DE2855847C2 - Thermosetting coating compound - Google Patents

Description

wherein n - \ to 2 and R are alkyl, cycloalkyl and / or aryl radicals; (C) an amine resin crosslinking agent; and (D) up to 45% by weight based on the total weight of (A), (B), (C) and (D) one

hydroxy-functional additive with a

numerical average molecular weight (M _n ) between 150 and 6000 and possibly customary additives, characterized in that component (A) consists of an epoxy-functional film-forming copolymer with a numerical average molecular weight (M _n ) between 1500 and 000 and a glass transition temperature (Tg) between -25 ° C and 70 ⁰ C consists of

(1) Monofunctional copolymers with bound epoxy functionality, the copolymers being 10 to 30% by weight monoethylene unsaturated glycidyl esters and / or glycidyl ethers and 90 to 70% by weight acrylics and / or other monoethylenically unsaturated vinyl monomers, and / or

(2) bifunctional copolymers with hydroxy functionality and bound epoxy functionality wherein the copolymer of (i) 5 to 25 wt .-% monoethylenically unsaturated glycidyl esters and / or glycidyl ethers and 5 to 25 wt .-% hydroxyalkyl acrylates, which by reaction from dihydric Cr to Cs alcohols and

'Acrylic or methacrylic acid w wur- the formed wherein the total amount of monoethylenically unsaturated monomers which either the Glyzidylfunktionalität or hydroxy carry, instead of the 30 wt .-% of the copolymer constitutes more and (ii) from 90 to 70 wt .-% acrylates and / or other mono-ethylenically unsaturated vinyl monomers and wherein the acrylate monomers comprise at least 50% by weight of the total monomers in the film-forming copolymers and> o consist of esters of monohydric Ci- to Cir alcohols and acrylic acid and / or methacrylic acid and that the organophosphate ester in the Compound is contained in an amount sufficient to provide 0.67 to 1.4 equivalents of acid functionality "for each equivalent of pendent epoxy functionality on the film-forming copolymer,

and wherein the amine resin crosslinking agent is present in the bulk in a sufficient amount w> is included to have at least 0.67 equivalents of nitrogen crosslinking functionality for each Equivalent to give hydroxy functionality in the mass (i) as a hydroxyl group the hydroxy functional additive, (ii) as the η hydroxyl group on the film-forming copolymer, or (iii) as a result of the esterification of the pendant epoxy functionality of the The invention relates to a thermosetting coating composition which can be used for stoving applications at low temperatures Temperature is suitable and which contains greater than about 60 weight percent non-volatile solids, based on Epoxy resins, amine resin crosslinking agents, polyols and phosphoric acid esters as well as customary additives if necessary.

The composition according to the invention is a rapidly curing, thermosetting coating composition with a high Solid content, which is suitable for the production of a car top coat the hardness, high gloss, excellent durability and excellent resistance to solvents and water results. The top coat can contain metal flakes as pigment.

Due to increasingly strict regulations regarding the emission of solvents in recent years Low solvent emission paints became very desirable. A number of High solids paint compositions have been proposed to meet these needs in terms of low solvent emissions. However, many of these crowds are due to the Difficulty of application, slow curing speeds, lack of flexibility, worse Durability and poor solvent and water resistance are disadvantageous. Many of the proposed measures were considered deficient in particular Car top coats, especially if the top coat should contain metal flakes as pigment.

The disadvantage with masses that include metal flakes results from undesirable reorientation of the Metal flakes during the application and curing of the coating. The flake reorientation results mainly due to the thin coating masses used very low viscosity resins to accommodate high solids. The minor one Thixotropic is not enough to immobilize the flakes, which tend to re-establish on their own distribute to give "swiveling" and uneven distribution.

The coating compositions of the invention combine the desirable properties discussed above and low application viscosity with rapid cure so that the disadvantages of heretofore proposed high solids materials are eliminated, and thereby "A coating compound with a high solids content is achieved, which is particularly suitable for car top coatings and is especially suitable for car top covers. which contain metal flakes as pigment.

The thermosetting coating composition of the invention contains greater than 60% by weight of non-volatile solids, preferably more than 70% by weight and is capable of rapidly to harden at low temperature.

The invention relates to a thermosetting coating composition with more than 60% by weight non-volatile Solids from (A) an epoxy resin, (B) at least one organophosphate ester of the formula

(RO) _n - P- (OH), -,

where n = 1 to 2 and R is alkyl, cycloalkyl and / or aryl radicals; (C) an amine resin crosslinking agent; and (D) up to 45% by weight, based on the total weight of (A), (B), (C) and (D), of a hydroxy-functional additive having a numerical average molecular weight (M _n ) between 150 and 6000 and possibly customary additives, which is characterized in that component (A) consists of an epoxy-functional film-forming copolymer with a numerical average molecular weight (M _n ) between 1500 and 10,000 and a glass transition temperature (Tg) between - 25 ° C and 70 "C consists of

(1) monofunctional copolymers with bound Epoxy functionality, the copolymers consisting of 10 to 30% by weight of monoethylenically unsaturated Glycidyl esters and / or glycidyl ethers and 90 to 70% by weight of acrylates and / or other monoethylene unsaturated vinyl monomers are built up, and / or

(2) bifunctional copolymers with hydroxyl functionality and bound epoxy functionality, the copolymers of (i) 5 to 25% by weight of monoethyienically unsaturated glycidyl esters and / or glycidyl ethers and 5 to 25% by weight of hydroxyalkyl acrylates, the duich implementation of Dihydric C2 to Cs alcohols and acrylic acid or methacrylic acid were formed, the total amount of the monoethylenically unsaturated monomers, which either carry the glycidyl functionality or the hydroxy functionality, not more than 30 wt .-% of the copolymer and (ii) 90 to 70 wt .-% acrylates and / or other mono-ethylenically unsaturated vinyl monomers and wherein the acrylate monomers comprise at least 50% by weight of the total monomers in the film-forming copolymers and consist of esters of monohydric C 1 to C 2 alcohols and acrylic acid and / or methacrylic acid
and that the organophosphate ester is contained in the bulk in an amount sufficient to provide 0.67 to 1.4 equivalents of acid functionality for each equivalent of pendant epoxy functionality on the film-forming copolymer,

and wherein the amine resin crosslinking agent is included in the composition in an amount sufficient to provide at least 0.67 equivalent of nitrogen crosslinking functionality for each equivalent of hydroxy functionality present in the composition (i) as a hydroxyl group on the hydroxy functional additive, (ii) as a hydroxyl group on the film-forming copolymer or (iii) as a result of esterification of the pendant epoxy functionality of the film-forming copolymer during curing of the coating composition.
The alkyl group of the organophosphorus is preferably

phatmonoesters a predominantly straight-chain residue with 2 to 6 carbon atoms.

Preferably at least one alkyl group of the organophosphate diester consists of predominantly one straight-chain radical with 2 to 6 carbon atoms.

The organophosphate ester is contained in the mass in an amount sufficient to between about 0.67 and about 1.4 equivalents, preferably between about 0.8 and about 1 equivalent, of acid functionality for each Equivalent epoxy pendant functionality dps copolymers to surrender. The amine resin crosslinking agent is in the bulk in a sufficient amount contain at least about 0.67, preferably between about 0.75 and about 3.75 equivalents, of nitrogen crosslinking functionality for each equivalent of hydroxy functionality to give in bulk either (i) as a hydroxyl group on the copolymer, (ii) a hydroxyl group on the optional hydroxy functional additives or (iii) as a result of the esterification of the pendant epoxy functionality of the copolymer is contained during the curing of the coating composition. Furthermore, the erfindungsgernäßc Coating compound with a high solids content Contain additives, such as catalysts, antioxidants, UV absorbers, flow regulators or wetting agents, antistatic agents, pigments, plasticizers, solvents and the same.

In US-PS J9 60,979 and 40 18 848 are High solids coating compositions which are suitable for Suitable for use as a can coating material. The masses essentially consist of (i) aromatic epoxy compositions having two or more epoxy groups on an epoxy resin having a molecular weight of not more than 2500, (ii) an amino crosslinking agent, (iii) an inorganic one or organic monomeric or polymeric acid which acts as a reactive catalyst and (iv) a flexible making polyol.

The masses according to these patents have the advantage of rapid reaction and more effective application viscosity, however, they lack durability and are therefore not well exposed to weathering. This is possible partly due to the presence of ether bonds in the aromatic epoxides. As such, the Compounds according to the patents cited above are not desirable for use as automotive topcoats. In the patents mentioned, the compositions are described as a slow-curing system. If however, taking into account the specific teachings of these patents, it is found that the mass is a Excess epoxy resin contains, apparently with the purpose of removing excess catalyst after completion destroy the hardening reaction. Excess epoxy resin in the mass remains with the Low-temperature stoving range of the specified stoving temperatures unhardened, none results full cure and no desired hardness, persistence, or solvent resistance. at When heated to higher temperatures than required in the examples, excess epoxy groups also react excess hydroxy functionality to give even more ether bonds. These so obtained Ether bonds have another detrimental effect on durability and make the materials particularly unsuitable for use as car top coats. The necessary high stoving temperatures, to achieve the consumption of these excess epoxy groups, make the Mass from the energy standpoint due to the required

union high baking temperatures undesirable. Furthermore must, since the epoxy / catalyst reaction takes place in the early stages of curing and thus the Catalyst is destroyed, the melamine / hydroxy curing reaction take place essentially without the advantage of> catalysis. The hardening reaction proceeds thus slow and requires the high temperatures indicated in the examples of the patents mentioned.

The masses according to the invention with a high solids content eliminate the disadvantages of previous masses with a high solids content, including the masses according to the above patents, and provide a system which is particularly suitable for such applications, which have high gloss, hardness, durability and high solvents . oil and water resistance as well as a rapid rate of cure at low temperatures, for example about 75 ° C to about 150 ° C, preferably about 110 ° C to about 130 ° C. The desired properties of the coating compositions according to the invention are due to the carefully controlled mixing of the special components while achieving practically complete consumption of the functionality of the reactants in a rapid and effective manner. j-,

The respective components of compositions with a high solids content, the amounts of the respective components which are necessary to achieve the desired results of the invention, and a method for applying the composition are hereinafter described in detail so on.

Epoxy functional film-forming polymer

As mentioned above, the epoxy-functional film-forming material of the compositions according to the invention can r, from monofunctional copolymers, the pendent Carrying epoxy functionality or bifunctional copolymers that have both pendant epoxy functionality as well as carry hydroxy functionality. These film-forming copolymers, which are a Represent the main material of the coating compositions according to the invention with a high solids content, can by conventional, free radical induced polymerization of suitable unsaturated monomers can be prepared. The term "copoiymeres" used here means a copoiymeres of two or more different monomers.

The copolymers used in the compositions of the invention with a high solids content have a numerical average molecular weight (M _n ) between about 1500 and about 10,000, preferably between about 2000 and about 6000 and a glass transition temperature (Tg) between about -25 ° C and about 70 ° C , preferably between about -10 ° C and about 50 ° C.

For the production of the monofunctional copolymers The monomers used contain between about 10 and about 30% by weight of one or more mono-ethylenically unsaturated monomers which carry glycidyl functionality. This mono-ethylene Unsaturated monomers can be glycidyl ethers or & o glycidyl esters. The epoxy-functional ones are preferred Monomers, however, glycidyl esters of monoethylenically unsaturated carboxylic acids, e.g. B. glycidyl acrylate or glycidyl methacrylate. These monomers deliver that Copolymers with its pending epoxy functional-,

The monomers which are used for the preparation of the bifunctional which can be used in the compositions of the invention Copolymers used contain between about 5 and about 25 weight percent of one or more of the glycidyl functional copolymers and discussed above between about 5 and about 25% by weight of one or more monoethylenically unsaturated monomers, which carry hydroxyl functionality, the total amount of mono-ethylenically unsaturated monomers, bearing either epoxy or hydroxy functionality, no greater than about 30% by weight of the Monomers in the copolymer.

The mono-ethylenically unsaturated hydroxy-functional monomers that make up the bifunctional copolymer with its hydroxy functionality can be selected from a long line of hydroxy-functional Monomers are selected. However, the hydroxy-functional monomers are preferably acrylates and can from the group of the following esters of acrylic acid or methacrylic acid and aliphatic Alcohols can be selected, but not limited to:

2-hydroxyethyl acrylate,

3-chloro-2-hydroxypropyl acrylate.

2-hydroxy-1-methylethyl acrylate,

2-hydroxypropyl acrylate,

3-hydroxypropyl acrylate,

23-dihydroxypropyl acrylate,

2-hydroxybutyl acrylate,

4-hydroxybutyl acrylate,

Diethylene glycol acrylate,

5-hydroxypentyiacrylate,

6-hydroxyethyl acrylate,

Triethylene glycol acrylate,

7-hydroxyheptyl acrylate,

2-hydroxymethyl methacrylate,

S-chloro ^ -hydroxyDropyl methacrylate,

2- hydroxy-1-methylethyl methacrylate,

2-hydroxypropyl methacrylate,

3-hydroxypropyl methacrylate,

2,3-dihydroxypropyl methacrylate,

2-hydroxybutyl methacrylate,

4-hydroxybutyl methacrylate,

3,4-dihydroxybutyl methacrylate,

5-hydroxypentyl methacrylate,

6-hydroxyhexyl methacrylate,

1,3-dimethyl-3-hydroxybutyl methacrylate,

5,6-dihydroxyhexyl methacrylate and

7-hydroxyheptyl methacrylate.

While one skilled in the art will recognize the many different hydroxy-bearing monomers that can be used, including those identified above, the preferred hydroxy-functional monomers for use in the bifunctional copolymers of the invention are C5-Cz-hydroxyalkyl acrylates and / or C-, - Cg-hydroxyalkyl methacrylates, ie esters of divalent C2- Q-alcohols and acrylic acid or methacrylic acid.

The remainder of the monomers which make up the epoxy functional film-forming polymer, i.e. H. between about 90 and about 70% by weight of the monomers of the copolymer, and other monoethylenically unsaturated Monomers. These monoethylenically unsaturated monomers are preferably a ^ -olefinically unsaturated ones Monomers, d. H. Monomers that have olefinic unsaturation between the two carbon atoms in the λ- and ^ position with respect to the end of an aliphatic plastic-carbon chain. Among the ", ^ - olefinically unsaturated monomers, that can be used are acrylates (in the

Meaning of esters of either acrylic acid or Methacrylic acid) and mixtures of acrylates and vinyl hydrocarbons. Preferably are more than 50% by weight of the total amount of the copolymer monomers esters of monohydric Ci-Ci! Alcohols tint! Acrylic or methacrylic acid, for example methyl meth acrylate, ethyl acrylate. Butyl acrylate, butyl methacrylate. llexyl acrylate, 2-ethylhexyl acrylate, lauryl methyl acrylate and the same. Among the monovinyl hydrocarbons suitable for use in preparing the copolymers are those that contain 8 to 12 hydrocarbon atoms and include styrene, Λ-methylstyrene. Vinyl toluene. tert-butyl styrene and Chlorostyrene. If such monovinyl hydrocarbons are used, they should be less than 50% by weight of the copolymer. Other monomers such as vinyl chloride. Acrylonitrile. Methacrylonitrile and vinyl acetate can be included in the copolymer as modifying monomers. if however, if they are used, these modifying monomers should only be br, about 30% by weight of the monomers in the copolymer.

In the manufacture of monofunctional or bifunctional copolymers are the monomers carrying the desired epoxy and hydraulic functionality and the remaining mono-ethylenically unsaturated monomers mixed and by customary by free Radical initiated polymerization implemented in such proportions that the desired copolymer is obtained. A large number of Frciiadikdlischcr Initiators are known in the art and are suitable for clic purposes. This includes:

Benzoyl peroxide. l.aiiryl peroxide.

ten. -Bu ty! hydroxy perox id.

Acetylcyclohexane. Sulfonic hydroxide, Diisobutyl peroxide.

Di- (2ethylhexyl) -pero \\ di carbonate.

Diisopropyl hydroxydicarbonate.

ten-butyl peroxypivalate decanoyl peroxide.

Azobis (2-meth \ lpropionitrile)

and the same. The polymerization is preferably carried out in solution using a solvent, ir. that the epoxy-functional copolymer is soluble. Included among suitable solvents are toluene. Xylene. Dioxane. Butanone and the like. When the epoxy functional copolymer is in solution is produced, the solid copolymer can be precipitated by the solution at low speed into a non-solvent for the copolymer such as hexane. Octane or water below suitable stirring conditions is poured.

The mono- or bifunctional copolymers suitable in the compositions of the invention can also by Emulsion polymerisation, suspension polymerisation, polymerisation in bulk or combinations therefrom or by other suitable methods. With these methods of manufacture chain transfer agents may be required to reduce the molecular weight of the copolymers To regulate copolymers to the desired range. If chain transfer agents are used, Care must be taken that they do not affect the shelf life of the mass by induction reduce premature chemical reactions.

Organophosphate ester

A second essential component of the invention Coating compounds with high- ^. Solids content is an organophosphate mono- or diester or a mixture of such mono- and diesters. Such Organophosphate esters are preferably made by esterifying phosphoric acid or its anhydrides or by gc.-rge! ■ - hydrolysis of alkyl, Cycloalkyl- or Arylhal «. · ^ Phosphates produced. In Organophosphate esters useful in the compositions of the invention are those of the following formula

IROI ₁ -P-MII), "

■ wherein / i-1 to 2 and R is alkyl, cycloalkyl and / or Represent aryl groups. The mono or diesters are preferably alkyls and the hydrocarbon sub Any alkyl group can be substituted in these cases be including methyl. Ethyl-. Butyl, amyl.

■ 2-ethylhexyl, lauryl and stearyl groups and the like chen. without being limited to it. Most preferred alkyl groups contain from 2 to 6 carbon atoms and are predominantly straight-chain residues.

The organophosphating component of the invention. according to the coating composition with a high solids content is a reactive catalyst which leads to the The mass hardens rapidly at a low temperature. The acid functionality of the mono- or diester or the Mixture * of such esters reacts with the

■ ■ the epoxy functionality of the epoxy-functional film former with formation of an ester and a hydroxyl group. It is precisely this kydroxyl functionality that is networked with the amine resin crosslinking agent. To achieve the desired results of the mass according to the invention

.. Senes with a high solids content, ie to make them suitable for use as an auto topcoat. it is critical that the amount of the organophosphate ester be sufficient ^; st. to substantially all of the epoxy functionality on the copolymer

'Desired hydroxy functionality through esterification reaction to convert. Therefore, the organophosphate ester is in a sufficient amount in bulk incorporated to between about 0.67 and about 1.4 equivalents, preferably between about 0.8 and about 1 -. Equivalent to. Acid functionality for each equivalent of pendant epoxy functionality on the copolymer to surrender. As can be seen from the equivalent amount given above, the amount of organophosphate ester acid functionality not in stoichiometric

There are Vi amounts of epoxy functionality. this is based on the fact that during the hardening of the upper coating mass with a high solids content residual water present in the mass part of the esterification product hydrolyzed back to the acid and this

5; hydrolyzed product in turn with additional) Epoxy functionality reacts

Amine resin crosslinking agent

A third essential component of the invention According to high solids paints, an amine resin crosslinking agent is used. Amine crosslinking agent, the materials that are suitable for crosslinking hydroxy functionality are known in the art known Typically, these crosslinking materials are products of the reactions of melamine or Urea with formaldehyde and various alcohols with up to and including 4 carbon atoms. Preferably d'e are suitable according to the invention

Amine crosslinking agents amine-aldehyde resins such as Condensation products of formaldehyde with melamine, substituted melamine, urea, Benzoguanamine or substituted benzoguanamine. Preferred members of this class are methyücrtc Melamine-formaldehyde resins such as hexamethoxymethylmelamine. These liquid crosslinking agents are practically 100% non-volatile C / est constituents, measured according to the film method at 45 "C for 45 minutes. For the purposes of the invention, it must be ensured that i '; s is important. None introduce external diluents which lower the final solids content of the coating would.

Particularly preferred crosslinking agents are amine resins, which are sold by American Cyanamid under the trademark "Cymel". Special suitable in the compositions of the invention are Cymel 301. Cymel 303 and Cymel 1156. the alkylated Are melamine formaldehyde resins.

The amine resin materials act as crosslinking agents in the composition of the invention by reacting with (i) any hydroxy functionality that may be present in the epoxy functional film former, (ii) hydroxy functionality, that by esterification of the pendant epoxy functionality on the epoxy functional copolymer and (iii) hydroxy functionality on the hydroxy functional additive, if any Material is contained in the mass.

To achieve excellent properties, which makes these coating compositions particularly suitable as Car top coat materials are made, it is essential that the amount of amine crosslinking agent is sufficient to completely crosslink the hydroxy functionality in the coating composition. Hence should the amine resin crosslinking agent may be included in the composition in an amount sufficient to at least about 0.67 equivalents, preferably between about 0.75 and about 3.7 equivalents, nitrogen crosslinking radio tionality for each equivalent in bulk of either (i) as the hydroxyl group on the epoxy functional Film film binders, (ii) as a hydroxyl group on the optional hydroxy functional additive or (iii) as a result of esterification of the pendant epoxy functionality of the epoxy functional To give Filmbüdners hydroxy functionality present during the curing of the coating composition.

Optionally present hydroxy-functional additive

Additional hydroxyl functionality that deviates from the epoxy functionality of the epoxy-functional copolymer present on the film former or that achieved by esterification can be achieved by adding a hydroxyl-functional additive in amounts up to about 30% by weight, based on the total amount of the three components discussed above and of the hydroxy-functional additive itself. Such a material serves to provide additional hydroxy-functional additive, so that a more intimate Vemetzungsstruktur in the final cured product is formed The suitable in the compositions hydroxy-functional additives are preferably selected from different Poryolen with a numerical average molecular weight (M _n) between about 150 and about 6000 , preferably selected between about 400 and about 2500 The term "polygol" used here means a use with two or more hydroxyl groups.

The polyols suitable according to the invention are preferably selected from the group consisting of made of: (i) hydroxy-functional polyester, (ii) hydroxy-

Ί functional polyethers, (iii) hydroxy-functional Oligoesters, (iv) monomeric polyols, (v) hydroxy-functional copolymers, which are produced by free-radical Polymerization of monoethylenically unsaturated monomers can be obtained, one of which has hydroxy functionality and that in the copolymer in an amount in the range from 2.5 to about 30% by weight and (vi) mixtures of (i) to (v).

The hydroxy-functional polyesters suitable according to the invention are preferably completely saturated -, te products derived from aliphatic dibasic acids with 2 to 20 carbon atoms, such as Succinic acid, glutaric acid, adipic acid, azelaic acid and the like and short chain glycols with up to unci including 21 carbon atoms such as

2 (i wise

Ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, I.2-butylene glycol.
1,3-biitylene glycol, 1,4-butylene glycol,
Neopentyl glycol, 1,4-cyclohexanedimethanol,

> \ 1,6-hexamethylene glycol and

2-ethyl-2-methyl-1,3-propanediol,
getting produced. The molecular weight of these materials ranges from about 200 to about 2500 and the hydroxyl number ranges from about 30 to

in about 230. The hydroxyl number is expressed as the number in Milligrams of potassium hydroxide defined for each gram of sample used to neutralize the Reaction between the polyol and excess acetic anhydride generated acetic acid is necessary.

r> The polyester polyols used according to the invention are low melting soft waxy solids that are easily melted in the molten state can be held.

Among preferred polyesters are products that are

i.i from the esterification of ethylene glycol and 1,4-butanediol with adipic acid. Ethylene glycol and 1,2-propylene glycol derive with adipic acid, azelaic acid and sebacic acid copolyester diols and their mixtures.

Under suitable Poiyätherdiolen are

4i polytetrafluoroethylene ether glycol. Polyethylene glycol, polypropylene glycol and the same.

The hydroxy functions useful as hydroxy functional additives in the compositions of the invention Oligoesters are oligoesters. the preferably one

γι have a molecular weight between about 150 and about 3000. Such oligoesters can be selected from the group consisting of: (1) Oligoesters, which are prepared by reacting a dicarboxylic acid with a monoepoxide such as an alkylene oxide,

(2) oligoesters made by reacting a polyepoxide are produced with a monocarboxylic acid and (3) oligoesters, which are obtained by reacting a hydroxy-functional monocarboxylic acid with a mono- or Polyepoxide are produced, can be selected.

The oligoester made by reacting a dicarboxylic acid with an alkylene oxide is a low molecular weight adduct that has a narrow molecular weight distribution compared to similar compositions made by normal polyester manufacturing techniques. The adduct is prepared by reacting a divalent carboxylic acid with alkylene oxides, preferably ethylene oxide or propylene oxide, in the presence of a catalyst

Preferred dicarboxylic acids are aliphatic G 1 -Cij acids such as adipic acid, azelaic acids, sebacic acid or dodecanedicarboxylic acid. Mixtures these acids or mixtures of the aliphatic dicarboxylic acids with aromatic dicarboxylic acids also make suitable hydroxy-functional oligoesters.

The production of oligoesters from carboxylic acids and polyepoxides is known and is described for example in US-PS 24 56 408 and 26 53 1341st Numerous hydroxy-functional oligoesters within this general category are familiar to those skilled in the art.

The third type of hydroxy functional oligoester, i. H. those made by implementing a hydroxy-functional Monocarboxylic acid are prepared with an epoxide is described in US Pat. No. 3,440,018. Although the epoxides used according to this patent are polyepoxides, oligoesters in same way to the Harin hpsrhriehenpn Wpiw be prepared by adding a monoepoxide, e.g. B. an alkylene oxide and a hydroxy-functional monocarboxylic acid used as described therein. Numerous monoepoxy materials suitable for this purpose will be apparent to those skilled in the art.

Among the numerous monomeric polyols that jls The hydroxy-functional additives that can be used are the various short-chain ones Glycols of up to and including 21 carbon atoms used in the manufacture of the hydroxy functional polyester are suitable. Other common polyhydric alcohols such as glycerine and Sugar alcohols are also among the numerous monomeric polyols known to those skilled in the art Area are familiar.

The copolymer carrying hydroxy functionality which is suitable as a hydroxy-functional additive can be formed from monoethylenically unsaturated monomers with about 2.5 to about 30% by weight of hydroxyl functionality .

The long range of hydroxy-functional monomers that can be used in these hydroxy-functional copolymers includes, but is not limited to, the following esters of acrylic or methacrylic acid and aliphatic alcohols:
2-hydroxyethyl acrylate, S-chloro ^ -hydroxypropyl acrylate, 2-hydroxy-1 -methylethyl acrylate,

2- hydroxypropyl acrylate,

3- hydroxypropyl acrylate, 23- dihydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, diethylene glycol acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, triethylene glycol acrylate, 7-hydroxyheptyl acrylate, 2-hydroxy-hydroxymethyl methacrylate, 2-chloro-hydroxymethyl methacrylate, 2-chloro-hydroxymethyl methacrylate, 2-chloro-hydroxymethyl methacrylate, 2-chloro-hydroxymethyl methacrylate, 2-chloro-hydroxymethyl methacrylate, 2-hydroxymethyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxymethyl methacrylate, methylethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 23-dihydroxypropylniethacrylat, 2-hydroxybutyl methacrylate, 4-hyäroxybiiiyiinethacrylat, 3,4-dihydroxybutyl methacrylate, 5-hydroxypentyimethacrylate,

6-hydroxyhexyl methacrylate,

1,3-dimethyl-3-hydroxybutyl methacrylate,

5,6-dihydroxyhexyl methacrylate and

7-hydroxyheptyl methacrylate.

Although one skilled in the art will recognize that many different hydroxy bearing monomers, including of those listed above could be used are the preferred hydroxy functional ones Monomers for Use in the Hydroxy Functional Resin of the Invention Cs-C; -Hydroxyalkyl acrylates and / or Cs-Ca hydroxyalkyl methacrylates, i.e. Esters of dihydric C> - Ci alcohols and acrylic acid or methacrylic acid.

The remainder of the monomers forming the hydroxy-functional copolymer, ie between about 90 and about 70% by weight, are other mono-ethylenically unsaturated monomers. These monoethylenically unsaturated monomers are, as discussed above, pnnYvfiinktinnpllp Cnnnlvmprp vnrvnpswpUp / v ß-nlpfi-

i -f ι - * σ- - τ

nically unsaturated monomers. As with the epoxy functional copolymer, these are preferred x./f- olefinically unsaturated monomers acrylates and are preferably used in greater than 50% by weight of the total copolymer. Preferred acrylate monomers are esters of monohydric Ci-Ci2 alcohols and Acrylic acid or methacrylic acid. Monovinyl hydrocarbons and other modifying monomers can can also be used in the same proportion as used in the epoxy functional copolymer discussed above can be used.

Other materials

In addition to the components discussed above, other materials can be incorporated into the high solids coating compositions of the invention. These include materials such as catalysts, antioxidants, UV absorbers, solvents, surface modifiers and wetting agents, and pigments. The solvents used in the coating compositions of the invention are those which are commonly used. Typical solvents which are suitable in the coating compositions facilitate spray application when the solids content is high and these include toluene, xylene, methyl ethyl ketone and acetone. 2-ethoxy-1-ethanol, 2-butoxy-1-ethanol, diacetone alcohol. Tetrahydrofuran, ethyl acetate. Dimethyl succinate, dimethyl glutarate, dimethyl adipate or mixtures thereof. The solvent in which the epoxy-functional copolymer of the coating composition is prepared can be used as the solvent for the coating composition, whereby the need for drying the epoxy-functional copolymer after preparation, if this is desired, is eliminated.As mentioned above, the content of the coating composition high solids non-volatile solids at least 60%, and preferably 70% or more, thereby limiting the amount of solvent entrapped in the mass.

Surface modifiers or wetting agents are common additives for liquid paints. The exact mode of action of these surface modifiers is not known, but it is believed that their presence for better adhesion of the coating composition to the surface to be stripped contributes and promotes the formation of thin upper layers, especially on metal surfaces. These surface modifiers are for example by

Arryl polymers with a content of 0.1 to 10 wt .-% a copolymerized monoethylenically unsaturated carboxylic acid such as methacrylic acid, acrylic acid odor itaconic acid, cellulose acetate butyrate, silicone oils or their mixtures. of course is the choice of surface modifier or wetting agent depends on the nature of the too coating surface and the choice of the same is clearly within the ability of the person skilled in the art.

The coating compositions of the invention with a high solids content can also contain pigments. As indicated above, the high solids compositions of the invention are particularly useful when the coating composition contains metal flakes as pigment. The rapid solidification and hardening of the mass eliminates the difficulties associated with redistribution of the metal flakes. The amount of pigment in the high solids coating composition can vary, but is preferably from about 3 to about 4%, pui .o / n Kp7r * cTf »n on the weight of the coating composition. If the pigment is metallic flake, "0, the amount will range from about I to about 7 wt .-%.

Application techniques

The coating composition with a high solids content can be prepared by customary methods known to the person skilled in the art be applied. These methods include roller application, spray application, dipping, or Brushing and of course the particular application technique will depend on the particular too coating substrate and the environment in which the coating process is to take place is selected.

A particularly preferred technique for applying the high solids coating compositions, in particular when applied as auto topcoats, the spray coating is through the nozzle a spray gun.

High solids paints have in the past caused some difficulties with the Spray coating techniques due to the high viscosity of the materials and the difficulties resulting therefrom the clogging of the spray gun. However, the masses of the invention as they are relatively low Viscosity given the high solids content, applied by spray coating techniques will.

The invention is further elucidated with reference to the following detailed examples, without it to be limited. Unless otherwise stated, all data relating to “parts” relate to parts by weight.

example 1

The following mixture of monomers was used for a polymer synthesis:

Weight (g) wt%

Butyl methacrylate

Ethylhexyl acrylate

Glycidyl methacrylate

Styrene

127.5
180
195
2iQ

37.5

17th
24
26th
28

37 g of tert-butyl perbenzoate becomes the above Added monomer mixture and the resulting solution over a period of 1 hour and 10 minutes added to 500 g of refluxing methyl amyl ketone under nitrogen. Heat and stir continued for half an hour after he added is complete, and then 2 g of tert-butyl perbenzoate are added in portions. The reaction mixture will refluxed for an additional two hours and then allowed to cool to room temperature. The calculated 7j? Value of the polymer obtained is 9 ° C. and the solution viscosity is 41 Seconds, Ford Mug No. 4.

83 '/ j parts of the above polymer solution and 30 parts Hexamethoxymethylmelamine are dissolved in 25 parts of butyl acetate and 11 parts of acid butyl phosphate (a mixture of monobutyl and dibutyl phosphates, Equivalent weight 120) are added to the solution. The formulation obtained is on steel test plate

130 "C baked in for 20 minutes, with a glossy (82/20 °) coating with excellent hardness, adhesion and resistance to solvents (Xylene and methyl amyl ketone) is obtained. The coating shows no loss of gloss or adhesion Muh fortnightly exposure in a Cleveland humidity chamber.

Example 2

4 parts of aluminum flakes (65% in naphtha) are mixed well with 80 parts of the polymer solution prepared according to Example 1. 30 parts of hexamethoxymethylmelamine and 25 parts of butyl acetate are added to the above mixture and the resulting material is filtered through a coarse filter cloth. 11 parts of acid butyl phosphate (equivalent weight 120) are added to the filtrate and the resulting formulation is applied directly to primed steel plates by spraying in a triple coat application. The intermediate evaporation time is 1 minute and the final evaporation time is 5 minutes. The plates are baked at 110 ° C for 20 minutes, whereby coatings excellent in adhesion and resistance gege, "solvent (YxIoI and methyl ethyl ketone) are obtained. There does not occur. ^C ichtbare Aluminiumreorientierung in. And the gloss is 62/20 ° C .

Example 3

Fin epoxy functional copolymer is made from the following monomers:

Weight (g) wt%

Butyl methacrylate

Ethyl acrylate

Glycidyl methacrylate

Methyl methacrylate

Styrene

120
142.5
195
255

37.5

16
19th

26th
34

The polymerization is given as in Example 1, using 500 g of methyl amyl ketone and 30 ε tert-butyl perbenzoate carried out. The addition of initiator and the monomer mixture takes 2 hours finished, and the reaction mixture is for a aeha'.ten another hour under reflux. 2 e des

Initiator is then added and the reaction mixture is refluxed for 2 hours. The molecular weight is determined by gel permeation chromatography and was found to be M "= 3168 and MJM" = 2, \ 5. The 7 value of this polymer is calculated as 20 ° C. 27 parts of the above polymer solution and 10 parts of Cymel 301 are dissolved in 8 parts of butyl acetate dissolved and 2.8 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates) are added to this solution. The mass is mounted on a steel test panel and baked at 130 ⁰ C for 20 minutes The top pull has excellent hardness, adhesion and solvent resistance (xylene and methyl ethyl ketone).

Example 4

27 parts of the polymer described in Example 3, 13 parts of hexamjihoxymethylmelamine and 5 parts of acrylic polymer with 30% hydroxyl functionality MC 1000. v / ground 3.7 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphate) dissolved in 10 parts of butyl acetate above solution is added, and the formulation obtained is drawn up on steel test plates. It is baked at 130 ° C. for 10 minutes, with a glossy coating with excellent hardness. Adhesion and solvent resistance is obtained.

Example 5

12 ethyl phosphorus dichloridate in 150 ml Dissolved butyl acetate, placed in a round bottom flask and cooled with an ice-water mixture. 28 g cold water are added dropwise with stirring and simultaneous application of vacuum with a water pump admitted. The reaction mixture is stirred under vacuum for 3 days and then titrated with sodium hydroxide, whereby a monoethyl phosphate solution with an acid equivalent weight of! 12 is obtained.

80 parts of the polymer solution prepared in Example 1, 10 parts of bis (hydroxypropyl) azelate (product of propylene oxide and azelaic acid) and 35 parts of ethoxymethoxymethylbenzoguanamine are in 25 parts of butyl acetate dissolved, and 10.1 parts of the above acidic ethyl phosphate solution are added to this solution. the The formulation obtained is applied to primed steel plates by spraying and kept at 130 ° C during Baked for 20 minutes, leaving hard glossy coatings with excellent adhesion and solvent resistance can be obtained.

Example 6

A butyl acetate solution of monocycloxylmethyl phosphate having an equivalent weight of 145 is used prepared from cyclohexylmethylphosphorus dichloridate according to the procedure given in Example 5.

25 parts of the polymer solution prepared in Example 3, 13 parts of hexamethoxymethylmelamine (Cymel 301, American Cyanamid) and 5 parts of caprolactone-based hydroxy ester PCPO300 (Union Carbide) are sold in 10 parts of butyl acetate dissolved. 4.2 parts of the acidic phosphorus prepared above become the above Solution is added and the resulting formulation is sprayed onto primed steel test panels upset. The plates get hot! 30 "C during 20 Baked in minutes, with coatings of excellent hardness. Liability. Gloss and solvent resistant wedge (Xylene and methyl ethyl ketone).

Example 7

The following mixture of monomers is used in a polymer synthesis:

Butyl methacrylate
Glycidyl acrylate
Methyl methacrylate
Styrene

Wt%

25th

30th

40

The polymerization is carried out as indicated in Example 1, with a 50% strength solution of the polymer being obtained executed

ι ä 70 parts of the polymer solution, 15 parts of bis (hydroxypropyl) azelate (Reaction product of propylene oxide and azelaic acid) and 25 parts of hexamethoxymethylmelamine (Cyme! 301) are dissolved in 10 parts of butyl acetate. Acid amyl phosphate (mixture of monoalkyl-

M and dialkyl phosphates [13.3 parts]) becomes the above Solution is added and the resulting formulation is applied to primed steel sheets by spraying. The plates are kept at 130 ° C for 20 minutes to obtain glossy (87/20 °) coatings with excellent

2-, branded adhesion, hardness and solvent resistance (xylene and methyl ethyl ketone).

Examples

A hydroxy acrylic copolymer is made from the following monomers:

Weight (g) wt%

Butyl methacrylate 1000 50 1 hydroxyethyl acrylate 400 20th Methyl methacrylate 400 20th Stvrol 200 10

100 g of tert-butyl perbenzoate are added to the above monomer mixture, and the obtained Solution is added dropwise to 1400 g of reflux over a period of 2 hours Methyl amyl ketone added under nitrogen. The heating and stirring is after half an hour Completion of the addition is continued and 5 g of tert-butyl perbenzoate are added in portions to the reaction mixture admitted. The reaction mixture is refluxed for an additional 90 minutes and left then cool to room temperature. The molecular weight is determined by gel permeation chromatography certainly:

M _n = 2450, ÄU M _n = 1.94.

40 parts of the above polymer, 45 parts by weight of the glycidyl methacrylate polymer from Example 1 and 31 parts of hexamethoxymethyl melamine are dissolved in 20 parts of butyl acetate. 53 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates, equivalent weight 120) are added to the above solution, and the resulting formulation is applied to primed steel test panels by spraying. The plates are ^{baked at 130 °} C. for 20 minutes, with glossy coatings of excellent hardness. Adhesion and resistance to solvents (xylene and methyl ethyl ketone) can be maintained.

230; i8 - f, l3

Example 9

25 parts of the polymer from Example 3, 25 parts of hydroxy polymer from Example 8 and 25 parts of hexabutoxymethylmelamine are dissolved in 15 parts of butyl acetate 3.4 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates, equivalent weight 120) are added to the above solution, and the resulting formulation is applied to primed steel panels by spraying the plates are baked at 130 ⁰ C for 20 minutes with shiny upper coatings with excellent hardness, adhesion and solvent resistance can be obtained.

Example 10

30 parts of the glycidyl methacrylate polymer from Example 3, 5 parts of bis (hydroxypropyl) azelate and 15 parts Ethoxymethoxymethylbenzoguanamine are dissolved in 10 parts of butyl acetate, 4.4 parts of acid butyl phosphate (Mixture of monobutyl and dibutyl phosphates, equivalent weight 120) become the above solution added, and the resulting formulation is applied to primed steel panels by spraying Panels are baked at 130 ° C for 20 minutes, with hard, glossy outer layers excellent adhesion and solvent resistance (xylene and methyl ethyl ketone) can be obtained.

Example 11

25 parts of glycidyl methacrylate polymer from Example 1, 20 parts of hydroxy polymer from Example 8, 5 parts Bis (hydroxypropyl) azelate and 17 parts butoxymethyltjykoluril are dissolved in 15 parts of butyl acetate 3.3 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates, equivalent weight 120) added to the above solution, and the resulting formulation is applied to primed steel panels Spray applied The panels are heated at 130 "C Baked for 20 minutes with hard glossy coatings with excellent adhesion and solvent resistance (Xylene and methyl ethyl ketone) can be obtained.

Example 12

30 parts of glycidyl methacrylate polymer from Example 3, 7 parts of the acrylic polymer given in Example 4. 25 parts of butoxymethylurea resin are dissolved in 20 parts of butyl acetate. 4.4 parts of acid butyl phosphate (Mixture of monobutyl and dibutyl phosphate equivalent weight 120) become the above solution added, and the resulting formulation is applied to primed steel panels by spraying Plates are baked at 130 ° C. for 20 minutes to give a hard, glossy coating.

Example 13

The following mixture of monomers is used to synthesize a polymer:

Wt%

Allyl glycidyl ether 30th Butyl methacrylate 25th Methyl methacrylate 30th Styrene 15th

Methyl amyl ketone.

31 parts of the above polymer, 30 parts of the hydroxy polymer of Example 8 and 17 parts of hexamethoxymethyl melamine are dissolved in 10 parts of butyl acetate 5.1 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates) are added to the above solution and the resulting formulation is applied primed steel plates applied by spraying The plates are at 130 ° C for 20 minutes baked in with hard glossy coatings with excellent adhesion and solvent resistance (Xylene and methyl ethyl ketone).

Example 14

Monophenyl phosphate is made from phenyl phosphorus dichloridate prepared according to the procedure described in Example 5. The acid equivalent weight this solution turned out to be 144.

40 parts of the glycidyl methacrylate copolymer of Example 1.30 parts of the hydroxy polymer of Example 8 and 25 parts of hexamethoxymethylmelamine are dissolved in 20 parts of butyl acetate. The phenyl phosphate solution (7.2 parts) is added to the above solution and the resulting formulation is primed Steel plates sprayed on by spray application The plates are under at 130 ° C for 20 minutes Baked to obtain hard glossy coatings with excellent adhesion and solvent resistance

Example 15

The following monomers are used to synthesize a polymer:

Wt%

Butyl methacrylate 40 Glycidyl methacrylate 15th Methyl methacrylate 40 Styrene 5

The polymerization is carried out as indicated in Example 3 to give a 52% solution of the polymer in The polymerization is carried out in methyl amyl ketone using 1.8% (% by weight of the monomers) of the initiator. The molecular weight from gel permeation chromatography was found to be M _n = 5750, MjM _n = 2.4. The solids content was 54% by weight.

60 parts of this polymer solution, 70 parts of the polymer from Example 8 and 50 parts of hexameihoxymethylmelamine are dissolved in 30 parts of butyl acetate. 4.1 parts Acid-butyl phosphate (mixture of monobutyl and Dibutylphosphaten. Eq ^ alentgewicht 120) are added to the above solution, and the resulting formulation is applied to primed steel panels sprayed The plates are baked at 13O ⁰ C for 20 minutes, whereby coatings excellent in Hardness, adhesion and solvent resistance (xylene and methyl ethyl ketone) can be obtained.

Example 16

10 parts of 2-ethyl-1,3-hexanediol and 4 parts of hexamethoxymethylmelamine are added to the formulation described in Example III. The received The formulation is applied to primed steel panels by spraying in three coats using one Intermediate evaporation of 1 minute and a final evaporation of 5 minutes. The plates are at 120 "C for 20 minutes to obtain a clear coating with excellent hardness,

Adhesion, gloss (90/20 °) and solvent resistance Baked in (xylene and methyl ethyl ketone)

Example 17

The paint formulation described in Example 2 is made using 6 parts of aluminum flake and 10.4 parts of acid butyl phosphate. The application and baking conditions are repeated the same as in Example 2. The coating provides excellent physical properties.

Example 18

5 parts of polypropylene glycol and 2 parts of hexamethoxy- ι s methylmelamine are added to the formulation described in Example 3. The formulation obtained is applied to primed steel test panels by spraying in three coat applications The panels are at 130 ° C for 15 minutes to obtain 2n Coatings with excellent gloss (91/20 °), excellent adhesion, hardness and resistance to solvents burned in

Example 19

350 g of titanium dioxide are mixed with 350 parts of the acrylic polymer given in Example 4 and 25 parts Butyl acetate mixed The above mixture is taken up in a porcelain bottle containing porcelain beads and placed on a roller mill for 16 hours with 40 doors of the above grinding base with 28 parts of polymer from Example 1, 5 parts of hydroxy ester alkyd resin, 11 parts of hexamethoxymethylmelamine and 20 parts of butyl acetate mixed. 3.8 parts of acid butyl phosphate (mixture of monobuty! - and dibutyl phosphates, equivalent weight 120) are added to the above mixture, and the The resulting formulation is applied to primed steel panels by spraying. The panels are at Baked at 120 ° C. for 20 minutes to give coatings with excellent physical properties

Example 20

500 parts of titanium dioxide and 250 parts of ferrite yellow are mixed with 500 parts of that given in Example 4 Acrylic polymers 7.8 parts of a common dispersant and 200 parts of butyl acetate mixed; the Grinding base is prepared as described in Example 19, 35 parts of this grinding base are made with 50 parts of polymer from Example 3, 23 parts of hexamethoxymethylmelamine, 3 parts of 1,4-cyclohexanedimethanol and 22 parts of butyl acetate mixed. 6.8 parts of acid butyl phosphate (equivalent weight 120) are added to the above mixture and the resulting formulation is applied to primed steel panels applied by spraying. The plates are left at 115 ° C. for 20 minutes to give coatings baked with excellent physical properties.

Example 21

50 parts of the blue pigment Phthalo blue are mixed with 500 parts of the acrylic polymer given in Example 4 and 44 parts of butyl acetate mixed together, the milling base

-13 is milled as described in Example 19.

25 parts of the above grinding base are mixed with 41 parts of the polymer solution from Example 3, 6 parts Aluminum flakes (65% in naphtha), 15 parts of bis (hydroxypropyl) azelate, 29 parts of hexamethoxymethylmelamine (Cymel 301) and 20 parts of butyl acetate mixed. 5.6 parts of acid butyl phosphate (equivalent weight 120) are added to the above mixture, and the resulting formulation becomes on primed steel panels in four coats using a one minute evaporation time applied between the coats by spraying. After 5 minutes of final evaporation, the plates at 130 ° C for 20 minutes to a blue baked metallic coating with excellent hardness, adhesion and solvent resistance.

Example 22

750 ml Toluene brought to reflux under nitrogen The following mixture of monomers containing 15 g of 2 ^ -azobis- (2-methyl-propionate) dissolved in 50 ml of acetone is added dropwise to the refluxing Toluene added:

Weight (g) Weight - ⁰ ,,,

Butyl methacrylate 150 50

Glycidyl methacrylate 45 15

Hydroxypropyl methacrylate 30 10

Methyl methacrylate 60 20

Styrene 15 5

The addition of the initiator and the monomer solution is complete in 3 hours. The reaction mixture is a refluxed for a further half an hour and then 10 ml of an acetone solution containing 2 g of the above initiator were added dropwise, and the reaction mixture was left on for half an hour Held at reflux. Part of the solution is distilled off in order to bring the solids content to 66%.

13 parts of the above polymer solution are mixed with 3 parts of hexamethoxymethylmelamine, and that Mixture is dissolved in 3 parts of butyl acetate 1 part of acid butyl phosphate (mixture of monobutyl and Dibutyl phosphate) is added to the above solution and the mixture is applied to a steel test plate raised. The plate is at 100 ° C for 20 minutes to obtain a glossy (85/20 °) Coating with excellent hardness, adhesion and solvent resistance (xylene and methyl ethyl ketone) burned in.

Example 23

10 parts of the copolymer described in Example 22, 7 parts of hexamethoxymethylmelamine and 7 parts of a hydroxy ester alkyd resin are dissolved in 8 parts of butyl acetate. 1 part of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates) is added to the above solution and the resulting formulation is drawn down on a steel test plate. The plate is baked at 100 ° C for 20 minutes, with a glossy (92/20 °) coating

excellent hardness, adhesion and solvent resistance (xylene and methyl ethyl ketone) is obtained.

Example 24

A copolymer is made according to the procedure described in Example 1 in methyl amyl ketone 125 ° C using the following monomers:

Wt%

Butyl methacrylate 50 Ethylhexyl acrylate 10 Glycidyl methacrylate 15th Hydroxypropyl methacrylate 10 Methyl methacrylate 10 Styrene 5

Tert-butyl peroctoate (5.25% of the monomers) is used as the initiator, and the solids content found in the composition is 66.6% by weight. The calculated Tg value of the copolymer is 25 ° C. and the molecular weight based on gel permeation chromatography was found to be M _n - 4220 and MJM _n = 1.90.

A mill base is made by dispersing titanium dioxide into the polymer with a high speed paddle stirrer. The composition of the mill base is as follows: 15% polymer (100% non-volatile substances), 65% titanium dioxide and 20% methyl amyl ketone. 72 parts of this milling base, 31 parts of the polymer, 12.5 parts of bis (hydroxypropyl) azeiate, 30 parts of Cymel 301 and 29 parts of methyl amyl ketone are placed in a plastic bottle. 3.6 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates. Equivalent weight 120) are added to the above mixture and the resulting formulation is applied to both primed and unprimed steel panels by spraying. The plates are ^{baked at 130 °} C. for 20 minutes to give hard, glossy coatings with excellent adhesion. The coating had excellent solvent and moisture resistance.

Example 25

(a) Following the procedure described in Example 24, a copolymer is obtained from the following Monomers produced:

Weight ΊΌ

Butyl methacrylate 60 Glycidyl methacrylate 20th Hydroxyethyl acrylate 10 Styrene 10

Copolymer (a) 21% (100% not volatile substances) Titanium dioxide 61% Methylamylcion 18%

65 parts of this grinding base, 26.4 parts of the polymer solution, 12.5 parts of bis (hydroxypropyl) azelate, 31 parts of hexabutoxymethylmelamine and 25 parts of methyl amyl ketone are placed in a plastic bottle brought. 7.3 parts of acid amyl phosphate (mixtures of monoamyl and diamyl phosphates, equivalent weight 162) are added to the above mixture, and the The formulation obtained is applied to both primed and unprimed panels by spraying upset. The plates are at 130 ° C for 20 Baked in minutes, hard glossy coatings with excellent adhesion and solvent resistance can be obtained. The coating shows when placed in a Cleveland moisturizer for 14 days does not show any deterioration in general physical properties.

Example 26

Following the procedure described in Example 22, a copolymer is made from the following monomers manufactured:

Weight ^u / o

The calculated Tg of the polymer is 25 ° and the solids content was found to be 54.9% by weight. The molecular weight based on gel permeation chromatography was M _n - 1809 and MjM _n = 2.44.

(b) As described in Example 24, a milling base was prepared from the following materials:

Butyl methacrylate 49 Glycidyl methacrylate 20th Hydroxypropyl methacrylate 10 Methyl methacrylate 16 Styrene 5

The calculated Tg of the polymer is 43 ° C and the solids content was found to be 52%. The molecular weight based on gel permeation chromatography was M _n = 2906 and MJM _n = 2.31.

As described in Example 3, a grinding base is prepared with the following composition:

Weight%

Titanium dioxide 65 40 the above polymer 13th (100% non- volatile substances) Methyl amyl ketone 22nd

69 parts of this grinding base, 37 parts of the polymer, 17.5 parts of bis (hydroxypropy!) Azelate, 31 Parts of Äthoxymethoxymethylbenzogufnamin and 22 parts of butyl acetate are in a plastic bottle brought. 4.8 parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates, equivalent weight 120) is added to the above mixture and the resulting formulation is applied to primed test panels applied by spraying. The plates are baked at I15'C for 20 minutes, wherein glossy hard coatings with excellent solvent resistance (Xylene and methyl ethyl ketone) can be obtained. This coating shows no loss of gloss, adhesion, or solvent resistance after exposure to a Cleveland humidity cabinet during It days.

Example 27

Following the procedure described in Example 21, a copolymer is refluxed in Methyl amyl ketone made from the following monomers:

Glycidyl methacrylate
Hydroxyethyl acrylate
Butyl methacrylate
Styrene

Wt%

20th
10
60
10

2% tert-butyl peroctoate is used as initiator. The solids content is 53.6%. On the basis of the field penetration chromatography, the molecular weight was found to be: M _n = 2746 and MjKI _n = 2.33.

As described in Example 24, a milling base is prepared with the following ingredients:

Wt%

Titanium dioxide 56 the above polymer 26th (100% not volatile substances) Methyl amyl ketone 18th

71 parts of this grinding base, 14.6 parts of the polymer, 12.5 parts of bis (hydroxypropyl) azelate, 31 Parts of butoxymethylglycoluril and 25 parts of methyl amyl ketone are placed in a plastic bottle. 4.8 parts acidic butylphosphai (mixture of monobutyl and dibutyl phosphates. equivalent weight 120) become added to the above mixture, and this formulation is sprayed onto primed test panels upset. These plates are left at 130 ° C. for 20 minutes to give glossy hard coatings Baked in with excellent solvent resistance (xylene and methyl ethyl ketone). The coatings do not show any loss of gloss, adhesion or solvent resistance after exposure to a Cleveland humidity chamber for 14 days.

Example 28

Following the procedure described in Example 22, a copolymer is refluxed in Toluene made from the following monomers:

Butyl methacrylate

Ethylhexyl acrylate

Glycidyl methacrylate

Hydroxypropyl methacrylate

Stvrol

Weight o / o

50
20th
15th
10
5

1000 g of total monomers. 700 ml of toluene and 50 g of tert-butyl peroctoate are used. The calculated Tg of this polymer is 6 ^C C. and the solid content is 59 wt .-%; gel permeation chromatography gives a molecular weight of M _n = 4337 and MjM _n = 2.14. The viscosity of this polymer solution is 133 Stokes.

50 parts of the above polymer solution, 5 parts of bis (hydroxypropyl) adipate and 29 parts of butoxymethylurea resin are dissolved in 15 parts of n-butyl acetate 3.7 Parts of acid butyl phosphate (mixture of monobutyl and dibutyl phosphates, equivalent weight 120) added to the above solution, and the resulting formulation is primed by spraying Steel plates applied The plates are applied at 130 ° C Baked for 20 minutes, with coatings of excellent hardness. Adhesion, excellent Gloss and excellent solvent resistance (xylene and methyl ethyl ketone) can be obtained.

Example 29

125 g of ethyl phosphorus dichloride are dissolved in 150 m of butyl acetate, placed in a round bottom flask and unc cooled with an ice-water mixture. 28 g of cold water are added drop by drop while stirring and at the same time! Application of vacuum by means of a water jet pump added. The reaction mixture is under Stirred in vacuo for 3 days and then with sodium hydroxide to obtain a monoethyl phosphate solution with an acid equivalent weight titrated by 112.

20 parts of the polymer solution from Example 1. 8 parts of hexamethoxymethylmelamine and 2 parts of bis (2-hydroxyethyl) adipate are dissolved in 9 parts of butyl acetate steel test panels aufzgezogen The plates are baked at 110 ⁰ C for 15 minuter, wherein a hard gloss finish mi excellent adhesion and solvent resistant speed (xylene and methyl ethyl ketone) is obtained.

Example 30

A butyl acetate solution of monocyclohexylmethyl phosphate with an acid equivalent weight of 14! is prepared from cyclohexylmethylphosphorus dichloridate according to the procedure given in Example 29 The paint becomes more acidic as described in Example 4 using 6.5 parts of the above Phosphate solution formulated instead of acid amylphospha. The paint is applied by spraying Primed steel plates are applied and at 120 ° C baked for 20 minutes, with coatings with excellent gloss, excellent hardness. Haf processing and solvent resistance (xylene and methyl ethyl ketone) can be obtained.

Example 31

A hydroxy acrylic copolymer is made from the following monomers:

Butyl methacrylate
Hydroxyethyl acrylate
Methyl methacrylate
Stvrol

100 g of tert-butyl perbenzoate are added to the above monomer mixture and the solution is added dropwise over a period of; Hours added to 1400 g of refluxing methyl amyl ketone under nitrogen Da; Heating and stirring are continued for half an hour after the addition is complete, and then 5 g of tert-butyl perbenzoate is added in portions to the reaction mixture. The reaction mixture is refluxed for a further 90 minutes and then allowed to cool to room temperature. The molecular weight is determined on the basis of gel permeation chromatography to be M _n = 2540 and Mw> M _n = 134. Monophenyl phosphate is prepared from phenyl phosphorus dichloridate by the method described in Example f. The acid equivalent weight of this solution is 144.

Weight (el Ciou.- HXIO 50 400 20th 400 20th 200 10

40 parts of the above hydroxy polymer solution, 40 parts the polymer solution of Example 21 and 27 parts of hexamethoxymethylmelamine are in 24 parts Butyl acetate dissolved. 4.8 parts of the above-described acidic phosphoric phosphate solution becomes the above Solution is added and the resulting formulation is sprayed onto primed steel panels upset. The plates are kept at 130 "C for 20 Baked in for a few minutes, giving hard, glossy coatings with excellent adhesion and solvent resistance (xylene and methyl ethyl ketone).

Example 32

Following the procedure described in Example 24, a copolymer is made from the following monomers manufactured:

Wt%

Butyl methacrylate Hydroxypropyl methacrylate Methyl methacrylate

Styrene

40 20th 10 20th 10

The solids content in methyl amyl ketone is determined to be 55% by weight.

25 parts of the above polymer and 7 parts of hexamethoxymethylmelamine are dissolved in 4 parts of butyl acetate. 2.6 parts of acid butyl phosphate (mixture from monobutyl and dibutyl phosphates, equivalent weight 120) are added to the above solution, The formulation obtained is drawn onto primed steel plates. The plates are at 130 "C Baked for 20 minutes to obtain coatings with excellent physical properties.

B e i s ρ i e I 33

Following the procedure described in Example 22, a copolymer is made from the following monomers manufactured:

Wt%

Allyl glycidyl ether 10 Butyl methacrylate 30th Hydroxypropyl methacrylate 15th Methyl methacrylate 25th Styrene 20th

Toluene is distilled off in order to bring the solids content to 59% by weight.

85 parts of the above polymer, 10 parts of a caprolactone-based hydroxy ester and 23 parts Hexamethoxymethylmelamine is dissolved in 20 parts of butyl acetate, 53 parts of acid butyl phosphate (Mixture of monobutyl and dibutyl phosphates, equivalent weight 120) become the above solution added, and the resulting formulation is applied to primed steel panels by spraying Plates are kept at 130 ° C for 20 minutes baked, giving hard, glossy coatings with excellent adhesion and solvent resistance (xylene and methyl ethyl ketone).

Example 34

90 parts of the polymer solution from Example 22 are mixed with 12 parts of Ahiminiumfflakes (65% in naphtha) mixed and dJsper well with a camel hair brush greed. 20 parts of butyl acetate become the above Mixture added and filtered through a coarse cloth. 30 parts of hexamethoxymethylmelamine and 5 parts Bis (hydroxypropyl) azelate is added to the above mixture and it is stirred well. 7.5 parts Acid butyl phosphate (mixture of monobutyl and dibutyl phosphates) become the above mixture added, and the resulting formulation is applied to primed steel panels in three coats

ίο Spray applied. The intermediate evaporation time is 1 minute and the final evaporation time is 5 minutes. The plates are incubated at 12O ⁰ C for 20 minutes to obtain a silver metallic coating with excellent hardness, adhesion, aluminum control and solvent resistance (xylene and methyl ethyl ketone) baked in.

Example 35

4 parts of 1,4-cyclohexanedimethanol and 2 parts of 2c hexane-methylme'-ethylme'amine are added to the formulation described in Example 22. The formulation obtained is drawn onto primed steel plates. The plates are baked at 12O hard ⁰ C for 20 minutes to obtain a gloss coatings with _n excellent adhesion and solvent resistance (xylene and methyl ethyl ketone).

Example 36

8 parts of 2-ethyl-i, 3-hexanediol and 3 parts of hexamethoxymethylmelamine are added to the formulation described in Example 3, and the resulting formulation is applied to primed steel test panels by spraying. The plates are ^{baked at 120 °} C. for 20 minutes, with} 5 coatings with excellent physical properties being obtained.

B e i s ρ i e I 37

3 parts of polypropylene glycol and 1 part of hexamethoxymethylmelamine are added to that described in Example 22 NEN formulation added. The paint obtained is drawn onto primed steel plates and the plates are at 125 ° C for 20 minutes baked to give coatings with excellent physical properties.

Example 38

350 g of titanium dioxide are mixed with 350 parts of the acrylic polymer given in Example 4 and 25 parts Butyl acetate mixed The above mixture is placed in a porcelain bottle containing porcelain beads and placed on a roller mill for 16 hours. 32 parts of this grinding base are mixed with 10 Parts of bis (hydroxypropyl) azelate 30 parts of polymer solution from Example 22.25 parts of hexamethoxymethylmelamine and 20 parts of butyl acetate mixed together 2.7 parts acid butyl phosphate (equivalent weight 120) are added to the above mixture, and the obtained The formulation is sprayed onto primed steel plates. The plates are kept at 125 ° C. for 20 Baked for minutes to obtain coatings with excellent physical properties.

B e i s ρ i e I 39

there are 50 parts of blue pigment Phthalo Blue with 500 Parts of the acrylic polymer specified in Example 4 and 44 parts of butyl acetate are mixed, and the mahogany base is milled as described in Example 17. 25th

Parts of the above grinding base are mixed with 42 parts of the polymer solution from Example I, 5 parts of bis (hydroxypropyl) azelate, 21 parts of hexamethoxymethylmelamine, 4 parts of aluminum flakes (65% in naphtha) and 10 parts of butyl acetate mixed. 3.9 parts of acid butyl phosphate (equivalent weight 120) are added to the above mixture is added, and the resulting formulation is applied to primed steel plates in four Coatings applied by spraying with a one minute evaporation time between the coatings. To After 5 minutes of final evaporation, the plates become a blue metal coating with excellent hardness, adhesion and strength at 130 ° C. for 10 minutes Baked in solvent resistance.

The invention has been described above on the basis of preferred embodiments, without being limited thereto to be.

Claims (3)

Patent claims: 1. Thermosetting coating composition with more than 60 wt .-% non-volatile solids from (A) a Epoxy resin, (B) at least one organophosphate ester of the formula Il (RO) _n -P- (OH) ₁ -, IO film-forming copolymers is contained during the curing of the coating composition 2. Composition according to claim 1, characterized in that the alkyl group of the organophosphate monoester has a predominantly straight-chain radical with 2 represents up to 6 carbon atoms. 3. Composition according to claim 1, characterized in that at least one alkyl group of the organophosphate diester consists of a predominantly straight-chain radical having 2 to 6 carbon atoms