DE2935066A1 - ALKALINE-RESISTANT ORGANIC COATINGS FOR CORROSION-RESISTANT SUBSTRATES - Google Patents

Description

DR. A. KOHLER .VI. SCHROEDER PATENT LAWYERS PROFESSIONAL REPRESENTATIVES BEFORE THE EUROPEAN PATENT OFFICE TELEPHONE: C08S) 37 47 42 «MÖNCHEN 40 TELEGRAMS: CARBOPAT MÖNCHEN FRANZ-JOSEPK-8TRA8SE

us - 986

Ford-Werke AG,
Cologne

Alkali-resistant organic coatings for those susceptible to corrosion Substrates

Crosslinkable compositions of (a) an optionally at least partially neutralized reaction product of di- or Polyepoxides and oxyamines and (b) amino resin crosslinking agents cure to alkali-resistant coatings, even in the absence of corrosion-inhibiting pigments such as Protect chromates against corrosion. The compositions can be mixed with both solvent-based primers as well as water-based, which harden in a conventional manner. "The hardening temperature can can be reduced by phosphate catalysts with reactive hydroxyl groups without reducing the sensitivity to moisture of the cured coating increases.

030010/0319

The present invention is concerned with and is particularly concerned with the prevention of corrosion in substrates such as ferrous metals Resins that delay the corrosion of such substrates, even when formulated in primers by corrosion-inhibiting Pigments, such as chromates, are free.

The corrosion of steel in an aqueous environment can be frequent be reduced to an acceptable rate by adding corrosion inhibitors soluble in the aqueous medium admits. Are steel structures only periodically corrosive Exposed to environment or under conditions that permit the incorporation of a corrosion inhibitor into the corrosive medium exclude, one often works with organic protective coatings. One of the main functions of such coatings is to act as a reservoir for poorly soluble inorganic corrosion inhibitors, which reduce the rate of corrosion slow down the incipient anodic corrosion in damaged areas of the coating and in other areas. The most effective inhibitors include the inorganic chromates, their harmlessness for the environment however, it is occasionally questioned. The elimination of these pigments could therefore be desirable; it was however, found that in the absence of effective corrosion inhibiting pigments, significant adhesion deficiencies in the area damage to the coating and blisters that can occur and finally to the unchecked spread of corrosion to lead. It is generally assumed that the main cause of the inadequate adhesion of a coating caused by corrosion Displacement and / or degradation of the coating resin by cathodically generated hydroxyl ions, suppress corrosion inhibitors this effect by slowing down the overall rate of corrosion and the amount of alkali produced limit »In the absence of corrosion inhibitors must therefore

the coating resin is exceptional against displacement and / or degradation by the hydroxide formed during corrosion be resistant.

The main aim of the invention is therefore to provide resins which can be used in organic Coating compounds are suitable and are also extremely resistant to degradation by alkali. Another goal is deployment organic coating compounds that can be used to protect ferrous substrates that may not be contain harmful corrosion-inhibiting pigments. Furthermore, the organic coating compositions should be suitable for use as a primer on automotive steel substrates and their application properties, including storage stability, are said to be consistent with conventional requirements match the paint processing.

The invention relates to formulations and methods by which the corrosion of susceptible substrates is reduced while not using the conventional amounts of corrosion inhibiting pigments such as chromates. In particular, it relates to primers for use on automotive steels and other such substrates. In particular, these are crosslinkable mixtures that are applied to bare or treated Hardening steels into coatings and spreading corrosion, particularly damage to the coating starting out, resist.

The crosslinkable compositions contain (I) the reaction product of (a) epoxide and (b) amine, (II) crosslinking agent Amino resin and (III) optionally a di- or polyhydroxy compound, wherein the amine consists of a secondary or primary and secondary amine and largely

030010/0919

- / - 44-

molar basis, which is an oxyamine. According to one embodiment (a) and (b) do not have to be fully implemented before application to the substrate. Surprisingly such compositions can be cured in technically acceptable curing sequences without volatilization of the amine with the production of coatings ^ which under corrosive conditions against degradation / displacement are extremely resistant and those in the presence of a catalyst are advantageous at even lower ones Temperatures can be hardened.

According to one embodiment, the crosslinking mixture is formulated into solvent-based coatings as a primer spray and develops considerably better corrosion resistance than certain conventional primers. The inventive crosslinking mixtures can also can be formulated into water-based primers ^ which also show desirable properties.

According to a further embodiment it has been found that Certain reactive catalysts lower the curing temperature * the primers can be crosslinked with the above Mixtures need * while maintaining or improving the film-forming properties compared to conventional catalysts will.

The_found new possibility for corrosion prevention in Presumably this is due to the absence of corrosion-inhibiting pigments on a different mechanism than the inhibition of corrosion by pigments such as chromates. The previous Test results suggest that those described below cured coatings less the overall rate of corrosion by retarding anodic dissolution

Q30i10 / 0SiS

of iron slow down as an adherent network is formed, which is against degradation / displacement by cathodically generated Hydroxide is extremely resistant and therefore limits the • area on which corrosion reactions can take place.

The obligatory components of the crosslinkable compositions according to the invention are certain epoxy compounds, C: c.y- (or Hydroxy) amines and amino resin crosslinking agents. the Ingredients are combined in such a way that the crosslinking mixture is solvent-based as well as aqueous primers Base is usable.

The components of the mixture are described below:
A. Reaction product of epoxy and amine

The reaction product of epoxide and amine is produced in a non-aqueous medium by reacting a di- or polyepoxide (preferably without carboxylic acid ester bridges connecting the epoxy groups) with certain amines.

1. epoxy.

The epoxy should essentially contain an average of at least about two epoxy groups per molecule and can have 3 or more epoxy groups

Molecular weights of preferably more than about 300 (numbers

medium) and up to about 10,000 or more, depending on the desired properties, such as viscosity and solids content.

One class of suitable epoxy compounds are the reaction products of mono-, di- or polycyclic di- or polyhydroxy compounds with epihalohydrins of the formula

0
/ \

X-CH ₂ -CY-CH ₂

030010/0919

wherein X is a halogen such as chlorine and Y is hydrogen or a lower alkyl radical such as methyl or .Jthylrest. Examples of such epihalohydrin reaction products are, for example, straight-chain epoxy-terminated compounds with glycidyl ether groups such as reaction products Bisphenol A and epichlorohydrin, which are commercial products, such as the Epon 828, 1001 or 1004 (commercial products of Shell Chemical Company). These products contain for the purposes according to the invention preferably average at least about one aromatic group such as the benzene radical, and in particular at least about two on average Groups per terminal epoxy group. Are particularly suitable Reaction products of bisphenol A and epichlorohydrin in large proportions with up to 10 or more bisphenol units in the backbone of the reaction product, for example with molecular weights in a range up to about 8,000, preferably from 700 to 6,000 (number average) »

Further examples of epoxy compounds that can be used as the epoxy are also commercially available polyepoxy compounds (on average more than about two / epoxy groups per molecule). These epoxy compounds include the novolak epoxy resins, for example Epon 152 and 154 (commercial products of the Shell Chemical Company) "These polyepoxy resins include the epoxidized phenol / formaldehyde resins which contain terminal glycidyl ether groups from aromatic radicals" ~ -. _

Also aliphatic and cycloaliphatic epoxy compounds with an average of at least about two epoxy groups per molecule can be used for these aliphatic Epoxy compounds include epihalohydrins and reaction products of aliphatic di = "or © poxldlerter polyol © wi @ glycols,

Butadienes, vinylcyclohexene dioxide and dipentene dioxide. Hydrogenated bis-phenol A / epichlorohydrin reaction products can also be used be used.

Any mixtures of epoxides which are compatible with one another are also suitable.

According to a preferred embodiment, an epoxy compound of relatively high molecular weight (for example number average above about 700) which has hydrophobic groups (for example reaction products of epihalohydrin with a diol such as bis-phenol A) has been found to be present in the epoxy reactant increased moisture resistance is imparted to the cured coatings compared to products containing epoxy compounds of lower molecular weight. As will be described in more detail below, however, certain low molecular weight epoxy compounds with primary or secondary alkanolamines]! are reacted with the formation of reaction products that show a similarly improved resistance to the effects of moisture. Preferably, however, the epoxidic reactant contains higher molecular weight epoxy compounds such as those bis-phenol A / ELpichlorohydrin reaction products which contain at least about 25 mol # (preferably at least about 75 mol #) compounds with two or more, for example about J> to 10, aromatic groups have per epoxy group. >

2. amine.

The amine reactant preferably contains secondary or primary and secondary amine, suitably with a total of up to about 20 carbon atoms per amine nitrogen, being at least about 75 #

030010/0813

of the amine reaction part of at least one oxyarnine

© Ε

with one or more (preferably two) primary hydroxyl groups on carbon atoms, the amine nitrogen atoms
are not adjacent exist. Typically, secondary amines are suitable for reaction with higher molecular epoxy compounds, while mixtures of primary and secondary amines are advantageously reacted with low molecular weight epoxy compounds in order to increase the molecular weight of the reaction product of epoxide and amine. "Secondary
Monoamines are usually used along with polyepoxides
3 or more epoxy groups are used per molecule.

The hydroxyl group of the oxyamine serves as a residue, which presumably reacts chemically with at least part of the amino resin crosslinking agent during curing to form a crosslinked coating. The oxyamine preferably contains primary hydroxyl groups on aliphatic carbon atoms. Furthermore, at least one amine nitrogen of the oxyamine is preferably only substituted by "aliphatic carbon, that is, it is an aliphatic oxyamine,
although the aliphatic carbon chain by not
interfering heteroatoms such as oxygen, or interrupted by aromatic radicals such as aryl radicals or tertiary amino groups
can be substituted.

Aliphatic secondary oxyamines ^ especially secondary ones
Monoaminoalkanols, in many cases, are used with success as
Amine reactants used, being particularly
Hydroxyalkylamines are favorable, the alkyl radical of which is
wise a lower "alkyl radical with, for example, up to
7 carbon atoms. According to a preferred embodiment, the amine consists totally or almost totally (for example 90 molar Jfc or more) of secondary amine in the form of a

/ os ti

Amino alcohols, and in particular one amino alcohol with two hydroxyalkyl substituents, for example from diethanolamine.

One class of preferred oxyamines corresponds to the following formula

R-N-R '

wherein R and R ¹ , independently of one another, represent hydrogen or straight-chain or branched aliphatic radicals each having up to about 10 carbon atoms, with the proviso that (a) at least one of the radicals R and R ^{1 is} not hydrogen and (b) at least one the radicals R or R ¹ is substituted by a hydroxyl group on a primary carbon atom which is not adjacent to any amine nitrogen. R and R 'can also be part of a ring, such as a six-membered ring. Preferably, R and R ^{1 are} independent alkyl radicals with> suitably each up to 7 carbon atoms, and in particular for aqueous-based formulations, primary hydroxyalkyl radicals each with up to 4 carbon atoms.

However, various amines, such as primary and secondary, can also be used successfully together Amines, which form mixtures of alkylamines and hydroxyalkylamines. The key condition is that it is sufficient Hydroxyl groups, in particular primary hydroxyl groups, are present in the reaction product of amine and epoxide in order to be adequate Ensure reaction with the amino resin crosslinking agent.

030010/0919

Preferably, however, 90 or more mol% of the amine reactant consists of amino alcohols with primary hydroxyl groups, and especially of hydroxyalkyl monoamines, which preferably have a primary hydroxyl group on both alkyl radicals.

J5. Reaction conditions in the implementation of Epoxy and amine.

The epoxy and amine reactants are under Conditions reacted with one another that allow the opening of the epoxy ring by amine nitrogen and deliver a gel-free reaction product. Secondary amines generally give tertiary amino groups, while primary amines provide secondary amino groups with an unreacted epoxy group of the same or presumably another molecule can continue to react, whereby the chain is extended »

The reaction medium is preferably non-aqueous and preferably polar in character and serves to facilitate contact of reactants to control the rate of reaction to produce a desirable viscosity to maintain and perform other known functions «Suitable solvents and diluents for the Reactions include aromatic and aliphatic hydrocarbons, halides, ethers, alcohols and ketones such as Me thy lamy! ketone, n-amyl ether, xylene., Butanols containing oxygen! Solvents such as propylene glycol monopropyl ether, Cellosolves such as 2-methoxyethanol and 2-butoxyethanol, carbitols such as ethoxybutoxyethanol and the like, furthermore corresponding mixtures can be di- and polyhydroxy compounds of the following

030010 / 091S

serve as part of the reaction medium.

In order to promote the reaction between epoxide and amine, elevated reaction temperatures can be used, and the reaction can also be carried out in stages. The reaction is complete as soon as the product is essentially free of unreacted epoxy groups, since almost equivalent amounts (for example about 0.9 to 1.0 amine equivalents per 1 to 1.1 epoxy equivalents, where amine equivalents = 1 for 1 mole of secondary monoamine and = 2 for 1 mole of primary monoamine and 1 mole of diepoxy compound has, for example, 2 equivalents). The reaction product of epoxide and amine should therefore contain less than 20% of the original, unreacted epoxy groups and, preferably, less than 10 or 5 % or less of unreacted epoxy groups, based on the amount originally present.

B. Amino resin crosslinking agents

The amino resin crosslinking agent can be added to the reaction product (A) in amounts of about 5 to 30% by weight based on the total weight of (A) and optional ingredients (C) are admixed in the manner described below. Preferred Amino resin crosslinking agents are the known and commercially available products that are essentially condensation products from amino or amido compounds and aldehydes and by monohydric alcohols of ordinary can be modified up to about 4 carbon atoms.

Particularly preferred amino resin crosslinking agents are partially alkylated melamines (modified by alcohols

030010/0910

Melamine / formaldehyde resins), for example partially methylated or butylated melamines. Another preferred crosslinking agent is a urea / formaldehyde condensate that is produced by Alcohol is modified, for example butylated urea resin. Mixtures of crosslinkers as well as mixtures of alkylated Melamines and alkylated urea resins were found to be particularly useful, for example in solvent-based primers, namely when using butylated types in weight ratios of (a) butylated melamine resin to (b) butylated urea resin of a; b between 1: 1 and 10: 1.

Further suitable crosslinkers are amino resins such as glycoluril resins and benzoguanimine resins.

C. Optional Ingredients

Di- and polyhydroxy compounds of various types can can be used to modify the film properties, as well as solvents and reaction solvents in the crosslinkable mixture. These compounds can also give increased elasticity and can be used in primer sprays "from (A) and (B) reduce the tendency to crater.

A preferred group of hydroxy compounds are those aliphatic dihydroxy compounds, especially glycols "and glycol ethers of the formula:

H0- (C _a H _2a 0) - (C _b H _2b 0) _y H,

where a, b, χ and y are integers independent of one another, a and b are numbers from 2 to 6 and χ and y are from 0 to 10, the sum of χ and y being a number from 2 to 10. Examples of such compounds are ethylene glycol, dipropylene glycol and 1,6-hexanediol. Another class of glycols are the

0 3001!) / Ö 81

Polybutadienes with a terminal hydroxyl group and hydrogenated ßis-phenol A, these hydroxyl compounds in general are hydrophobic and have molecular weights with preferably a number average of about 100 to 5,000. Higher boiling Solvents (for example boiling point above about 180 ° C, for example 190 to 250 ° C) tend to be polar in character to react with the crosslinkable mixture and in this way allow higher solids contents.

The primers according to the invention can use pigments in the usual way ■ rfeise included, but no chromate pigments needed to achieve good corrosion resistance. Examples of pigments are titanium dioxide, silica, Carbon black and barite, which are pigment: binder in weight ratios (that is, the sum of (A) and (B)) from about 40: 60 to 60:40 are used. Further components such as solvents, diluents, surface-active substances can also be used Agents, catalysts and the like can be added to perform the respective functions.

In order to accelerate the curing of the primer mixture according to the invention, for example by lowering the curing temperatures, which are required for crosslinking for 15 to 50 minutes at about 180 to 140 ° C. or even less, catalysts, in particular acid catalysts, can be used. Among the acid catalysts include protic compounds or Lewis acids, preferably in amounts of about 0.5 to 5.0 wt.% Of the primer mixture. Typical acids include strong acids such as phosphoric acid, p-toluenesulfonic acid, and substituted boron compounds such as trialkoxyboron compounds, although certain of these catalysts can produce films that are less resistant to moisture than desired.

030010/0919

A preferred embodiment of the invention uses a reactive, hydroxyl-containing, preferably aliphatic phosphate ester as a catalyst for the crosslinkable mixture, which phosphate ester is obtained by reacting phosphorus pentoxide with a diol or triol. This catalyst, which is preferably used in amounts between about 0.1 and 5% by weight of the total weight of (A) reaction product of epoxy and amine. and (3) amino resin crosslinking agent, is applied not only leads to reduced curing temperatures, but it is in contrast to other conventional strong catalysts also have the advantage _s that he, the sensitivity of certain Pormulierungengegenpeuchtigkeit, in particular the moisture sensitivity of primers solvent based not increased and water-based primers such as primer sprays can result in improved corrosion resistance. The reactive phosphate consists of an organophosphate with a functional hydroxyl group, which is present in the mixture according to the invention as a mono- or diester or a mixture of mono- and diesters. The organophosphate esters which can be used in the mixtures according to the invention include those of the formula

(RO) _n J (0H) _{> ni} - -: ■ - ■

where η = 1 to 2 and R is a hydroxy-substituted hydrocarbon radical, preferably denote a mono- or dihydroxyalkyl, cycloalkyl or aryl radical. Preferably included the alkyl, cycloalkyl or aryl radicals have 3 to 10 carbon atoms and particularly advantageous are hydroxyl-substituted aliphatic or "cycloaliphatic radicals, which may or may not be can be interrupted by heteroatoms such as oxygen or aryl groups »

030016/0010

Suitable functional mono- or dihydroxy radicals "are: 2-ethyl-3-hydroxyhexyl, 4-methyl-cyclohexylmethyl, 2,2-diethyl-3-hydroxypropyl, 8-hydroxy-octyl, 6-hydroxyhexyl, 2,2-dimethyl- 3-hydroxy-propyl, 2-ethyl-2-methylj5 -hydroxypropyl, 7-hydroxyheptyl, 5-hydroxypentyl, 4-methylolbenzyl, 3-hydroxyphenyl, 2,3-dihydroxypropyl, 5j6-dihydroxyhexyl, 2- ( j3-hydroxycyclohexyl) -2-hydroxyethyl and 2-0- hydroxypentyl) -2-hydroxyethyl.

The radicals listed are only exemplary; numerous other radicals are in accordance with the organophosphate esters above definition possible. Most preferred radicals include the mono- or dihydroxyalkyl radicals J5 to 10 carbon atoms.

A preferred process for preparing the hydroxyl functional organophosphate esters is as follows Esterification of an alkyl, cycloalkyl or aryl diol or triol or corresponding mixtures with phosphorus pentoxide. If a triol is used, at least one of the hydroxyl groups should preferably be secondary. The reaction between Diol or triol and phosphorus pentoxide is generally carried out in such a way that the phosphorus pentoxide is added in portions to the excess diol or triol added in the liquid state or in solution in a suitable solvent. A preferred temperature for carrying out the reaction is between about 50 and about 60 C. Because of the multiple Hydroxyl punctiformity of diol or triol arise in this reaction also includes smaller amounts of polymeric acid phosphate and certain cyclic phosphates. These polymers and ring-shaped materials also serve as reaction catalysts and therefore do not have to be made from the hydroxyphosphate esters to be segregated. In preferred embodiments

030010/0819

of the invention, it is advantageous in the crosslinkable mixture all reaction products, i.e. the organophosphate esters with functional hydroxyl groups, the lower ones Use amounts of polymeric acid phosphate and cyclophosphate and excess diol or triol. Excess Diol or triol in these cases can be taken as the whole or serving as part of the optional hydroxyl functional additive. Manufactured in the above / preferred manner Catalysts generally contain an organophosphate mono- to diester ratio of about 1: 1.

Another preferred method of making the organophosphate esters with functional hydroxyl group which can be used in the mixtures according to the invention consists in the esterification of phosphoric acid with an alkyl ™, cycloalkyl or aryl monoepoxide. This reaction is accomplished by adding about 1 to about 2 moles, and preferably between about 1 and 1.5 moles of monoepoxide are added to 1 mole of phosphoric acid or its solution in a suitable solvent. While a hydroxyl group is formed during the esterification one having a hydroxyl group as a reactant Use monoepoxide »In this process, the known monoepoxides such as monoepoxy ethers and monoepoxy esters are preferred and alkylene oxides. Examples of preferred monoepoxides for this esterification are: propylene oxide, butylene oxide, Cyclohexene oxide, styrene, n-butyl glycidyl ether and Ethyl glycidyl ether. Of course that is changing Ratio of monoester to diester formed during the reaction with the molar ratio between monoepoxide and phosphoric acid. If 1 mole of epoxide is used per mole of phosphoric acid, the result is mainly monoester, while with a molar ratio from 2: l is mainly formed diester. A

0 ^: 3001Ö / Ö91S

ORIGINAL INSPECTED

1.5: 1 molar ratio results in an approximate 1: 1 mixture from mono- and diester. In any case, smaller amounts of the Trieste are created. This Trieste serves obviously not as a catalyst, but crosslinks with the amine crosslinking agent in admixture and therefore can can be readily incorporated into the mixture.

The organophosphate ester with functional hydroxyl group in the crosslinking mixture according to the invention is a reaction catalyst, which allows the mixture to cure quickly at a low temperature. The acid group of the Mono- or diesters or the ester mixture reacts with the reactive hydroxyl function, for example im Amino resin crosslinking agent, and thus builds the phosphate into the network, so that this increases the resistance of the coating against the effects of moisture and in some cases the corrosion resistance is even improved.

Formulation of the primer

The crosslinkable mixtures containing reaction product of epoxy and amine, amino resin crosslinking agent and optionally Di- or polyhydroxy compounds, can be made into various primer formulations, including those in a non-aqueous medium or those on an aqueous basis. These primers can be used as coatings bare and treated steels (conversion coated with phosphates) and as guide coats over previously applied Primers applied by electrodeposition can be used. In the primer formulation you can conventional modifiers be present, for example agents to control flow behavior, pigment dispersants, Thixotropes, aids against

030010/0919

-r-

Cratering, light stabilizers and the like.

1. Solvent-based primer , - "-

These primers show good thermal and storage stability and can be applied to metal substrates using conventional techniques, for example by Spraying, dipping and other such coating processes. - -

£. ~ Water-based primer _r -

Water-based primers can be taken from the erf induri. ^ S ^ emclssen crosslinking mixtures are produced. At least partially neutralized lipoxide-amine reaction products are used here. Used as an amino resin crosslinking agent one water-soluble or water-dispersible agent of the type described here in similar amounts. The primers can be used as sprays or through Electro-coating can be applied (compare the one on the same side Filed patent application (preparation mark US-987)).

Spray primer on an aqueous basis are zweckrnässig, "in water-compatible solvents and diluents such as ethylene glycols and alkylated glycols -; prepared, for example in oxygen-containing solvents such as cellosolves and carbitols _ _ anschMessend and at least partially acid-especially ,, weak -OR- ~ ~~ ganic acids such as formic acid, acetic acid or butyric acid, neutralized. Coupling agents are advantageously used. _

The water-based spray primers can be formulated with large amounts of water, for example more than 10 % _s, for example about 30 to 50% by weight, and still cure.

under conventional conditions such as ISO ° C for 20 to 30 minutes or even less if certain people are present Catalysts such as, for example, the phosphate catalysts described herein with a reactive hydroxyl group.

Particularly advantageous water-based spray primers can be formulated as stable emulsions by epoxide and amine are reacted in a water-miscible solvent, the amine being one or more water-soluble Amino alcohols with up to about 20 carbon atoms, especially water-soluble hydroxyalkylamines and especially secondary amines with at least two primary hydroxyl groups such as diethanolamine or dipropanolamine.

Particularly suitable water-miscible solvents (that is to say solvents which form a continuous phase with the water at 25 ° C. and 20% by volume or more) are, for example, monohydroxy ethers such as

Glycols etherified with C, -C> residues, for example Verbin-Jο

fertilize the formula

R- ^ O (CH ₂ ) _x _7 _y -0H,

where R is an alkyl radical having 1 to 8 carbon atoms, χ is a number from 2 to 4 and y is a number from 1 to 10 mean, especially those with boiling points below about 180 C such as 2-methoxyethanol, 2-ethoxyethanol and propylene glycol monopropyl ether. Other suitable solvents include ethanol, propanol, Isopropanol and the like. High-boiling solution

Medium, for example glycols boiling above about 180 ° C can be used as co-solvents.

In an expedient manufacturing process, a concentrate is used formed from the reaction product of epoxy and amine

in. a water-miscible solvent and: then -_-. -: with a weak "organic acid with up to 4 carbon atoms such as formic acid * acetic acid or oxalic acid in the presence of the amino resin crosslinking agent at least partially neutralized to give a concentrate which is easy to use in spray processes can be dispersed in water.

Partially methylated or butylated melamine resins are also preferred. Conventional pigment dispersants can also be used and other additives including silanes and organotitanates can be used.

^. Merfocomponent coating compound

Epoxy and amine can also be used along with the aminoplast resin crosslinking agent and preferably the di- or polyhydroxy compound as described above on the to be coated Substrate are implemented with each other. According to this embodiment, epoxide and amine and, advantageously, the Di- or polyhydroxy compound (preferably with boiling points of more than about 200 C) intimately mixed on the substrate to be coated applied and cured there »According to this embodiment, the amine reactant also consist only of a primary amine in the form of an oxyamine. However, the primary amine is usually combined used with diepoxides.

Preferred primary amines for this embodiment, the contain primary hydroxyl groups, are hydroxyl-substituted tute lower alkyl amines such as ethanolamine, propanolamine., Pentanolamine and the like. If hydroxyl-substituted secondary amines are used, these are "preferred"

030010/0419

2?

2935086

also lower aliphatic amines such as dialkanolamines with up to 7 carbon atoms, for example diethanolamine, or lower-alkyl-substituted alkylamines such as 2- (methylamino) ethanol.

In this embodiment it is for corrosion resistance It is important that the primer formulations shortly before, i.e. less than a few hours, but appropriately mixed together more than half an hour before application and curing. It is advisable to use catalyst-free multicomponent, crosslinkable mixtures cured according to conventional curing processes, optionally with catalysts be accelerated. On the other hand, it is important that amino resin crosslinking agents and epoxy be used before

Amine,
Formulation with the primary / containing amine reactant and application to the substrate should not be left to stand unduly long (for example several times). The multicomponent system is preferably applied to the substrates within a period of between approximately 30 and 600 minutes after mixing.

As already mentioned, in this embodiment preferably also di- or polyhydroxy compounds are used, these being used, for example, as solvents, which allow crosslinkable mixtures and coating compositions with high solids contents that can be used as primers. Also the Film properties such as elasticity can be improved by using the di- or polyhydroxy compound will. In this regard, glycols are the

Formula HO-fC H _Oa 0) _v - (C. H _OK 0) H, where a and b, independently a ca χ υ CD y

of one another, a number from 2 to 6 and χ and y, independently of one another, a number from 0 to 10 and the sum of χ and y is a number from 2 to 10, preferably used.

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Jt

The multi-component coating mass is advantageously used as Solvent-based primer formulated to work on various Species can be applied to the substrate, for example by dipping, spraying, curtain covering and the like.

In the following examples, parts mean parts by weight, unless otherwise specified.

example 1

A thermosetting coating composition for use on automobile parts is made from a bis-phenol A / epichlorohydrin ' epoxy resin, alkanoiamine and an amino resin crosslinking agent in the following way:

Part A; ~ _

Production of the epoxy / alkane oil amine resin

materials Parts by weight Epon 10 (4 (1) 625 Diethanolamine 70: Me thylamyIke clay 625 Butanol 200 Reactor loading Diethanolamine 70 Methyl amyl ketone 625

(1) Product of Shell Chemical Company, reaction product of epichlorohydrin and bis-phenol A, solid from Pp 95 to 105 ° C, Gardner-Holdt viscosity at 25 ⁰ C = QU (40 ^ solution in butyl-dioyitol) epoxy equivalent 875 to 1000 (grams of resin per gram-squivalent of epoxy), '"! equivalent weight (amount of resin in grams at

0-30010 / -Ö91S

Esterification of 1 mole of acid) 175 (data sheet SC: 69-58).

The Reaktorbeschickling is heated in a flask equipped with stirrer, reflux condenser and thermometer boiler 70 to 8O ⁰ C. Then the Epon 1004 is added over the course of 4 hours. The temperature is maintained during the addition of the epoxy resin and another 4 hrs. At 70 to 80 ⁰ C. The resulting epoxy Alkanolaminharz is then cooled to 5O ⁰ C and diluted with butanol. The resin is then cooled to room temperature, filtered off and formulated into a primer as described below.

Part B;

Formulation of the primer

materials Parts by weight butylated melamine resin (RN 602) (2) 46 Urea resin (RN 512) ^ 6.7 Titanium dioxide pigment 15th Carbon black pigment 15th Silica pigment ; 11 Barite pigment 102 Xylene 50

Epoxy-alkanolamine resin

Part A 399

The unpigmented primer is made by dissolving the epoxyalkanolamine resin, butylated melamine and urea resin in xylene and butanol. Then a grinding concentrate or a grinding base is prepared from 1/3 of the unpigmented resin and the above pigments. The remaining unpigmented primer is then added and carefully distributed in the grinding concentrate. The resultiertende primer is filtered, sprayed onto cold-rolled steel sheets unphosphatierte and cured for 20 min. At 180 ⁰ C.

030010/0319

The cured coating shows excellent corrosion resistance in the salt water spray test, good solvent resistance to xylene and good elasticity and hardness.

(2) Product of Mobil Chemical Company, described as butylated melamine / formaldehyde resin with a viscosity of VX, proportion of non-volatile 58%, ^S: iurezahl 2, solvent is n-butanol.

(3) Mobil Chemical Company product, described as butylated urea / formaldehyde resin, viscosity WY, non-volatile content 50 % + 2%, acid number 3.5

up to 4.5 * staining according to Gardner maximum, solvent - 80 % n-butanol and 20 % ethylbenzene.

Example 2

The procedures of Example 1 are repeated with the following Deviations:

Epon 1004 is replaced by Epon 1001 Cl) «All others Components for the production of the epoxy-alkanolamine resin and the finished primer are used in the type and amount as in Example 1.

Materials - parts by weight

Epon 1001 (1) 334

(1) Product of Shell Chemical Company, described as Solid with viscosity (Gardner, -Holdt) D-G, 1.0-1.7 Poise (ASTMD-445) i η 4θ $ iger solution in butyl-diox ^ tol, Epoxy equivalent 450 to 550.

Unphosphated steel sheets coated with the primer show excellent corrosion resistance to salt water spray, good solvent resistance to xylene,

03001: 0/0919

good elasticity and hardness.
Example j?

The procedures of Example 1 are repeated with the following difference: Epon 1004 is replaced by Epon 828 . All other materials for the production of epoxy / alkanolamine resin and finished primer are used in the type and amount as in Example 1.

Materials parts by weight

Epon 828 (1) 12b

(1) product of Shell ehemical Company, described as a liquid with the viscosity (ASTM D-445) 110-150, epoxy equivalent I85 to 192, Gardner color than 3 1.16 g / cm ³ (68 ⁰ C).

Unphosphated steel sheets coated with this primer show excellent corrosion resistance when sprayed with salt water, good solvent resistance against xylene, good elasticity and hardness. One observes some sensitivity to condensing moisture. "- ■ - - ';. ■ -". "". "

Example 4

The procedures of Example 1 are repeated with the following Deviation: the 2-methylaminoethanol is replaced by diethanolamine replaced. All other materials for the production of epoxy, alkanolamine resin and finished primer are of the same type and amount as in Example 1.

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-γ-

135066

Materials parts by weight

2- (methylamino) ethanol 49

Unphosphated steel sheets coated with this primer show excellent corrosion resistance when sprayed with salt water, good solvent resistance to xylene, good elasticity and hardness,

Example 5

A thermosetting coating composition "for use on automotive parts is made from an epoxy, alkanolamine resin and an amino resin crosslinking agent. That Epoxy, alkanolamine resin in this case consists of the Condensation product of low molecular weight bis-phenol A, Epichlorohydrin-epoxy resins and mixtures of primary and secondary alkanolamines The resin production and The formulation of the primer is carried out as follows:

Part A:

Production of the epoxy / alkanolamine resin Parts by weight materials 190 Έροη 828 (1) 52 Diethanolamine 15th Ethanolamine 200 Me thy lamy Ike ton 15th Butanol Reactor loading 52 Diethanolamine 5 Ethanolamine 200 Methyl amyiketone

The reactor charge is heated ^{to 70 to 80 °} C. in a kettle equipped with a stirrer, reflux condenser and thermometer. The Epon 828 is added in the course of 1 hour. During the addition of the epoxy resin, and even 1 hour longer. The temperature is maintained at 70 to 80 ⁰ C. The remaining ethanolamine is then added and the reaction mixture is kept at 70 to 80 ° C. for another hour. The resulting epoxy / alkanolamine resin is cooled to 50 ° C. and then diluted with butanol. The resin is then cooled to room temperature, filtered off and formulated into a primer as described below.

Part B;

Formulation of the primer

materials Parts by weight Epoxy / alkanolamine resin from part A 532 butylated melamine resin (RN602) ' 69 Urea resin (RN512) & ) 10 Titanium dioxide pigment 23 Carbon black pigment 23 Silica - - 16 Barite 153 Xylene 75 Butanol 113

The primer is pigmented as in Example 1 B.

(1) Shell Chemical Company product, see Example 3.

(2) and (3) Mobil Chemical Company products, compare

example 1

030010/0919

Example 6

A thermosetting coating composition for use on automotive parts is made from a bis-phenol A epichlorohydrin epoxy resin, an alkanolamine, an amino resin crosslinking agent and glycol in the following manner:
Formulation of the primer:

materials Parts by weight Epoxy / alkanolamine resin from part A, example l 399 butylated melamine resin (RN6O2) (1) 80 Urea resin (RN512) (2) 10 Triethylene glycol 40 Methyl amyl ketone 100 Butanol 10 (J - Titanium dioxide pigment 15th Carbon black pigment 15th Silica pigment 11 Barite pigment 102

The unpigmented primer is made by dissolving epoxy alkanolamine resin, butylated melamine resin, urea resin and triethylene glycol in xylene and butahol. The primer is then pigmented as described in Example 1B. The finished primer is filtered, applied to cold- rolled, unphosphated steel sheets and cured at 180 ° C for 20 minutes. The coating shows satisfactory corrosion resistance in the salt spray test «. .

(1) See Example 1, product of Mobil Chemical Company.

(2) See Example 1, product of Mobil Chemical Company.

03-0010 / 0818.

-31

example ¹ y

The procedures of Example 6 are repeated with the following Deviation: the triethylene glycol is replaced by hydrogenated bisphenol A replaced. All other materials are the same in type and quantity as in Example 6.

Materials parts by weight

hydrogenated bis-phenol A 20

Unphosphated steel sheets coated with this primer show excellent corrosion resistance and elasticity and hardness.

Example 8

The procedures of Example 6 are repeated with the following difference: the triethylene glycol is replaced by poly bd R-45HT, a polybutadiene resin with a terminal hydroxyl group. All other materials for the production of the primer are the same in type and quantity as in Example 6.

Materials parts by weight

Poly bd R-45HT (1) 2 G

(1) Product of ARCO / Chemical Company, Dept. Atlantic Richfield Company.

Unphosphated steel sheets coated with the primer show excellent corrosion resistance and elasticity and hardness.

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Example 9

a) parts for application to automotive suitable thermosetting coating compositions are prepared according to the procedure of Examples 1 to 8 * with the exception that the primer is added 2.5 wt.% phosphoric acid "By the addition of small amounts of acid catalyst is lowered the curing temperature.

b) A thermosetting coating mass suitable for application to automobile parts is made from a bis-phenol A, - splehlorhydrin-epoxy resin, Alkanolamine and amino resin crosslinking agents produced in the following way:

Part A: ■ Parts by weight 625 Production of the spoxide / alkanolamine resin 70 materials 625 Epon 1004 (1) 200 'Diethanolamine Methyl amyl ketone 70 Butanol 625 Reactor loading Diethanolamine Methyl amyl ketone

(1) Shell Chemical Company product, compare "Example 1

The reactor charge is heated to 70 to & 0 ° C in a kettle equipped with a stirrer, reflux condenser and thermometer. Then the Epon 1004 is added over the course of 4 hours. The temperature is maintained during the addition of ■ Spoxyharzes and then for a further 4 hr. At 70 to 80 ⁰ C. That

The resulting epoxy / alkanolamine resin is ^{cooled to 50 °} C. and diluted with butanol. The resin is then cooled to room temperature, filtered off and formulated into a primer as described below.

Part 3;

Formulation of the primer

materials Parts by weight Epoxy / alkanolamine resin from part A 39.9 butylated melamine resin (RN6O2) (2) 4.6 Urea resin (RN512) (3) Oy.67 Titanium dioxide pigment 15th Carbon black pigment 15th Silica pigment 11 Barite pigment 102 Xylene 50 Butanol 75

Reaction product from
2-ethyl-1,3-hexanediol + P ₂ ° 5

1 %, based on resin solids (4) 0.23

Unpigmented primer is made by dissolving the epoxy, alkanolamine resin, butylated melamine, urea resin and the reaction product of 2-ethyl-1,3-hexanediol and phosphorus pentoxide in the butanol and xylene. Then, a Mahlkonzentrat is prepared from _1/3 of unpigmented primer and above pigments. The remaining clear primer is then added and carefully mixed with the grinding concentrate. The resulting primer is filtered, sprayed onto cold-rolled steel sheets unphosphatierte and cured for 20 min. At ⁰ C l40. The hardened one

030010/0918

Coating shows excellent corrosion resistance in salt spray test, good solvent resistance against xylene, good elasticity and hardness. -

(2), (5) Mobil Chemical Company products, compare

Example 1. _
(4) Manufacture as follows:

2500 g of dry (dried over molecular sieves) 2-ethyl-1,3-hexanediol are poured into a three-necked round bottom flask equipped with a stirrer, dropping funnel and thermometer. Then 450 g of phosphorus pentoxide are added in portions with constant stirring, an exothermic reaction taking place. The "were to admit the phosphorus pentoxide is such that the temperature at 50 ⁰ C bleibt-. After complete addition, the reaction mixture is stirred Γ hrs. At 50 ° C and then filtered. The acid determined by titration with sodium hydroxide '■' quivalentgewicht is

Example 10

This example illustrates that epoxy resins with ester groups are used in the manufacture of the epoxy alkanolamine resins should be avoided »observed in this example one poor corrosion resistance of the primer coating., - injdem Araldite Cy 179 is used as an epoxy.

Part A;

Production of the epoxy / alkanolamine resin

Materials parts by weight

Araldite-Cy 179 (1) 126

Diethanolamine "" "105

Butanol 130. - _

030010 / 09-19

'.fa'

Reactor loading parts by weight

Diethanolamine 105

Butanol 100

The reactor charge is heated to 70 to 80 ^° C. in a kettle equipped with a stirrer, reflux condenser and thermometer. Then a solution of the Araldite Cy 179 in 30 parts of butanol is added dropwise. The temperature is maintained at 70 to 80 ° C. during the addition and for a further 20 hours thereafter, then the resin is cooled and, as described below, formulated into a primer.

Formulation of the primer

Materials parts by weight

Epoxy / alkanolamine resin 67 10, part A butylated melamine resin 39 (RN602) (2) 19th Triethylene glycol 4th Iron (III) oxide pigment 4th Titanium dioxide pigment 3 Silica 29 Barite 15th Butyl acetate 15: Xylene

The unpigmented primer is made by dissolving the epoxy / alkanolamine resin, butylated melamine and triethylene glycol in butyl acetate and xylene. The pigmentation is then carried out as described in Example 1B. The primer is then filtered, applied to cold rolled steel and cured unphosphatierten 20 min. At ⁰ C l8o. The coatings obtained in this way show very poor corrosion resistance.

030010/0919

■ -. . ■: ■ ■■ - ■ ■. ■■ "■ --.- ■ - ■. ■■ / ^; - - ■ ^:. " ^: ";' \ -2935066 ■

(1) Product of Giba-Geigy Corporation, by ester groups linked diepoxide »

(2) Compare Example 1, a product of Mobil Chemical Comp.

Test results

The following table shows those for some of the above Examples obtained results “Standard laboratory tests were made carried out * which should determine the properties of the primers or base coats »The following test procedures were applied: ~ "".

24 hour salt spray test according to ASTMB IYJ-62, 64 Salt Spray Test; - -. "_. 10-day salt spray test according to ASTMB 117-62, 64 Salt Spray Testj

Condensing moisture test, combined from ASTMD 2246 and 2247 under continuous condensing Humidity j

cathodic alkali resistance according to the instructions of A. G. Smith and R. A. Dickie, Ind. Eng »Chem. Prod» Res. Dev. 17 (1), 45 (1978), a test in which the persistence of the Coating against displacement / degradation by cathodically generated

- Hydroxide is measured «.

test üpoxy-
Ester
Primer
(D 1 2 Examples:
3 4th; 7 (2) 7th "10 A. 10 10 10 - 10 0 (2). B. "_ 9 8th NA (3) NA (3) 9 - C. 10 9 7th 2 9 8th 9 D. 3 10 10 10 10 0

A = salt spray test 24 hours
B = salt spray test 10 days

030010/0919 '

C = condensing moisture (10 days) 2935066 D = cathodic alkali resistance (8 hours)

0-2 = Total flaking or swelling of the coating 3-5 = Considerable loss at the score line, or severe

Red discoloration or blistering in the coating 6-8 = no or little loss of adhesion at the scratch line, however minor defects, regardless of cracks, minor

Blistering
9-10 = no or very little loss of adhesion

(1) Primer modified with tall oil with Epon 828 epoxy ester, crosslinked with a melamine / formaldehyde resin

(2) Attempt terminated at this point

(3) no values available.

Example 11

A multi-component thermosetting coating composition for Application to automotive parts is made from a bis-phenol A / -epichlorohydrin epoxy resin, Alkanolamine, a glycol and an amino resin crosslinking agent prepared in the following way:

Part A:

Preparation of the unplugged primer formulation Parts by weight materials 34 Epon 828 (1) 12.2 Ethanolamine 19.4 Triethylene glycol 39 butylated melamine resin (2) 30th Xylene

030010/0919

An unpigmented primer is made by Epoxy resin> Ethanolamine, triethylene glycol and butylated melain resin dissolve in xylene. The mixture is left for 45 minutes stirred vigorously, a slight increase in temperature being observed. Then the primer is applied to cold-rolled, Unphosphated steel sheets are sprayed on and cured at 18o C for 20 minutes. The cured coating shows excellent Corrosion resistance when sprayed with salt water, good solvent resistance to xylene, good elasticity and hardness. _ ■

(1) Compare example "3, product of Shell Chemical Comp.,

(2) Compare Example 1, a product of Mobil Chemical Comp.

Part B: -

Preparation of the complete primer _-. _

materials Parts by weight unpigmented primer Part A 134.6 Titanium dioxide pigment 4.1 Iron (III) oxide pigment 4.1 Silica pigment 2.7 Barite pigment 28.6

The freshly prepared, unpigmented primer solution from Part A is immediately combined with the titanium dioxide, iron oxide, silica and barytes. The pigment is dispersed, then the primer is filtered and immediately sprayed onto cold-rolled, unphosphated steel sheets. After 20 minutes of curing at l8ü ⁰ C, the coating exhibits excellent corrosion resistance in the salt spray test and good solvent Beständigkeite

030010/0319

Example 12

The procedures of Example 11 are repeated with the following difference: the ethanolamine is replaced by 2- (methylamino) ethanol replaced. All other materials for the production of unpigmented and finished primer are in The type and quantity are the same as in Example 11.

Materials parts by weight

2- (methylamine) ethanol 15

Unphosphated steel sheets coated with this primer show excellent corrosion resistance and good solvent resistance against xylene and good elasticity.

example

The procedures of Example 11 are repeated with the following difference: the ethanolamine is replaced by 3-aminopropanol replaced. All other materials used to make unpigmented and finished primer are the same in type and quantity as in the example

Materials parts by weight

^ -Aminopropanol. 7 * 5

Unphosphated steel sheets coated with this primer show excellent corrosion resistance, good solvent resistance to xylene and good elasticity.

030010/0919

2335066

ExampleΓl4 : _ -: "■ ~ _

The procedures of Example 11 are repeated with the following exception: the Epon 828 is replaced by the Epon 1001 replaced- All other materials for the production of unpigmented and finished primer are in kind and Quantity same as in example 11 »

Materials _ parts by weight

Epon 1001 (1) 50

Unphosphated steel sheets coated with this primer show excellent corrosion resistance. " good solvent resistance to xylene and good elasticity.
(1) Compare example 2, product of Shell Chemical Comp «

Example 15

This example illustrates that high amounts of alkanolamine are required to achieve good coating properties in a multicomponent Irish system. In this example, poor corrosion resistance of a coating was observed which was made from a primer formulation with too high a secondary alkylamine content.

Part A:

Preparation of the unpigmented primer

Materials parts by weight

Epon 828 (I) ". 34

Triethylene glycol 19., 4 Ethanolamine 6.1

Diethylamine / ^ l, ^ » butylated melamine resin (RN602) 39 xylene 30

. - 030..010 / 08Ji ^;

BAD ORIGfNAL

The unpigmented primer is obtained by combining epoxy resin, triethylene glycol, ethanolamine, diethylamine and butylated melamine resin in xylene. Once the mixture is homogeneous, this mixture is pigmented 11 B of Part A by the procedure of example, The fully formulated primer is applied to cold rolled steel panels and cured unphosphatierte 20 min. At ⁰ C l80. The resulting coating was not satisfactorily cured.

(1) Compare Example 3, a product of Shell Chemical Comp.

(2) Compare Example 1, a product of Mobil Chemical Comp.

Example 16

This example illustrates that primers with poor corrosion resistance can be obtained if only the epoxy resin is used is reacted with primary alkanolamine and glycol.

materials Parts by weight Epon 828 (1) 34 Triethylene glycol 19.4 Ethanolamine 12.2 butylated melamine resin (RN602) (2) 39: _ Xylene 30th Methyl ethyl ketone 25th Butanol 40 Reactor loading Ξροη 828 (1) 34 Triethylene glycol 19.4 Ethanolamine 12.2 Methyl ethyl ketone 12th

030010/0919

The reactor charge is stirred in a kettle equipped with a stirrer, reflux condenser and thermometer. the Solution is initially clear and of low viscosity. After stirring for 5 to 10 minutes, an exothermic begins Reaction, and after 1 1/2 hours the temperature rises spontaneously to 60.degree. After cooling to room temperature the feed consists of a very viscous material that is then diluted with butanol and xylene. The butylated Melamine is added and the mixture is pigmented according to the procedure of Example 11B. The primer so formulated is applied to steel sheets and, as described above, hardened. The resulting coating is very poor Corrosion resistance.

(1) Compare Example 3, product of Shell Chemical Company

(2) Compare Example 1, product of Mobil Chemical Company -

Example 17

This example shows that the multicomponent primer vcr the application on metal sheets should be aged for a certain period of time. This example describes a variant of example "11, which leads to coatings with poor Corrosion resistance leads.

Part A: ' -

Manufacture of the pigmented component materials Parts by weight Epon 828 (1) 34 Triethylene glycol butylated Melatninhara (2 j 39 Pigments from Ex. IB 39.5 Xylene 10

030010/0919

The pigmented component is obtained by carefully mixing the pigments in epoxy resin, triethylene glycol and Melamine dispersed. This pigmented component is stable for 3 months at room temperature.

Part B;

Two-component primer system

Materials parts by weight

pigmented component

Part A 1 ^ 1.9

Ethanolamine 12.2

A sprayable primer is obtained by carefully mixing the pigmented component from Part A with the ethanolamine. The resulting primer is sprayed on after 10 minutes and cured at 180.degree. C. for 20 minutes. The resulting ^ft Plating has low corrosion resistance.

(1) See Example ~ 5, product of Shell Chemical Company

(2) Compare Example 1, product of Mobil Chemical Company

Example l8 -. \ -

The procedures of Example 17 are repeated, with the difference that after the addition of the ethanolamine, the formulation is stirred vigorously for 45 minutes, then sprayed on and ^{cured at 180 °} C. for 20 minutes. The coating thus obtained has good corrosion resistance.

030010/0919

Example 19

The procedures of Example 11 are repeated with the Deviation that hydrogenated bis-phenol A is used instead of triethylene glycol »This is a satisfactory one Get primer.

Example 20

The procedures of Examples 11 and 12 are repeated, with the difference that instead of the butylated Melamine uses the following amino resin crosslinking agent, namely a glycoluril resin called Cymel 1170 (American Cyanamide). Either way it will be a satisfactory one Primer achieved with the equivalent amount of this crosslinking agent.

Example 21

A heat-hardenable coating compound on an aqueous basis for Application to automotive parts is made from epoxy, amine reaction product and "Amino resin crosslinking agent prepared as follows:

Part A: ': "■

Preparation of the epoxy / alkariolamine reaction product

- Materials _ _ weight, parts

Epon 1004 (1) 405.27

Diethanolamine. 45/41

Propas Oil P (2) 299.31

030010/091 '

- y'-vo *

Reactor loading parts by weight

Diethanolamine 45.41

Propasol P (2) 299.31

(1) Compare Example 1, product of Shell Chemical Company

(2) Propylene glycol raonopropyl ether (Union Carbide Corporation)

The reactor charge is heated to 80 to 85 ° C. in a kettle equipped with a stirrer, reflux condenser and thermometer. The Epon 1004 added over 2 hrs., The temperature during the addition and for a further 16 hours is. Then held at 80 to 85 ⁰ C. The epoxide "AU" anolamine reaction product thus formed is then cooled to room temperature and used to formulate an aqueous primer as follows:

Part B: Parts by weight Production of the grinding concentrate ■. . ■ Materials 160.00 Epoxy ,, alkanolamine 41.04 Reaction product from Part A 115.64 Propasol P- 15.84 Barite pigment 15.84 Titanium dioxide pigment 11.08 Iron oxide Silica

41.04 parts of Propasol P are added to 160 parts of the epoxide / alkanolamine reaction product and the mixture is shaken for > 0 min. This gives a homogeneous solution to which the above pigments are added, whereupon it is shaken for 6 hours. A Hegmann score of 6 to 7 is then obtained. The concentrate is then used to produce the complete pigmented primer.

030010/0 919

Complete, water-based primer

materials Parts by weight Grind concentrate from part B 79.6 butylated melamine resin (RN 602) (1) 2.4 acetic acid 1.04 KR-55 (2) 0.40 Water (distilled) 69.30

The grinding concentrate is placed in a stainless steel container Weighed in steel. To this end, the melamine resin is then added and the mixture is stirred well with a disperser. Then the Addition of the KR-55 coupling agent, after which it is mixed well. The acetic acid is weighed into 10 parts of water in a glass container and then the mixture of grinding concentrate, melamine resin and KR-55 added with stirring. Then the remaining rfass is added over the course of 10 to 15 minutes vigorous stirring. The whole mix is done in 15 to 20 minutes. The resulting full primer will be • filtered, sprayed onto cold-rolled, unphosphated steel sheets and cured for 20 minutes at 180 CT. The hardened one Coating shows excellent corrosion resistance in the salt spray test, good solvent resistance to xylene, good elasticity and hardness.

(1) Compare Example 1 “ Product of Mobil Chemical Company

(2) Ken-React TTMDTP-55, titanate coupling agent made from tetra- (2,2-diallyloxymethyl-l-butoxy) titanium di (di-tridecyl) phosphite, Manufacturer Kenrich Petrochemicals, Ν «J.

Example 22

The procedures of Example 21 are repeated with the

following deviation: the coupling agent KR-55 is replaced by the same weight ent srnenge KR-2J58S '' while all other materials remain the same in type and quantity.

Coated with the pigmented primer of this example, unphosphated steel sheets show excellent corrosion resistance in the salt spray test, good solvent resistance to xylene, good elasticity and hardness.

(1) Di- (dioctyl-pyrophosphato) -ethylene titanium, manufacturer Kenrich Petrochemicals, N.J.

Example 23

The procedures of Example 21 are repeated with the following exception: the titanate coupling agent KR-55 is replaced by the hydroxy-phosphate from Example 9 B * furthermore, the amount of melamine resin is increased to 4.8 parts by weight. All other materials are used in the manner and amount as in Example 21.

Unphosphated steel sheets coated with this pigmented primer show excellent corrosion resistance, good resistance to xylene, elasticity and hardness.

example

The procedures of Example 21 are repeated with the following exceptions: The grinding concentrate is mixed with 30.5 parts of Propasol P instead of 4l, 04 parts and the fully pigmented one

030010/0919

Primer contains more water. The nature of the ingredients remains the same.

Part B;

Production of the grinding concentrate

materials - parts by weight Epoxy / alkane oil amine
Reaction product from part A _ß
Example 21 160.00 Propasöl P (1) 30.50 Barytes 115.64 Titanium dioxide 15.84 E. iseiDxide 15.84 Silica 11.08

Mixing is carried out as described in Example 2I ₁ Part B «, fully formulated primer:

"" "" Grind concentrate from part B B7.2 Melamine resin (RN6O2) (2) 2,4 acetic acid Ij, 39

KR-55 (3) 0.40

water . 94.40

Unphosphated ones coated with the fully pigmented primer Steel sheets show excellent corrosion ..- resistance to salt water spray, good resistance to xylene, Elasticity and hardness.

(1) Compare Example 2I ₁ product of Union Carbide Corp.

(2) Compare example I ₁ product of Mobil Oil Chem. Comp.

(3) Compare Example 2Ij, titanate coupling agent

030010-Λ09Ϊ9

Example 25

The procedures of Example 24 are repeated with the following exception: the titanate coupling agent is replaced through the titanate coupling agent KR-2J58S (Ken-React, Manufacturer Kenrich Petrochemicals, presumably di- (dioctylpyrophosphato) -ethylene titanate). All other materials for the production of the epoxy / alkanolamine resin and the finished primer correspond in type and quantity to the components according to example 24.

Materials parts by weight

KR-238S (1) 0.4

Unphosphated steel sheets coated with the pigmented primer show excellent corrosion resistance against spraying with salt water, good resistance to xylene, elasticity and hardness.

Example 26

The procedures of Example 24 are repeated with the following exception: the coupling agent KR-55 is through Hydroxy-phosphate will be replaced and the melamine resin amount will elevated. All other 'materials for making the fipoxid, The type and amount of the alkanolamine resin and the primer correspond to the components according to Example 21.

Materials parts by weight

Hydroxy-phosphate (1) 0.24 butylated melamine resin

(RN602) (2) 4.80

030010/0919

Unphosphated steel sheets coated with the pigmented primer show excellent corrosion resistance in the spray test, good xylene resistance, elasticity and hardness.

(1) produced according to example 9 B.

(2) Compare example i, product of Mobil Chemical Comp.

Example 27

a) A thermosetting coating composition on an aqueous basis, which is suitable for use on automobile parts, is made from a bis-phenol A / epichlorohydrin epoxy resin,

Alkanolamine and Amino Resin Crosslinking Agents Made in the Following Way?

Part A;

Production of the epoxy / ATtonolamine resin

' Materials parts by weight

Epon 10C4 (1) 312.34 Diethanolamine 35.00

Propasol P (2) 230.68

(1) See Example 1, product of Shell Chemical Company

(2) See Example 21, a product of Union Carbide Corp.

To the mixture of diethanolamine and Propasol P in a flask equipped with a reflux condenser and thermometer, three-neck flask is added the Epon 1004 in small portions over a period of 2 hrs. At reflux temperature of 95 to 100 ⁰ C. The mixture is then refluxed for a further 18 hours at this temperature.

030010/0913

-SG-

Part B;

Formulation of the primer

materials Parts by weight Epoxy / alkanolamine resin from part A 40.00 Me lamin resin (RN6O2) 4.80 Propasol P 16.50 Titanium dioxide pigment 4.40 Iron oxide pigment 4.40 Silica pigment 3.08 Ba ry t - Pigmen t 32.40 Glacial acetic acid 1.04 distilled water 73.94 Production of the grinding concentrate

To 1/3 (13.3 parts) of the epoxy, alkanolamine resin becomes 1/3 (1.60 parts) of the melamine resin is added, then all of the (16.30 parts) Propasol P is added. The pigments are dispersed in this mixture in the ball mill.

Preparation of the complete primer

The remainder (26.7 parts) of the epoxy / alkanolamine resin is added to the grinding concentrate, followed by the addition of the remaining butylated melamine resin (3.2 parts). Then 1.04 parts of glacial acetic acid are added, which neutralizes the epoxy. The amount of alkanolamine resin required in 10 parts of distilled water is slowly added with stirring. The remaining water is added with vigorous stirring over the course of 5 minutes. The resulting complete primer is filtered, sprayed onto cold-rolled, unphosphated steel sheets and left for 20 minutes ^{Cured to 0} C. The cured coating shows excellent corrosion resistance in the salt spray test, good solvent resistance to xylene, good elasticity and hardness.

030010/0919

-5 / -S1-

2135066

b) Repeating the procedure of Example 27 (a) replacing the melamine resin RN6O2 with the same Amounts by weight of LTX-127 (partially methylated melamine,

Manufacturer Monsanto), equivalent film properties are achieved and the complete primer shows increased resistance to dispersion compared to the primer according to part (a).

c) Repeating the procedure of Example 27 (a), however, replacing the melamine resin RN602 with equal amounts by weight of Cymel Il4l (American Cyanamide),

so one obtains equivalent film properties and the complete one Primer shows increased dispersion stability compared to the primer of part (a).

030-10 / 918

Claims (28)

DR. A. KÖHLER M. SCHROEDF.R PATENTANWÄLTE PROFESSIONAL REPRESENTATIVES BEFORE THE EUROPEAN PATENT OFFICE TELEPHONE: C088) 374742 β MÖNCHEN 40 TELEGRAMS: CARBOPAT MÖNCHEN FRANZ.JOSEPH-STRASSE 48 patent claims 1. Crosslinkable mass, especially for use in primers that prevent corrosion of susceptible substrates without the need for corrosion-inhibiting chromate pigments delay, characterized by A. an essentially gel-free, if necessary at least partially neutralized reaction product prepared by reacting in a non-aqueous medium of 1. not linked by carboxylic acid ester groups Epoxy having an average of at least about two epoxy groups per molecule and 2. secondary amine or a mixture of primary and secondary amine having a total of up to about 20 carbon atoms per amine nitrogen, the at least about 75 moles of oxyaraine with an or contains multiple primary hydroxyl groups which are around at least 1 carbon atom from amine nitrogen atoms are distantj, in equivalent amounts so that the reaction product (A) contains tertiary amino and primary and secondary hydroxyl groups and of unreacted epoxy groups is free in% \ resentlieen, Β »optionally a di- or poly hydroxy compound and 0» an amino resin Yernetzmigsniittel in an amount of about 5 Ms 55 wt. #, - tesogea on the total weight - of OO and (B), "' original Inspected 2. mass according to claim 1, characterized by about 0.1 to 5 wt. $, Based on the total weight of (A) and (C), one or more phosphate esters of the formula (RO) _n P (OH) ₃ ^ _n , where η is the number 1 or 2 and R is mono- or dihydroxy-substituted Mean hydrocarbon radicals with up to about 10 carbon atoms. 3. Mass according to claim 2, characterized in that R is a mono- or dihydroxy-substituted aliphatic Rest is. 4. Composition according to claim 1 or 2, characterized in that the component (B) is present and consists of one GIykol is made. 5. Composition according to claim 1, characterized in that the epoxy reactant is at least 25 mol-jS an epoxy compound having at least two aromatic groups per epoxy group. 6. Composition according to claim 1,4 or 5, characterized in that the amino resin Vernetzμng3mittel made of melamine resin and / or urea resin. 7. Composition according to claim 1, characterized in that the amine reactant (A) 2 of hydroxy-substituted secondary alkylamine. 030010/0919 8. mass according to claim. 2, characterized by "that the amine reactant (A) 2 is a hydroxy-substituted one aliphatic arain is. 9. Composition according to claim 2, 3, 4 or 8, characterized in that that the amino resin crosslinking agent is composed of alkylated melamine resin and / or alkylated urea Resin is made. 10. Composition according to claim 9, characterized in that the amine (A) 2 consists of dialkanolamine. 11. Composition according to claim 7 or 10, characterized in that the epoxy reactant (A) 1 consists of one Bis-phenol / epichlorohydrin reaction product with a Number average molecular weight greater than about 700. 12. Composition according to claim 11, characterized in that the hydroxyl-substituted secondary alkylamine consists of a di-alkanolamine with a total of up to about 7 carbon atoms. 13. Composition according to claim 11, characterized in that the di-alkanolamine from a di-alkanolarain with a total of consists of up to about 10 carbon atoms. 14. Solvent-based primer that works in the absence of corrosion-inhibiting chromate pigments the corrosion is delayed, characterized by A. an essentially gel-free epoxy / amine reaction product, produced by reaction in non-aqueous medium of 030010/0819 1. epoxy not linked by carboxylic acid ester groups with an average of at least about two terminal epoxy groups per molecule and 2. secondary monoamine or a mixture of primary and secondary conoaain with total up to about 20 carbon atoms per "minute nitrogen, which contains at least about 75 moles-5 & oxyamine with one or more hydroxyl groups, which are at least 1 carbon atom away from amino nitrogen atoms, in equivalent amounts, so that the reaction product (Λ) has tertiary amino and primary and secondary hydroxyl groups contains and is essentially free of unreacted epoxy groups, B. optionally a di- or polyhydroxy compound and C. an amino resin crosslinking agent in an amount of about 5 to 35% by weight based on the total weight of (A) and (B). 15. Primer according to claim H, characterized by about 0.1 up to 5 wt. ^, based on the total weight of (A) and (C), one or more phosphate esters of the formula (RO) _n P (0H) ₅ _n where η is the number 1 or 2 and R is mono- or dihydroxy-substituted aliphatic «mean radicals with up to about 10 carbon atoms. 030010/0919 16. Primer according to claim. 15 »characterized in that R denotes a monohydroxy-substituted radical ". 17. Primer according to claim 14 »characterized in that - the amine reactant from the hydroxy-substituted secondary aliphatic! Amin exists. 18. Primer according to claim 15s, characterized in that the Arain reaction participant from dialkanolamine with Ms consists of about 10 carbon atoms. 19. Primer according to claim 14 to 18, characterized in that the amino resin crosslinking agent consists of alkylated Melamine resin and / or alkylated urea resin consists. 20. Methods of delaying corrosion in those susceptible to corrosion Substrates by applying a primer, without the need for inhibiting amounts of chromate pigments in the primer, characterized in that one I. applies a crosslinkable hat to the substrate " containing A "an im \ u es borrowed gel-free reaction product" the_ optionally "at least partially_ neutralized, produced by reaction in non-aqueous Medium of 1. not linked by carboxylic acid ester groups Epoxy with an average of at least about two "epoxy groups. Per molecule and 2. Secondary amine or a mixture of primary and secondary amine has a total of up to about 20 carbon atotaea per amine nitrogen that at least about 75 Mo1- $ oxyamine with an or contains a plurality of primary hydroxyl groups which are around at least 1 carbon atom of Amine nitrogen atoms are removed, in equivalent amounts, so that the reaction product (A) contains tertiary amino and primary and secondary hydroxyl groups and of unreacted Epoxy groups are essentially free, B. optionally a di- or polyhydroxy compound and C. an amino resin crosslinking agent in an amount of about 5 "to 35 wt.% Based on total weight of (A) and (B), and II. The crosslinkable mass cures at a temperature of at least about 18 ° C for 20 "to 30 minutes. 21. The method according to claim 20, characterized in that in stage I is applied a composition which further comprises 0.1 to 5 wt.% Of one or more Phosphatester of formula 0
(RO) _n P (0H) ₃ _ _n contains, where η is the number 1 or 2 and R is mono- or dihydroxy-substituted alkyl radicals with up to about Mean 10 carbon atoms. 22. The method according to claim 20, characterized in that an epoxy reactant which is at least about 25 MoI- ^ epoxy compound with at least about two aromatic Contains groups per epoxy group is used. 030010/0919 23. The method according to any one of claims 20 to 22, characterized characterized as having an amine reactant Dialkanolamine is used. 24. The method according to any one of claims 20 to 23, characterized characterized in that as an araino resin crosslinking agent alkylated melamine resin and / or alkylated urea resin is used. 25. The method according to claim 21, characterized in that component (B) is applied. 26. Coated substrate obtained by the method according to any one of claims 20 to 25. 27. Substrate according to claim 26 _f, characterized by a coating applied by spraying. 28. Substrate according to claim 26, characterized by a coating applied by electrodeposition. 030040/0919