carbaxylate per gram of solids is in 90 parts Dissolved toluene and 10 parts of isobutanol, with a 55.6% by weight ige solution is obtained.

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b. Ethylene oxide (81.8 g)

c. Tetrapropylammonium bromide (1.25 g)

d. Toluene (50 g).

The constituents are stirred and heated ^{in an autoclave at 100 °} C. for a period of 4 hours. During this period the pressure drops from 2.1 to 0.35 ata. After cooling, the product is removed from the autoclave, which is rinsed with acetone. The rinse solutions are added to the product. In another vessel the product at 9O ⁰ C and a pressure of 10 mm Hg for a period of 2 hours is stripped. 525 g of a product with 1.05 milliequivalents of carboxylate per gram of solids and a hydroxyl number of 215 (corresponding to 50%. ': Hydroxyethyl methacrylate in the polymer) are stripped. This product is dissolved in water and DMAE at a pH of 9.0 to obtain an end product with the following properties:

Solids 73.3% pH 9.0

Viscosity 3300 centipoise

Weight average molecular weight 1220

Number average molecular weight 980

Heterogeneity Index 1.24 Example B13

The method and the device are similar to the method and the device according to Example B9. The polymerization is carried out for a period of 6 hours, the temperature between 146 and 154 ^° C. being maintained. The piston batch consists of

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415 g of butyl cellosolve and 30 g of 2-hydroxyethyl mercaptan. The initiator stream consists of 53.4 g of tert-butyl peracetate (75% in white spirit) .

The monomer flow is composed as follows:

Gram

n-butyl methacrylate 230

Methyl methacrylate 520

Methacrylic acid 250

After the 6 hour polymerization is complete, a scavenger is used to reduce the amount of unreacted monomer. The final solids content is 71.4% by weight (calculated and found). The M value is 5310 and the M value 1950 and the heterogeneity index is 2.6. 259.4 g of dimethylaminoethanol are added to neutralize the acid and reduce the solids to 61%. Then water is added to reduce the solids to 50% by weight. The viscosity is 10,000 centipoise at 25 ⁰ C.

Example B14

The method and apparatus are similar to the method and the
Device according to example B9. The polymerization is carried out over a period of 6 hours, the temperature between 146 and 154 ^° C. being maintained. The piston batch exists
from 415 g of butylcellosolve and 60 g of 2-hydroxyethyl mercaptan. The initiator stream consists of 8Q g of tert-butyl peracetate (75% in
White spirit). . The monomer flow is composed as follows:

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Gram 2626845 230 n-butyl methacrylate 520 Methyl methacrylate 250 Methacrylic acid

After the 6 hour polymerization is complete, a scavenger is used to reduce the amount of unreacted monomer. The final solids content is 69% by weight (found) while it is calculated to be 72%. The M value is 3650 and the M value is 1290, while the heterogeneity index is determined to be 2.8. 249 g of dimethylaminoethanol are added to neutralize the acid. The solids content is reduced to 60.9%. Then water is added. The solids content is reduced to 50%. The viscosity is 4900 centipoise at 25 ⁰ C.

Example C1

Hard coating system

The preliminary stability and compatibility test using the mixture of the colloidal solution polymer and the oligomeric copolymer is carried out first. Equal parts by weight of the oligomeric copolymer according to Example B1 and of the copolymer according to Example A5 are mixed, brought to a pH of 9.5 with dimethylaminoethanol and diluted with water to a total solids of 28%. The mixture shows no signs of gelation or phase separation when it is stored ^{at 60 ° C. for a period of 7 days.} Another aliquot stored at room temperature also shows no signs of gelation or phase separation. The solution itself is clear, as is a 38 μ film that has been poured from the solution and ^{burned at a temperature of 120 °} C. for a period of 20 minutes. The-

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This system is therefore acceptable for formulation into a coating .

From equal parts by weight, based on solids, Ti-Pure R-902 rutile titanium dioxide pigment and the copolymer latex according to
Example A5, which with water to a solids content of 25%
has been reduced and has been stabilized by adjusting the pH to 9.0 with dimethylaminoethanol, a mixture is prepared which is to be ground in a ball mill. Then _f 0 5% defoamer are added, and the mixture is ground in a ball mill for a period of 48 hours.

The following formulation (parts by weight) becomes a premix manufactured:

60 parts of the oligomeric copolymer according to Example B1,
reduced to a solids content of 40% with water

301 parts of hexamethoxymethyl melamine 100 parts isobutyl cellosolve (Union Carbide) 50 parts of n-butanol

50 parts of water.

2000 parts of the mixture milled in the ball mill and 750 parts of the copolymer latex from Example A5, reduced to a total solids content of 25% with water and solubilized at a pH of 9.0 with dimethylaminoethanol, are brought together with the premix. The coating constants of this system
are the following:

Titanium dioxide / binder: 5Q / 50 copolymer solids / melamine solids; 7Q / 3Q Total Solids: 46% Viscosity (Ford # 4 Cup): 80 seconds

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The mode of action in the case of direct roller application is observed using a Wagner coater test at fast, moderate and low speeds. The flow and the leveling of the coating are rated as very good to excellent. Fast, moderate and low speeds of this overdrawing device correspond to 90, 60, .bzw. 30 m per minute. The coating weighs 40 to 44 mg per 25 cm ² on the 40 kg tin plated steel backing. For convenience, a separate sample is prepared to test the film properties by potting on the tin plate with a wire wound rod. The coating is baked at 177 ° C for 10 minutes. The gloss at 20 ° is 69, at 60 ° 90. The resistance to damage is very good, the resistance of the like with respect to a sticking when the coated sheets front face to front face or front surface to the back surface for a period of 16 hours at 50 ⁰ C. 2.1 ata pressure and inspected for signs of sticking or damage. The GMX (General Motors Specification Test, which is carried out using an X-shaped coating) adhesion is okay in both dry and wet conditions (66 ° C water - 45 minutes). The gloss, flow and hardness of this system show that it is an excellent hard, lacquer-free white coating.

Examples C2, C3 and C4 oligomer acid content

To carry out these examples, the formulation and processing are the same as in Example C1, with the following components can be used:

The colloidally dissolved polymer to carry out these three components, games is that of example A3. In example C2 this is oli- '

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goitiere copolymers that of Example B1 (a butyl methacrylate / methyl methacrylate = 1/3 oligomer that hydrolyzes in this way that it contains 25% methacrylic acid). In example C3 that of example B4 is used (the same Oligomer that has been hydrolyzed and contains 15% acid). In example C4 that of example C3 (the same Oligomer that has been hydrolyzed and contains 7% acid).

As in example C1, the tests to determine the preliminary stability and tolerance give no indication of a Gelation or phase separation. The burned film is clear. Hence, these systems are acceptable for formulation into coatings .

The dope is prepared using the ball milling method and mixing method described in Example C1 is applied using the same crosslinking agent as well as the other components. A direct one Rolling on of coatings using the compositions of Examples C2 and C3 shows that they have excellent flow and Have flow properties. In contrast, the coating compound has according to example C 4 an unacceptable flow behavior. This is likely due to the fact that 7% acid is in the 01igomer component too low a content for an acceptable one are direct roller application.

When carrying out the other tests, coatings are obtained from the compositions of Examples C2 and C3 which are very resistant to water staining and have good adhesion to steel under sterilization conditions, ie after baking for a period of 50 minutes at 66 ^° C ^ the coating of example C2 is superior both in its flexibility, _a i _s also its damage resistance. The coating according to example C3 is less

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resistant to these special requirements.

Examples C5 to C11 Necessity of the binder components

The preliminary tests explained in Example C12 show acceptable stability and compatibility of the binder systems summarized in the table below. Coating compositions prepared using the ball milling and mixing steps described in Example C1 are applied to aluminum and tin plated steel substrates by direct roller application. An evaluation of the appearance of the coatings is summarized in the last column of the table. According to Examples C5, C6 and C1 , mixtures of solutions or colloidal solutions of materials with high molecular weight, oligomers and crosslinking agents are used. These mixtures work well with direct roller application. According to Example 8, a single polymer is used for the oligomer and the high molecular weight polymer of the mixture. This polymer has the same overall composition as the blend and about the same average molecular weight as the blend. However, it is homogeneous in terms of its molecular weight distribution, while the mixture must have at least two peaks in the molecular weight distribution curve. According to Examples C9 and C10, the components of Example C5 (or C6) are combined separately with the crosslinking agent. In each case an unacceptable coating is obtained. The oligomer component with no crosslinking agent also results in a topcoat which is unacceptable in appearance when applied using a direct roller applicator. From these results it can be seen that the excellent mode of action of the coating compositions according to the invention neither the components alone nor the overall compositions as well as the

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is attributable to the average molecular weight. Excellent, Formulations to be applied directly with a roller applicator become more compatible through mixing Systems, namely a very low molecular weight oligomer, a high molecular weight polymer and a Crosslinking means derived from an aqueous medium.

In the table, the parts by weight of the coating components relate to to the examples marked accordingly. Thus “44 A3” means 44 parts by weight of the composition according to Example A3.

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co
co
co
ro

Binder system (parts by weight plus 30 parts of hexamethoxyethyl melamine crosslinking agent)

Bei- polymer colloid]
game polymer solution

Solvent system

coating

70 B10

44 A3 44 A3

44 A3

70 A3

e oligomer Volume parts of the solution with
telcomponents percent
sentence
Pests viscosity
(Remark 1) Direct orders
by means of
a roller, off
see I. 26 B1 7 n-butanol / 93 water 47.5 66 excellent Cn
VO
I. 26 B1 6 2-butoxyethanol / 7 n-
Butanol / 87 water 47.5 66 excellent 26 B9 6 2-butoxyethanol / 7-n-
Butanol / 87 water 47.0 57 excellent - 20 2-ButcKyäthanol / 80 water 45.2 61 unacceptable - the same as in
Example C8 37.2 63 unacceptable 70 B1 the same as in
Example C8 58.3 71 unacceptable 100 B1
(no ver
wetting agent) the same as in
Example C8 57.4 31 unacceptable

Note 1: Flow time, in seconds, from Ford cup no.4.

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Example C12

Selection of stable, compatible systems

A series of preliminary tests are carried out using equal weight blends of the oligomeric polymer as well as the polymer high molecular weight at 28% total solids in one carried out aqueous solution which has been adjusted to a pH of 9.5 using dimethylaminoethanol. The tests are as follows:

Stability: The mixture is kept at 60 ^° C. for a period of 7 days. Partial or complete gelation of the sample or visible phase separation is an indication of instability.

Solution Compatibility: The mixture will be assessed for its clarity after mixing as well as after aging at room temperature observed over a period of 14 days. A phase separation, an opacity or cloudiness sufficient to make a newspaper illegible when it is 2 cm thick Mixture is read shows the lack of compatibility.

Film compatibility; The mixture is poured onto a metal substrate to produce a dry film with a thickness of 38 μ, which is ^{baked at 120 °} C. for a period of 36 minutes. Cloudiness or lack of clarity indicates that there is no tolerance.

The results of these tests, which were applied to some of the polymers in the A and B series of examples, are summarized in the following table:

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co ο co

Colloidal
Solution of the
Polymers More oligonuclear . BS Example A5 Example, B5 Il Il B12 Il . Il B7 Il It . B8 Example A4 Ex. B5 Μ Il B12 Il Il B7 Il Il B8 Example A3 Ex. B5 Il Il B12 Il Il B1 Il Il B7 Il Il B6 Il U B2 Il Il BS Example A2 Ex. B5 Il Il B12 Il Il B7 Il Il

Stability Solution compatibility

Well clear Well cloudy Well slightly cloudy Well cloudy Gels - Gels - Well slightly cloudy Gels - Well clear Gels - Well clear Well clear Gels - separation - separation - Well opaque Gels - Gels - Gels

Film compatibility

clear clear clear clear

clear clear

clear clear

Acceptable

clear

: a I. ro no cn cn Yes I. no no no Yes no Yes no Yes Yes no no no no no no no

K) CD

OO

-F-

The components of acceptable mixtures become clear and pigmented Coatings as formulated in Examples C1 and C23 to C26. The coatings are easy to transfer and flow also good if they are applied directly by rollers. Similarly, the coatings are also suitable for application after less demanding processes, for example by roll reverse coating and by spraying, brushing on, flowing on and by other known methods.

Example C13
Crosslinking agent component

A stable polymer blend is made using the following formulations:

Component Weight Volatile matter

Total polymer DMAE BuETOH nBuOH H ₃ O

- 109 g 15 g 8.4 g

Ex. A3 180 G 63 G 8th , 0 G Ex. B1 62 G 37 G 1 , 6 G DMAE 8th G - 8th , 0 G

Total 250g 100g 17.6g 15g 8.4g 109g

(DMAE is methylaminoethanol, BuETOH is 2-butoxyethanol, nBuOH is n-butanol),

650 g of TiPure R-902 titanium dioxide are added to 350 g of the mixture to produce a paste. The paste is made on a three roll mill ground, then with a mixture of 788 g of the mixture of 80 g of N, N-di- (3-hydroxyethyl) adipamide and 250 g. Water to form a base paint with a solid mixed content of 55.8%. This paint is mixed with 704 g of water and 176 g of 2-butoxyethanol to produce a coating composition diluted to a solids content of 43% and a viscosity of 43 seconds using the # 4 Ford Cup.

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26268A5

The application of this mass to a tin-plated steel plate with a weight of 40 kg gives a very good coating.

Similar results are obtained using other crosslinking agents obtained instead of the substituted adipamide, such as

1) IONAC PFAZ-300 and IONAC PFAZ-301, each water-soluble Crosslinking agents containing three aziridine groups per molecule (Ionac Chemical, a division of Sybron Corporation, Birmingha, N.J.)

2) Bis-Ν, Ν, N -trimethoxymethylureidomethyl ether.

3) A polymeric soybean oil epoxide with the following properties:

Molecular weight 1000, viscosity (25 ° C) 350 cps

Acid number 0.6

Saponification Count 182

Oxir number 6.4

Iodine number 13

4) pentamethoxymethyl methylol melamine.

5) Aqueous emulsion of bisepoxides, made from the following ingredients:

33.5 parts of Epon resin 1007, an epichlorohydrin / bisphenol A condensate having a molecular weight of approximately 3700 (Shell Chemical Co.) *

3.7 parts Epon Resin 1001, a lower condensate than Epon Resin 1007 with a molecular weight of approximately 1000 (Shell Chemical Co.),

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5.0 parts Alipal EP-110, a surfactant

(G.A.F. Corporation),

12.6 parts deionized water, first addition, 26.2 parts deionized water, second addition

16.9 parts of Natrosol 250-HR, 1% in water, a hydroxy

ethyl cellulose (Hercules, Inc.).

The two Epon resins are dissolved in an 80/20 (by volume) solution of ethyl amyl ketone / cyclosol solvent 63, a high-boiling aromatic solvent (Shell Chemical Co.) to form a 75% by weight solution. The emulsion is made as follows:

The Epon Resin 1007 and 1001 solutions as well as the Alipal EP-110 are added to a jacketed Waring mixer with thorough stirring. The temperature is increased to 66 ^° C. by heated water in the jacket. Mixing is continued for a period of 5 minutes after the temperature has been reached.

The first addition of water is made slowly over a period of 3 minutes. The water is mixed in thoroughly with vigorous stirring over a period of an additional 5 minutes. The temperature is kept at 66 ^° C. during this production stage.

The mixture of the Natrosol solution and the last portion of water is then added over a 3 minute period with moderate agitation. The pH of the system is increased to 7.0 7.5 adjusted with dimethylethanolamine with stirring.

Examples C14 through C17

Molecular weight of the oligomer

The preliminary tests discussed in Example C12 show one

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acceptable stability and compatibility of the binder systems given in the table below. The coating compositions that produced by the ball milling method and the mixing method according to Example C1 are coated with aluminum and tin plated steel backing applied by direct roller application. An evaluation of the appearance of the coatings can be found in the 6th and 7th columns of the table.

Example C14 is similar to Examples C2 and C5, but with a sample of oligomers prepared as a replicate of Example B1 is used, with a solvent system from 2 parts of 2-butoxyethanol and 1 part of n-butanol for Used. The other three examples in this group, namely C15, C16 and C17, are given using one over free Radical initiation carried out and represent a series with changing molecular weight. To carry out of Example C15 becomes a weight average oligomer the molecular weight of 8420 was used. This has unacceptable flow and leveling properties when it is passed directly through a Roller is applied. The oligomer with the next lower molecular weight, namely with an average weight of 5310 according to Example C17, has an acceptable coating for Episode.

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CTS CD CD OO OO ΙΌ

Binder system

Example Colloidal Oligomeric Polymer Solution

coating

Total solids viscosity,% seconds

C14

C15 C16

Example A3

Example A3 Example A3

Example B1

Example B11 Example B13

44.7

44.7 44.7

C17 Example A3

Ex. B14 44.7

72

80 64

60

Oligomer properties % 134 O ⁴ HI 2
Direct application
with a roller,
Appearance shine 177 O ⁴ 3140 1/3 excellent
net 8420 1950 2.7 unacceptably massive 5310 2.7 good massive
until
high

high

3650

1290

2.8

Determined using a No.

Determined by the quality of the flow of the coating, which has been applied directly by a roller.

A repetition of the same preparation as in Example B1. The properties are measured before hydrolysis.

Binder composition: 44 parts of colloidally dissolved polymer, 26 parts of oligomer, 30 parts of hexamethocymethylmelamine, based on the weight of the solids,

Solvent in 80 parts of water, 13 2-butoxyethanol, 7 n-butanol, based on the volume.

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Examples C18 to C22

Comparison with other binder systems

Commercially available metal decoration binder systems are ' to coatings for application by direct-working roller applicators formulated. The results summarized in the following table are achieved. Coating compositions that by the ball milling and mixing method described in Example 1 are made on steel substrates plated with aluminum and tin by direct application by means of applied to a roller. All contain an equal weight of TiOp and binder solids. The assessment of the appearance of the Coating is summarized in the second line of the table. The fourth line indicates the simplicity with which the roller applicator device can be cleaned when the specified coating formulation is used.

Example C2 in the table corresponds to that described above. The binder according to Example C18 is a three-component mixture, which consists of the following components:

1. An emulsion copolymer made from styrene, n-butyl acrylate, Methacrylamide and methacrylic acid,

2. an isopropanol solution of a stopped with methanol Urea / formaldehyde condensate and

3. a solution of a methanol-terminated melamine / formaldehyde condensate in equal parts isopropanol and isobutanol.

It also contains Carbowax 2OM (polyethylene glycol polymer) as a rheology modifier in an amount that is 1.3% of the binding agent.

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means corresponds to. The binder according to Example C19 is a Mixture of component 3 according to Example C18 and the colloidally dissolved copolymer of methyl methacrylate, ethyl acrylate, hydroxypropyl methacrylate and methacrylic acid with the same rheology modifier as in Example C18. In example C20 a mixture of a water-soluble polyester resin and a methoxymethylmelamine is used as a binder. One with water dilutable copolymer of methyl methacrylate, n-butyl acrylate, Hydroxyethyl methacrylate and methacrylic acid are the binders according to Example C21. Example C22 is different from all of them others in that it is a copolymer of styrene and ethyl acrylate and methacrylic acid mixed with a diepoxide made from bisphenol A and epichlorohydrin dissolved in one organic solvent, namely Solvesso 150 (a high-boiling aromatic) and cellosolve acetate.

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Property Example C2 Example C18 Example C19 Example C20 'Example C21 Example C22

σ »ο co co

mixture

Flow of the coating applied directly with a roller

Gloss: 60 °

65 90

Modified modified water-dissolving emulsion colloidal poly solution ester Water-soluble acrylic compound

Solvent-soluble acrylic compound

unacceptably unacceptable unacceptably unacceptably excellent

Time in the open off state and draws cleaning

23 65

moderate very bad good ^ 84
Well

excellent

Example C1

Selection of stable, compatible systems

A series of preliminary tests is carried out using mixtures with equal weights of the oligomeric polymer and the high molecular weight polymer for total solids of 28% in an aqueous solution that has been adjusted to a pH of 9.5 with dimethylaminoethanol, carried out. The following tests are carried out:

Stability: The mixture is at 60 ⁰ C during a

Period of 7 days held. A partial or complete gelation of the sample or a visible phase separation indicates instability.

Solution Compatibility: The mixture will contribute to its clarity after mixing as well as after aging Room temperature for a period of Observed for 14 days. A phase separation, opacity, or cloudiness sufficient to To make a newspaper illegible if it's' through a 2 cm thick layer of the mixture is read, indicates the lack of compatibility.

Film compatibility: The mixture is poured onto a metal base to form a dry film with a thickness of 38 μ. The film is then burned at a temperature of 120 ^° C. for a period of 30 minutes. A cloudiness or a lack of clarity indicates that there is no tolerance.

The results of these tests, which applied to some of the polymers in the

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A and B series of examples are used are summarized in the following table:

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Colloidal Oligomers Stability Solution Compatibility Film Compatibility Polj / mer solution

Ex. A5 Ex. B8 Well clear Il Il B5 Well cloudy Il Il B12 Well slightly cloudy 11 Il B7 Well cloudy Ex. A4 Ex. B8 Gels - Il Il B5 Gels «Μ Il Il B12 Well slightly cloudy ο
CD It it B7 Gels - CO Ex. A3 Ex. B8 Well clear Il Il B5 Gels - Il Il B12 Well clear <—> Il Il B1 Well clear Il Il B7 Gels - Il Il B6 separation - Il Il B2 separation - Ex. A2 Ex. B8 Well opaque Il Il B5 Gels - Il Il B12 Gels - Il Il B7 Gels

wearable: ; Annehnibar clear Yes clear no clear Yes clear no - no - no clear Yes - no clear Yes - no clear Yes clear Yes - no - no * - no clear no - no - no no

The components of acceptable mixtures become clear and pigmented Coatings as formulated in Examples C23 to C26. The coatings can be easily passed through when applied directly transfer an applicator roller and flow well. Similarly, the coatings are also suitable for post-application less demanding methods, for example by reversing— roller coaters, by spraying on, by brushing on, by flowing on and by other known methods.

Example C23 __

Lubricant coating

The materials are in open metal cups with a suitable Capacity using a laboratory propeller mixer or similar device is processed to a to ensure uniform mixing of the ingredients. the Components are generally introduced into the vortex created in the liquid by the mixer, the specified order is adhered to.

To 1500 g of high molecular weight component A, namely the polymer according to Example A3, with a solids content of 36%, 1150 g of water and 50 g of Dimethylamxnoäthano1 are added, creating a solubilized system with a pH of about 9.0 with a solids content of 20%. After sufficient stirring to achieve a uniform state, 2500 g of this solubilized system are in a transferred to another vessel, whereupon 1560 g of the partially hydrolyzed Oligomers according to Example B1 with a solids content of 46% are added. Then the addition of 60 g of 2-butoxyethanol, 100 g of n-butanol and 520 g of water. That Product is a lubricant coating with approximately 26% solids, a pH of approximately 9.5 and a viscosity of 80 centi-

609882/1041

-Vt-

poise (approx. 30 seconds in a Ford No. 4 cup) at 25 ° C. This coating is also required if a solids setting is required is suitable for use as a paint for metals, plastics, wood and other substrates.

Example C24 lubricant coating

The coating will partially hydrolyze with the as in Example C23 Oligomers, prepared according to Example Bt, prepared, with the exception that the final solubilization of the oligomer is achieved using aqueous ammonia (28% aqueous Ammonia) instead of dimethylaminoethanol. The lubricant coating produced has a solids content of about 26%, a pH of about 9.6 and a Viscosity of 75 centipoise (about 29 seconds in a Ford cup No. 4) at 25 ° C.

Similarly, other compatible mixtures of high molecular weight components, namely the example- Series A, as well as the oligomer components, specifically of the example series B, used for the formulation of lubricant coatings. Smaller settings, in particular with regard to the amounts of water, amine and solvent, for setting the respective Solids, the "respective pH value as well as the respective viscosity values are to adapt the formulation to the respective Applications possible, namely "taking into account the temperature, the type of application device, of the substrate and the speed of application.

Example C25

Thermoplastic varnish

A paste is made from 600 parts of a pigment-like titanium dioxide

609882/1041

(Ti-Pure R-902 - DuPont) and a mixture of 290 parts of the solubilized polymer according to Example A1 and 110 parts of the oligomer of Example B6, the mixture being diluted with water to a solids content of 26%. These Paste is milled on a three roll mill until the pigment disperses to a reading of about 8 on a Hegman machine is. Usually two or three passes are required in the mill. The paste is made with 3450 parts of a mixture of the polymer according to Example A1 and the oligomer according to Example B6 are mixed in the same ratio as indicated above and also to a solids content of 26% by the Addition of water stopped. The paint produced has a pigment: binder ratio of 40:60, and based on total solids, a total solids content of approximately 34%; and one pH around 9.3. This varnish is used for a variety of decorative coatings on various substrates, such as made of metal, plastics and wood. Further dilution with water is often necessary. For one Spray application, dilution to a viscosity of 25 seconds in a # 4 Ford cup is necessary for one Application by means of a roller, a dilution up to a viscosity of 60 seconds in the same cup and for a dip training a decrease to 30 seconds in the same Cups.

Example C 26
Sanding sealing tool for wood

A binder mixture of 30%, based on the weight of the Polymer solids, of the high polymer according to Example A4, which is solubilized with 2-ethylhexanol, and 70%, based on the weight the polymer solids, the oligomer according to Example B3 is diluted to a solids content of 26% with water. A

609882/1041

Cowles Dissolver (Cowles Dissolver Co.) / The low speed is running, is filled with the following components:

100 parts of water

100 parts of the binder mixture with a solids content from 26%

3.0 parts F ^ amaster TCX (Diamond Shamrock Corporation)

193 parts of barite - 30 μ BaSO ₄

290 parts Duramite - 10 μ CaCO- (Thompson Weinman Co.)

The speed is increased to effect grinding and is maintained for a period of approximately 15 minutes, to achieve good grinding. While stirring more slowly, the sealant is mixed with 610 parts of the binder mixture mixed with a solids content of 25%. The product has a pH of approximately 9.0 and is optionally further reduced with water to a viscosity of 40 seconds Use a # 4 Ford cup diluted. It is applied to raw wood as a sand sealant.

Example C 27

Comparison with a commercially available lubricant coating

The same device is used as in Example C24. The general methods are also similar. With suitable stirring, a premix is prepared consisting of 450 parts of the oligomer according to Example B1 with a solids content of 40%, 50 parts of n-butanol, 15 parts of 2-butoxyethanol and 120 Share water is made up. The polymer is placed in a separate container according to example A3 with a total solids content of 36% to a solids content of 20% with an 80/20 mixture Diluted water and isopropanol. The pH is below 9.0 Discontinued use of dimethylaminoethanol. 600 parts of the

60988 2/1041

Polymers according to Example A3, now with a solids content. ■ of 20%, are added with stirring to the above premix to produce a lubricant coating having a pH of 9.7 and a viscosity of 185 centipoise. This coating formulation is stable as evidenced by the fact that the pH remains at 9.7. The viscosity is only 200 centipoise after the formulation has ^{been stored for a period of 100 hours at 60 °} C. when an accelerated test was carried out. Calculated on a solids basis, this formulation contains 60 parts of the oligomer according to Example B1 and 40 parts of the polymer according to Example A3.

Using essentially the same method, a second formulation is made produced, in which the solids content is 50 parts of the oligomer according to Example B1 and 50 parts of the polymer according to example A3. A third formulation has the following composition: 10 parts of the oligomer according to the example B1, 85 parts of the polymer according to Example A2 and 5 parts of the polymer according to Example A3 (as% by weight solids). Films (when dry) approximately 5 microns thick are made from each of these formulations on cold rolled steel infused using a wire-wound rod (No. 6). Another plate comes with a commercially available one Lubricant coated to a similar thickness. The panels are then subjected to standard tests. The results obtained are summarized in the following table:

609882/10 41

σ> σ co οο

Composition based on Examples A and B versus a commercially available resin
Composition B1 / A3 50/50 B1 / A3 60/40 B1 / A2 / A3 10/85/5

none none none

Flash rusting

Removability

Air-dried

Dried 5 χ at 71 ° C

Manufacturing blocking

Commercially available lubricant
(CL)

none

dissolves' dissolves and stands out in strips

then dissolves

dissolves

dissolves in lorm einar foil
away

no scoring no scoring no scoring metal
of metal of metal

medium to good

Well

Moisture resistance

Solids Input,%

Stability (60 ° C / 100 ok hours)

well, something. very good, similar to CL
worse than CL

good, only slightly worse than CL

25th

in order

Well
25th

in order

dissolves dissolves very well on massive notches

Well
in order

ro cn co

The tests are described below:

1. Flash rusting

While the coating is drying and immediately afterwards, the plate is for the appearance of discoloration typical of rusting.

2. Removability

The plate is either air or force-dried and then immersed ^{in a 1% sodium metasilicate solution at 60 ° C. for 30 seconds.} Dissolution or lifting of the coating is observed. .

3. Processing

The coated metal is tested in an Erichsen deep drawing tester (manufactured by Erichsen, Hemer-Sundwig, West Germany) verforint. The coating is then removed, whereupon the metal is examined for notches.

4. Blocking

After drying, the plates are examined for front-to-front and front-to-back blocking after they have been ^{pressed together for a period of 1 hour at a temperature of 54 °} C. under a pressure of 2.1 ata . Both the extent of sticking and the extent of damage are assessed.

5. Moisture resistance

After the panels have been air dried for a period of 24 hours, they become an atmosphere

609882/1041

2626B45

Exposed to 100% relative humidity at 38 ° C. The degree of roasting is noted during the first 100 hours.

It can be seen that · the formulations according to the invention the im Commercially available lubricants in the processing test via " and, in some cases, not as good as in the case of the blocking test. In terms of removability it is it is generally convenient for the coating to dissolve, as is the commercially available lubricant and two of the three formulations according to the invention. In some cases it is preferable that the coating can be peeled off as a film, as is stated in the third formulation in the table.

When carrying out further investigations regarding the ratio of the experimental B1 to the experimental A3 component systems it was found that an increase in the B1 concentration above the concentration observed in these examples In addition, the moisture resistance and processing properties gradually decreased. One Increasing the A3 content gradually increases the blockage.

Example C28:

Lubricant coatings for metals

Using the methods described in Example C27, other coatings are prepared on cold rolled steel in piled up in the manner described and in. Compared to a commercially available resin-based lubricant coating examined. As an example for the production of these coatings, the most complicated production method was used, where a formulation was employed containing two high molecular weight copolymers and one oligomeric copolymer. The pre

609882/1041

mixture consists of 25 parts "of the oligomer from Example B1 with a solids content of 40%, 10 parts of water and 5 parts 2-butoxyethanol. The high molecular weight component is made up from 25 parts of the polymer of Example A2 with a solids content of 20% ', which at a pH of 9.3 with Dimethylmaihoäthanol has been solubilized, 267 parts of the material according to Example A2 with a solids content of 30%, the pH 8.2 solubilized with DMAE and 53 parts water. The formulations have a total solids content of 25%, a pH of 9.1 and a viscosity of about 200 centipoise (50 to 60 seconds in the # 4 Ford cup) at 25 ° C.

Films made from these materials as well as from the commercially available one

Resin based lubricants are poured onto steel and how

tested in example C27 ..- The results are in the table below summarized.

609882/1041

example C28a C2S4? ' very good Air dried C 28c C'28d C28e Dimensions A2. A2 / B1 90/10 Well A2 / A3 90/10 A2 / B1 85/10/5 In the trade he
Lubricant Flash rusting none none in order none none none • Removability moderate Well 25th Well excellent Well Processability no indented traces of
ben of. Notches
metal no Einker
ben of
metal no notching
• from .Metall massive one
■ exercises blocking Well very good very good very good CD
(- ι Moisture
resistance bad bad Well Well CD Stability ³ in order in order in order CO
CO
NJ Solids,% 25th 25th 25th CD
-P- coating on the

'Excellent front to back and good front to front
The mass is aged for 100 hours at 6O ⁰ C.

The results in this table show that the omission of the oligomeric copolymer from the formulation of the Examples C28a and C28c have poor moisture resistance and thus results in unacceptable properties.

609882/1041

Claims (26)

Claims 1. ^ Coating compound, characterized by an aqueous alkaline is made from the following components: A) an addition copolymer composed of (1) 3 to 30% by weight of an olefinically unsaturated monomer which contains a carboxyl group, or a mixture of such monomers, (2) at least an ester of acrylic acid and / or methacrylic acid and optionally (3) one or more other olefinically unsaturated monomers, the total amount of (1), (2) and (3) being 100%, the weight average molecular weight of the copolymer is between 10,000 and 500,000 and this is in the form of a solution or a colloidal solution is present in an aqueous phase, and B) an oligomeric addition copolymer of (1) at least one ester of acrylic acid and / or methacrylic acid, (2) 9 bis 50% of an olefinically unsaturated monomer with at least a carboxyl group and optionally (3) one or more other olefinically unsaturated monomers, the total amount of (1), (2) and (3) is 100% and the weight average molecular weight of the copolymer varies between 400 and 6000 and the molecular weight distribution is such that the heterogeneity index is 3 qder less. 2. Composition according to claim 1, characterized in that it is a thermosetting compound suitable for a roller coating of Substrates is suitable, with component (A) in solution in the form of a salt of a volatile amine or of ammonia is present, and wherein the mass is further (C) contains a crosslinking agent selected from the group consisting of the following: 609882/1041 (a) an alcohol-modified aminoplast resin, which consists of the condensation product of an aldehyde and a compound,
which is selected from ureas, polyamides and triazines, (b) a polyepoxide that has at least two adjacent epoxy groups contains, the epoxy oxygen atom with adjacent carbon atoms is linked, (c) a polyaziridine which contains at least two aziridinyl groups, and (d) a ß-hydroxyalkylamide of the formula: R ³ R ^e.g. 0 0 R ² R ³ (HOC — C — NC-) Z (-i — M — C-COH) Li, L ⁿ . · .1, LL ⁿ R ¹ ■ -R ¹ R ² R * which contains at least two β-hydroxyalkylamide groups, wherein Z is a bond, hydrogen, a monovalent or polyvalent one
organic radical referring to saturated or unsaturated alkyl
with 1 to 60 carbon atoms is aryl, tri-lower-alkylenamino or an unsaturated radical, R is hydrogen, lower-alkyl or hydroxyalkyl, 2 3 R and R are hydrogen, straight-chain or branched lower Al-. kyl, or a substituent R and an adjacent substituent R together can form a saturated cycloalkyl, η is an integer of 1 or 2,., and η is an integer, from 0 to 2, where, if η is 0 and η has a value greater than 1, a polymer or copolymer formed from the β-hydroxyalkylamide 609882/1041 when Z is an unsaturated radical, the material being in In the form of a dispersion or solution in water and in the mixture, based on solids, C) 5 to 50% by weight and A) plus B) makes up 95 to 50% by weight, where A) in an amount of 95 to 25% by weight and B) in an amount of 5 to 75% by weight, based on the total amount of A) plus B) is present, and wherein the mixture is a volatile aqueous phase of 70 to 95% by volume Water and 5 to 30% by volume of volatile organic solvents and contains between 15 and 70% by weight of solids, while the viscosity between 25 and 150 seconds, measured in a No. 4 Ford cup at 25 ° C. 3. Composition according to claim 1, characterized in that the amount of component (A) between 90 and 10% and the amount of the component (B) varies between 10 and 90 percent on a solids basis by weight. 4. Composition according to claim 1 or 3, characterized in that the aqueous phase consists of 70 to 95% by volume of water and 5 to 30% by volume consists of volatile organic solvents, the mass having a solids content between 15 and 70% by weight, a pH between 8.0 and 9.8 and a viscosity between 25 and 150 seconds, measured in a Ford cup No. 4 at 25 ° C, having. 5. Composition according to one of the preceding claims, characterized in that that component (B) selected from (1) approximately 50 to 91% by weight of mer units based on one or more monomers made of styrene, £> C-methyl is ty ro I, acrylonitrile, vinyl chloride, Vinyl acetate, vinyl pyrrolidone, vinylidene chloride and monomers of the formula: R 0 I Ii = C C- 609882/1041 can be recycled, where in the formula R is H or methyl and Y amino, (C ₁ -C ₄ ) -alkylamino, di- (C ₁ -C ₄ ) -alkylamino, hydroxy- (C ₁ -C ₄ ) -alkylamino, bis-hydroxy- (C ₁ -C ₄ ) -alkylamino , (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkylamino, bis- (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkylamino or a group of the formula -OR , where R ⁴ ..- rT. (C ₁ -C ₂₄ ) -Alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₁ -Cg) -aminoalkyl, alkylaminoalkyl with up to 6 carbon atoms, dialkylaminoalkyl with up to 6 carbon atoms, a group of the formula -A ¹ N (R ³ ) CXNR ¹ R ² , (C ₂ -Cg) -Isocyanatoalkyl, (C ₂ -Cg) -hydroxyalkyl, 1, S-oxazolidin-S-yl- (C ₂ -C ₄ ) -alkyl, optionally with up to two (Cj-C ₄ ) -alkyl substituents on the oxazolidinyl ring, allyloxyalkyl with up to 12 carbon atoms, alkoxyalkyl with up to 12 carbon atoms, aryloxyalkyl or aralkyloxyalkyl with up to 12 carbon atoms, aralkyl with up to 10 carbon atoms, acryloyloxy- (C ₁ -C ₄ ) -alkyl, methacryloyloxy- (Cj-C ₄ ) -alkyl or a polymerizable monoethylenically unsaturated molecule which has a cyclic ureido group of the formula: A. contains where R from H, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms or Alkoxyme.thyl with 2 to 5 carbon atoms consists, A is alkylene of 2 to 8 carbon atoms, 1 2 R, if not directly connected to R, H, phenyl, methylbenzyl, Benzyl, cyclohexyl, alkyl of 1 to 6 carbon atoms, hydroxyalkyl with 1 to 6 carbon atoms or N-alkoxyalkyl with 2 to Carbon atoms is 609882/1041 2 '1 R, if not directly connected to R .., H, phenyl, methylbenzyl, Is benzyl, cyclohexyl or alkyl of 1 to 6 carbon atoms, 1 2 R and R, if directly connected to one another, form the morpholino radical -C ₂ H ₄ OC ₂ H ₄ -, the piperidino radical - (CH ₂ ) ₅ ~ or the pyrrolidino radical - (CH ₂ ) ₄ -, X is hydrogen or sulfur, A is alkylene having 2 to 3 carbon atoms and R is selected from the group consisting of H, -CH ₂ OH and -CH ₂ OCH ₃ , and (2) 9 to about 50% carboxylic acid mer units, which can be derived from the monomers acrylic acid, methacrylic acid or itaconic acid. 6. Composition according to one of the preceding claims, characterized in that component (B) has a heterogeneity index of less than 1.5 and a weight average molecular weight between 500 up * 2500, 7. Composition according to one of the preceding claims, characterized in that that component (B) contains units based on esters or amides of acrylic acid or methacrylic acid or mixtures decrease from these substances with one another or with other olefinically unsaturated monomers. 8. Composition according to one of claims 5 to 7, characterized in that that R stands for methyl and R is a (C.-Cg) -alkyl. 9. Composition according to one of the preceding claims, characterized in that that component (B) is an alkoxide polymerized Polymer, wherein at least 80% by weight of the polymer is made up of molecules with chain lengths of from about n / 3 to about 3.3n mers exist, where n * is the average number of Mers in the Polymer chain means. 609882/1041 10. Composition according to one of the preceding claims, characterized in that that the alkoxide polymerized polymer is a hydrolysis product of a polymer from Mers of the structure: R '■ · .. *. -CH ₂ -C- O = COR ¹ * ·. · 4th
is, in which R and R have the meanings given above. 11. Composition according to one of the preceding claims, characterized in that the ester of acrylic acid or methacrylic acid or a mixture thereof of component A} contains a group consisting of (C.-C ₃₄ ) -alkyl, (C2 ~ C ₄ ) - Alkenyl, (C ₁ -Cg) -aminoalkyl, alkylaminoalkyl with up to 6 carbon atoms, dialkylaminoalkyl with up to 6 carbon atoms, a group of the formula -A ¹ N (R ³ JCXNR ¹ R ² , in which R is selected from H, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms and alkoxymethyl having 2 to 5 carbon atoms is selected A is alkylene of 2 to 8 carbon atoms, 1 2 R, if not directly connected to R, H, phenyl, methylbenzyl, Benzyl, cyclohexyl, alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 1 to 6 carbon atoms or N-alkoxyalkyl with 2 to 6 carbon atoms is, ■ 2 1 R, if not directly connected to R, H, phenyl, methylbenzyl, Is benzyl, cyclohexyl or alkyl of 1 to 6 carbon atoms, 1 2 R and R, if directly connected to one another, represent the morpholino radical -C ₃ H ₄ OC ₂ ¹¹ A "^ en piperidino radical - (CH ₂ J ₅ - or the pyrrolidino radical - (CH ₃ J ₄ - form, and X means oxygen or sulfur, 609882/1041 (CU-Co) -Isocyanatoalkyl, (C ₃ -C ₀ ) -hydroxyalkyl, 1,3-oxazolidin-3-yi- (C ₂ -G ₄ ) .- alkyl, optionally with up to two (Cj-C ₄ ) Alkyl substituents on the xazolidinyl ring, allyloxyalkyl with up to 12 carbon atoms ,. Alkoxyalkyl with up to 12 carbon atoms, aryloxyalkyl or aralkyloxyalkyl with up to 12 carbon atoms, aralkyl with up to 10 carbon atoms _r acryloyloxy- (C ..-- C ₄ ) -alkyl, methacryloyloxy- (C.-C ₄ ) -alkyl or polymerizable monoethylenically unsaturated molecules that have a cyclic ureido group of the formula: K — c:] sr - R- are selected, where A is alkylene having 2 to 3 carbon atoms, R ^{5 is} E, -CIL, OH or -CE-OCE- and. ■ X is oxygen or sulfur. 12. Composition according to claim 11, characterized in that the ester is a (C ₁ -C ₁₂ ) ~ acrylate or methacrylate, 13. Composition according to claim 12, characterized in that the ester is a (C.-C ₄ ) acrylate or methacrylate. 14. Composition according to one of the preceding claims, characterized in that that component (A) consists of a copolymer of a '(C.-C.) ester of acrylic acid and / or methacrylic acid and 3 to 30% carboxylic acid monomers selected from acrylic acid, methacrylic acid and ita-conic acid. 15. Composition according to one of claims 1, 2 and 5 to 14, characterized 609882/1041 characterized in that component (C) is a crosslinking agent which is an alcohol-modified aminoplast resin, which consists of the condensation product of an aldehyde with a urea or a melamine. 16. Composition according to one of claims 1, 2 and 5 to 15 in pigmented or non-pigmented thermosetting form suitable for direct application with a roller on substrates is characterized by a stable aqueous alkaline mixture of the following components: A) a copolymer of (1) 20 to 50% by weight styrene, methyl methacrylate or both compounds, 40 to 60% butyl acrylate and 10 to 20% methacrylic acid, the weight average being des Molecular weight of the copolymer between 20,000 and 75,000 lies, B). a partially hydrolyzed anionically polymerized Addition copolymers of methyl methacrylate and butyl methacrylate with an acid number between 100 and 200, the weight average molecular weight fluctuating between 500 and 2500 and the molecular weight distribution is such that the heterogeneity index is 1, -5 or less and C) a condensation product modified with a monomeric alcohol of formaldehyde and melamine in the form of a dispersion or solution in water, in which, based on solids, C) 15 up to 40% by weight and A) plus B) 85 to 60% by weight * and A) in an amount of 75 to 50% and B) in an amount of 25 to 50%, based on the total weight of A) plus B), wherein the mixture further contains a volatile aqueous phase consisting of 80 to 95% by volume of water and 5 to 20% by volume volatile organic solvents, and wherein further, the mass has 15 to 20% by weight solids and a vis- §09882 / 1041 viscosity from 25 to 150 seconds, measured in the Ford cup No. 4 at 25 ° C. 17. Composition according to claim 16 _r characterized in that - that the Äminoplastharz consists of Hexamethoxymathylmelaiain or Pentamethoxvmethylinelamin. 18. Composition according to one of claims 1 and 3 to 14 in pigmented or non-pigmented form, which is suitable for direct application by rolling onto substrates through a stable aqueous alkaline mixture of the following components: A) an addition copolymer composed of (1) 20 to 50% by weight of styrene, Methyl methacrylate or both compounds, 40 to 60% butyl acrylate and 10 to 20% methacrylic acid, with the weight average the molecular weight of the copolymer between 20,000 and 75,000 is, and B) a partially hydrolyzed alkoxide polymerized addition copolymer of methyl methacrylate and butyl methacrylate with an acid number between 100 and 200, the weight average being the molecular weight is between 500 and 2500 and the molecular weight distribution is such that the heterogeneity index is 1.5 or less, and in the mixture, based on solids, A) 70 to 20% by weight and B) 30 to 80% by weight, and the mixture has a volatile aqueous phase which consists of 70 to 95% by volume of water and 5 to 30% by volume of volatile organic solvents, and wherein furthermore the mass has a solids content between 15 and 70% by weight and a viscosity between 25 and 150 seconds, measured in a Ford cup no. 4 at 25 ⁰ C, and has a pH between 8.7 and 9.5. 609882/104 19. Procedures for lubricating, impregnating or otherwise Coating a surface or a substrate, characterized in that that on such a surface or on such a substrate a mass according to one of the preceding Claims is applied. 20. The method according to claim 19, characterized in that a mass according to any one of claims 1, 2 and 5 to 17 on a substrate by direct application by means of a roller and through Heating the coating until it is thermoset is applied. 21. The method according to claim 19, characterized in that a mass according to ¹ one of claims X ₁ 3 to 14 and 18 is applied to a substrate by direct application by means of a roller and drying or allowing the coating to dry. 22. The method according to any one of claims 19 to 21, characterized in that that the amount of the mass is such that a finished • cured or dried coating with a thickness between 0.25 and 127 µ (0.01 to 5 mils) is obtained. 23. The method according to any one of claims 19 to 21, characterized in that that a metal sheet is used as the substrate, the sheet being additionally mechanically deformed. 24. The method according to any one of claims 19, 21 and 22, characterized in that that the substrate used consists of a board, the method additionally comprising the measure, if appropriate to sand the board and to apply a top coat. 25. A method for lubricating according to claim 19 using a mass according to one of claims 1, 3 to 14 and 18, characterized in that the mass is removed again from the surface will. 609882/1041 26. The method according to claim 25, characterized in that it is applied to the cold rolling of metals. 609882/1041