DE2710032A1 - COATING DIMENSIONS - Google Patents

Description

MÜLLER-BOR ^ DEUFKL SCHÖN HERTKL PATENT LAWYERS

DR. WOLFQANa MULLKR-MORI

(PATKNTANWALTVON imt ins)

DR. PAUL DKUFKL. DIPL.-CMCM. DR. ALFRKD SCHÖN. DIPU-CMKM. WKRNKR HKRTKL. DlPL.-PMY *.

S / R 14-141

Rohm and Haas Company, Philadelphia, USA Upper tensile mass

The invention relates to coating compositions, the certain alkyd or Contain polyester resins and cyclic acrylic and / or methacrylic acid esters.

US Pat. No. 2,414,089 describes the preparation of esters of hydroxydicyclopentadiene with unsaturated monocarboxylic acids such as acrylic acid (Example 9), methacrylic acid (Example 8) and numerous other unsaturated acids listed in column 3, line 67 to Column 4, line 24 are indicated. The usage of esters as binders for paints, varnishes and similar coating materials is indicated in column 4, lines 25 to 27 and in

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the lines 62 to 75 of column 6 described. The linoleate (Example 3) is formed with a desiccant of a film which is baked to form a varnish-like coating. Other unsaturated higher fatty acids are suggested for this purpose. On lines 49 to 53

in column 4 it is stated that the new esters with drying oils, alkyd resins, hydrocarbons such as rubber or cyclized Rubber and other oils and resins can be mixed.

P.D. Bartlett and Abraham Schneider give in "J.A.C.S.", 68, 6 (1946) indicate the exact structure of the esters made by Bruson which he had erroneously called the result of his theory regarding their rearrangement.

US Pat. No. 2,462,400 describes the production of copolymers from 20 to 50% by weight of dihydrodicyclopentadiehyl methacrylate with monohydric saturated (Cg ^ C ₁₈ ) -aliphatic alcohol esters of methacrylic acid using an organic peroxide initiator. A solution of the copolymer containing a drying agent is then used to coat substrates. The cover is air-dried.

According to US Pat. No. 3,743,615, a vinyl monomer such as an alkyl acrylate is used or methacrylate, or styrene quickly in air drying oil modified alkyd resins added.

Dicyclopentenyl acrylate or * methacrylate have been approved for use in light-sensitized coating compositions which are polymerized by radiation, proposed (cf. US Pat. No. 3,650,669 and 3 772 062). However, such compositions require a photoinitiator system, and the products are often not durable. In addition, the use of high-intensity UV light sources in close proximity to the coated objects is necessary in order to prevent the

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Level of cure to be achieved in a practical amount of time is desired or necessary when performing on an industrial scale.

Commercially available autoxidizable coating or impregnating compounds based on oil-modified polyesters or alkyd resins, wherein the oil modifier is made up of at least one consists of unsaturated UI of the semi-drying or drying type, generally result in topcoat or impregnation films which often have limited hardness and many other properties miss. The films are particularly resistant to yellowing, discoloration, cracking, and shrinkage as well as other deformations. Furthermore, they are decomposed, removed by abrasion or by chemical attack, in particular by organic solvents and alkaline materials. Such films have poor toughness against the influences of the weather, such as against wind, rain and radiation, such as UV light radiation the sun as well as other natural rays such as cosmic rays, X-rays, β-rays and ^ JT-rays to radiation such as that emitted by lasers, X-ray machines and radioactive materials. Coating compounds ,, those used to manufacture fluorescent screens in oscilloscopes, TV tubes and electron microscopes are used, are examples of masses that are attacked by radiation.

It has now been found that air-drying coating compositions based on alkyd or polyester resins with at least an unsaturated component, especially those masses that have been modified by a drying or semi-drying oil and contain dxcyclopentenyl acrylate and / or methacrylate, no longer have these disadvantages and have balanced properties both with regard to the coating compositions themselves and the cured films produced from them.

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Dicyclopentenyl acrylate and dicyclopentenyl methacrylate are referred to below as DCPA and DCPMA, respectively. Both acrylates as well a mixture containing these two acrylates is referred to as DCP (M) A.

The reactive DCP (M) Α monomer or the reactive DCP (M) A monomers are optionally referred to as dihydrodicyclopentadienyl acrylate or methacrylate. These esters can be obtained by the addition of Acrylic acid or methacrylic acid can be obtained on one of the double bonds of dicyclopentadiene. This hydrocarbon compound is represented by the formula:

(I)

It has the following designation: 3a, 4,7,7a-tetrahydro-4,7 ~ methanindene- (ring index, Patterson, 2nd edition, page 293).

The (meth) acrylic acid ester of dicyclopentadiene possesses how to assumes the following formula:

RO C-C-O

(II)

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where R is H or CH ₃ 1 The (meth) acryloxy substituent can either be in the 5- or opposition, the commercial product being a mixture of the two isomers.

When using the numbering system of the formula I for the compound of the formula Xl, it becomes clear that the dicyclopentenyl acrylate or methacrylate shown can also be used as 3a, 4,5,6,7,7a-hexahydro-4,7-methanindenyl acrylate-5 (or -6 ) or methacrylate-5 (or -6) can be designated «

DCP (M) A is a reactive high-boiling liquid acrylic ester monomer or mixture of monomers which, when used in topcoats, has a combination of desirable properties conditional. These characteristic properties are low viscosity, volatility and toxicity, hydrophobicity as well as excellent hydrolytic stability even under acidic or alkaline conditions and excellent compatibility with a large number of polymeric and / or resin-forming condensates. It has been found that these monomers can optionally be mixed with a small amount of another solvent to form a solution or dispersion of a polyester or alkyd of the maleate / fumarate unsaturation type and / or a drying oil unsaturation can be used, for example an oil-modified alkyd, and indeed optionally together with another polymer and / or a resin-forming condensate. Such solutions or dispersions can be applied as coating or impregnation compounds or in coating or impregnation compounds with any suitable substrate. DCP (M) A reacts with an unsaturated alkyd, in particular with an oil-modified alkyd, optionally together with others non-volatile polymeric and / or resin-forming materials, especially in the presence of a metal-containing drying agent, the action of normal atmospheric conditions on a coating containing the reactive monomer, the

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oil-modified alkyd, optionally also another polymer and / or condensate, as well as a drying agent, optionally with other solid components, for example pigments, fillers, Plasticizers and dyes result in the formation of solid films with a desired combination of properties Has. In the case of compositions containing 100% solids, which contain no solvent other than the non-volatile reactive monomer component air dry to a solid state without the need for volatilization of any Solution materials so that there are no environmental and waste problems.

The invention provides an autoxidizable mass which is used for coating and / or impregnating a substrate can be used and consists of the following components:

(a) a reactive non-volatile monomeric material the end

(1) a monomeric material consisting essentially of dicyclopentenyl acrylate or methacrylate or a mixture thereof and

(2) a monomeric material from a preponderant amount Dicyclopentenyl acrylate and / or methacrylate and a minor amount of at least one other non-volatile liquid monoethylenically unsaturated monomers,

and, dissolved or dispersed in it,

(b) an unsaturated polyol / polycarboxylic acid alkyd or polyester resin, wherein the alkyd or the resin have at least one unsaturated component selected from the following constituents becomes: (I) maleic acid or maleic anhydride or fumaric acid components and (II) drying or semi-drying oil components, wherein the resin is selected from a polycarboxylic acid or from a polycarboxylic acid anhydride, and the alkyd is selected from

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the following components is selected:

(1) Alkyds in which the polycarboxylic acid precursor component consists of a dicarboxylic acid, which is 30 to 100% by weight composed of an aliphatic dicarboxylic acid or anhydride having 4 to 40 or more carbon atoms, and

(2) Alkyds in which the polycarboxylic acid precursor component is made up consists of a dicarboxylic acid of which 30 to 100% by weight is composed of an aromatic dicarboxylic acid or an anhydride,

where (a) (1) is used with (b) (1),

or (a) (1) is used with (b) (2) in a weight ratio of less than 25 to 75,

or (a) (2) with (b) (1) and / or (b) (2) is used in such a way that when component (b) is used (2) in bulk either a sufficient amount of the other non-volatile monomer is used or a sufficiently low amount The ratio of (a) (1) to (b) (2) is maintained, so that the resulting formed film, which is formed from the mass, is not excessively hard.

DCP (M) A acts as a non-volatile reactive diluent or Solvent in the coating compositions according to the invention. Contain these masses are commercially available oil-modified alkyd resins, whose polycarboxylic acid component is predominantly or mainly aromatic, for example o-phthalic acid or phthalic anhydride, then it was found that they sometimes give products that are extremely hard, for example if more as 25% by weight DCP (M) A can be used together with less than 75% by weight of such an alkyd resin. For some purposes

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such a hardness can be too great. Xn these cases can they can then be avoided if the DCP (M) A is the main component of the reactive diluent together with a smaller one Amount of at least one other non-volatile reactive liquid monoethylenically unsaturated monomer, such as an ester a (C-. q-Cjq) aliphatic alcohol with acrylic acid or methacrylic acid is used. This will be another reactive monomer used in an amount sufficient relative to the DCP (M) A to compensate for the excessive hardness in the film created by the DCP (M) A. Adjustment of the amount of non-volatile reactive component A generally has the effect of reducing the viscosity of the coating compositions to a suitable level Degree of consequence when one wants to avoid or keep to a minimum the use of a volatile non-reactive solvent in the compositions for a particular type of application, for example for spraying, brushing or roller coating.

The component A can consist of DCP (M) A if the component (b), for example an alkyd corresponding to type A (as defined), or when up to about 25% by weight DCP (M) A with about 75% or more of component (b), for example an alkyd, des Type B (as defined) can be used. However, component (a) can consist of a mixture of a major amount (more than 50% by weight) of DCP (M) A and a minor amount (less than 50% by weight) of another non-volatile monomer, for example of a higher aliphatic alcohol ester of acrylic or methacrylic acid, as mentioned, consist. In this case, component (b) can be either type A or type B or a mixture of which correspond. The relative proportions of the non-volatile reactive component of the binder and the alkyd can be anywhere within the ranges given below. It should be noted that in in practice, a volatile and non-reactive thinner or solvent as part of the binder in the top coat

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can be mixed, which is applied in the proportions given below, but is preferably a such solvent is used in small amounts, if used at all.

In compositions which contain the other nonvolatile monomer, ie compositions which contain component (a) (2), this component preferably consists of 60 to 90% by weight of DCP (M) A and 10 to 40% by weight of the other monomer . The other monomer can consist of one or more of the following components: (I) an ester of a (CQCJ-aliphatic alcohol with acrylic or methacrylic acid, (II) a vinyl ester of a (C ₁₀ -C _{2 (} ^ -aliphatic acid) and (III ) a dialkyl ester of maleic acid, fumaric acid or itaconic acid, each alkyl group containing 1 to 20 and preferably 1 to 8 carbon atoms, the acrylic or methacrylic acid ester being preferred.

According to one embodiment of the invention, which is referred to as type A, the alkyd or the polyester is based on a polycarboxylic acid, 30 to 100% by weight of which is composed of a composed of aliphatic dicarboxylic acid. Preferably the polycarboxylic acid is predominantly or exclusively aliphatic, i. to more than 50 or 100% by weight. The dicarboxylic acid can be saturated or unsaturated and at least 4 and up to 36 to Contain 40 or more carbon atoms. Preferably they are Carboxyl groups in the dibasic acid are separated by a hydrocarbon group having at least 2 carbon atoms. These Group can not be substituted and saturated or unsaturated but it can be, for example, by hydroxyl groups, as in the case of maleic acid, or by halogen atoms, for example be substituted by chlorine atoms.

Examples of the aliphatic dicarboxylic acids (either in the acid or anhydride form are suitable), which are

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treatment of these unsaturated polyesters or alkyds, including of the oil-modified alkyds that can be used are adipic acid, maleic acid, fumaric acid, pimelic acid, suberic acid, Azealic acid, glutaric acid and sebacic acid. Furthermore, the various commercially available dimer acids are, for example Contain 36 carbon atoms, which are obtained by polymerizing linoleic acid according to US Pat. No. 2,482,761 and J.Am. Oil Chemists Association, 24, 65 (1947) are suitable. The composition of such a dimer acid (which under the The name Emery 955 dimer acid is marketed by H.F. Payne in "Organic Coating Technology", Volume I, pages 275-277, John Wiley & Sons, Inc., N.Y., 1954. Such an acid apparently contains a small amount of trimers with three carboxyl groups.

Part of the result of modifying the alkyd with an oil unsaturation obtained with air drying properties, or all of the unsaturation obtained in this way, can be obtained by using a #, ß-ethylenically unsaturated d! carboxylic acid, such as Fumaric acid, maleic acid, maleic anhydride and unsaturated dimer acid, as part or as a full replacement for the polycarboxylic acid component, which is used to make the alkyd or polyester are replaced. Furthermore, the alkyd resins, which is based on an unsaturated diacid or anhydride of the mentioned Type decline, are supplemented, for example by graft polymerization with styrene, methyl methacrylate and / or other monoethylenically unsaturated monomers, for example esters of acrylic acid or other esters of methacrylic acid. Phthalic acid or phthalic anhydride or other aromatic polyacids can be part of the polycarboxylic acid component of the Form polyester, but it is preferable that at least 30% by weight and preferably at least 50% by weight of the Polycarboxylic acid component used to manufacture the polyester corresponds to the aliphatic type just defined .

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Any oil-modified compound can be used to produce compounds of type A Alkyd resin, with the exception of those resins based on a dicarboxylic acid component decrease, which is predominantly or completely aromatic, for example phthalic acid, as a component (b) can be used as long as it has a drying character. Examples are alkyds made with natural resins such as rosin, Copal resins or ester gum, are modified. With maleic anhydride modified types, phenol modified alkyd resins, and amino resin modified types can also be used. Maleinized olglycerides and rosin adducts can also be used use, i.e. materials that contain rosin or abietic acid, maleic anhydride and glycerine. The type of Alkyd resins known as terpene adducts can also be used. These various alkyds are discussed in the Encyclopedia of Chemical Technology ", Kirk-Othmer, Volume 1, published by of Interscience Encyclopedia, Inc., N.Y., 1947, on pages 521-528.

The polyols used to make the polyester or alkyd which is used in the compositions of the invention can have 2 to 6 hydroxyl groups and 2 to 8 carbon atoms exhibit. Examples include ethylene glycol, diethylene glycol, glycerine, propylene glycol, erythritol and pentaerythritol. There are no restrictions on the method by which the oil-modified alkyd resin is produced, as the method of manufacturing this component, if used in bulk, is known. The alkyds used can be long, medium or short oil products. In general, the short oil alkyds have about 52 to 50% oil per 45 to 39% the diacid used to make the alkyd. The middle oil alkyds contain 53 to 61% oil per 36 to 30% of the Diacid and the long oil alkyds approximately 64 to 70% oil per 28 to 23% of the diacid. Preferably the middle oil modified ones Alkyds and the long oil-modified alkyds in the invention

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wet masses used. Such oil-modified resins are generally suitable for air drying while the short oil modified alkyds are generally fired to perform need hardening. The oil content of the alkyd component (b) represents also represents a factor which can be used to partially or completely compensate for or even overcompensate for the hardness which is attributable to component (a). This leaves be achieved in that the relative proportions of the two components to achieve the desired effect be matched,

According to another embodiment of the invention, which is called type B is referred to, the alkyd or polyester is preferably based on a polycarboxylic acid, which is 30 to 100% by weight composed of an aromatic dicarboxylic acid. The polycarboxylic acid or an anhydride is preferably predominantly to exclusively aromatic, i.e. more than 50% by weight or too much 100% by weight.

This type of alkyd or polyester can be used to form a composition according to the invention in combination with component (a) (2), i. DCP (M) A together with another relatively non-volatile monomer, such as a methacrylic acid or acrylic acid ester long chain aliphatic alcohol, namely an aliphatic alcohol having 10 to 20 or more carbon atoms can be used. Such aliphatic esters are, for example, decyl acrylate, isodecyl acrylate, undecyl acrylate, lauryl acrylate, cetylacrylate, Pentadecyl acrylate, hexadecyl acrylate and octadecyl acrylate. In The corresponding methacrylates and the unsaturated. Analogs such as oleyl acrylate or methacrylate, linoleyl (raeth) acrylate and linolenyl (meth) acrylate.

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Instead of the (C ₁₀ -C ₂₀ ) -alkyl7 or (C ₁ QC ₂₀ ) -alkenyl acrylates and methacrylates, as mentioned above, or in addition to these, other ethylenically unsaturated monomers of non-volatile character can optionally be added. Examples include vinyl stearate, vinyl laurate, vinyl oleate and dialkyl fumarates, maleates and itaconates, the alkyl groups containing 1 to 20 carbon atoms. In this embodiment, the amount of such monomers can vary from 10 to% by weight of component (a), the DCP (M) A being present in a predominant amount and the remainder being up to 100%, namely 90 to 60% by weight % of the reactive monomer component (a).

It should be noted, however, that compositions according to the invention can be prepared not only by combining component (a) (2) with the type B alkyd just described, but also with the "soft" alkyds or polyesters of type A or a mixture of types A and B.

If component (a) consists essentially of DCP (M) A, then is it is preferable that component (b) is not based on an aromatic polycarboxylic acid or an anhydride or any other Part of the oil-modified alkyd decreases.

Typical drying oils used as the oil-modifying component of the Component (b) (either in the case of type A or of type B) can be used, mono-, di- and triglycerides are higher Fatty acids with a relatively high degree of unsaturation, such as linseed oil, jaflor oil, tung oil, soybean oil, dehydrated castor oil, oitizica oil, menhaden oil, etc. The alkyd of component (b) may contain one or more such drying oils, regardless of whether they are of the triglyceride, monoglyceride or diglyceride type or the corresponding carboxylic acid or an anhydride. Under the term "drying 01"

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Such oils are said to be either natural or man-made in origin be understood, which are characterized by a reaction with oxygen to form hardened solid products. This term is intended to include such so-called "semi-drying" oils "fall, which due to a low degree of unsaturation do not harden as quickly as most typical drying ones oils, which are therefore more often used in paints and varnishes. The oil-modified alkyds for the inventive Masses are suitable, therefore, are those in which at least part of the oil modification from a drying (or semi-drying) ul consists.

A preferred composition according to the invention consists of the following Components:

(a) a non-volatile monomeric material greater than 50 up to 100% by weight DCP (M) A and, dissolved or dispersed therein,

(b) a polyol / polycarboxylic acid polyester resin modified with a drying oil which is based on a polycarboxylic acid or an anhydride and consists of more than 50 and up to 100% by weight of at least one aliphatic dicarboxylic acid or an anhydride with 4 to 40 carbon atoms, in the case of a dicarboxylic acid, the carboxyl groups being separated by a hydrocarbon group having at least 2 carbon atoms . ■

Optionally, component (b) can consist of an unsaturated polyol / polycarboxylic acid polyester resin based on a polycarboxylic acid decreases, which is more than 50 to 100% by weight of at least one unsaturated aliphatic dicarboxylic acid or composed of an anhydride having 4 to 40 carbon atoms, wherein in the case of a dicarboxylic acid, the carboxyl groups are replaced by a hydrocarbon group with at least 2 carbon atoms

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are separated, the unsaturation of the dicarboxylic acid or the anhydride contributing to the hardening of the mass when used.

Preferably the polyester resin is derived from maleic anhydride, maleic acid or linoleic acid dimer or is by reaction modified with a drying oil.

Another preferred composition according to the invention consists of the following components:

(a) a non-volatile monomeric material comprising more than 50% by weight of DCP (M) A and less than 50% by weight of an ester of a (C-Q-CjJ-aliphatic alcohol with acrylic acid or methacrylic acid or a dialkyl maleate, fumarate or itaconate, each alkyl group containing 1 to 8 carbon atoms, as well as, dissolved or dispersed in it,

(b) an oil-modified polyol / polycarboxylic acid alkyd or polyester which is based on a polycarboxylic acid or an anhydride and more than 50 to 100% by weight consists of at least one aromatic dicarboxylic acid or an anhydride.

In the compositions according to the invention, component (a) 15 up to 75 and preferably 25 to 60% by weight and component (b) constitutes 85 to 25 and preferably 75 to 40% by weight, in each case based on the total weight of components (a) and (b).

The masses can (c) a metal salt or a complex as a drying agent in an amount of, for example, 0.0005 to 10 and preferably from 0.0005 to 2% by weight, based on the total weight of components (a) and (b). The desiccant can be any polyvalent metal-containing complex

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or salt which catalyzes the oxidative hardening of drying oils or alkyd resins modified with a drying oil. Examples of drying agents are various salts of polyvalent metals, such as calcium, copper, zinc, hangan, lead, cobalt, iron and zirconium as a cation. Simple inorganic salts are also suitable, for example halides, in particular chloride, nitrates and sulfates. However, it is preferable to use salts of organic acids, such as the acetylacetones. To use acetates, propionates and butyrates. These drying agents can also be complex reaction products made from metal oxides, acetates or borates as well as vegetable oils. In general, the suitable drying agents consist of salts of naphthenic acids or (Cg-C ₃₀ ) -aliphatic acids. Examples of the polyvalent metals are calcium, copper, zinc, manganese, lead, cobalt, iron and zircon. Examples of the aliphatic or fatty acid component or the anion of the salt serving as a drying agent are the components of naphthenic acids, resin acids, ie rosin acids, tall oil fatty acids, linseed oil fatty acids, 2-ethyl] caproic acid, lauric acid, palmitic acid, myristic acid, linoleic acid, oleic acid, linoleic acid , Cerotic acid, montanic acid and abietic acid. Preferred salts which act as drying agents are those of cobalt and manganese, such as cobalt octoate, cobalt naphthenate and manganese octoate and naphthenate. Mixtures of different drying agents can also be used. The drying agents mentioned in "Encyclopedia of Chemical Technology", Kirk-Othmer, Volume 5, published by Interscience Encyclopedia, Inc., NY (1950) on pages 195-205 can be used.

The desiccant can be added to the mass before storage, provided that such addition is absent by oxygen. It is also possible to add a volatile stabilizer (d) to the mass in order to have an oxidizing effect

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to inhibit or prevent the desiccant, whereupon the mass in sealed containers to prevent a Volatilization of the inhibitor is stored. The stabilizing agent can be used in a small amount, for example 0.1 to 2% by weight, based on the weight of components (a) and (b), can be used. The stabilizing agent is generally a volatile ketone oxime or aldehyde oxime. Specific Examples are methyl ethyl ketone oxime, methyl butyl ketone oxime, 5-methyl-3-heptanone oxime, cyclohexanone oxime and butyraldehyde oxime. The addition of such an inhibitor is essential if a long stability and useful life of the mixtures of components (a), (b) and (c) is desired.

Component (a) of the mass can act as the only binding agent, so that essentially no volatile solvent is used. This results in a mass that can be regarded as consisting of up to 100% solids, since all the components are included serve, the solid resinous mass in the oxidation and polymerization, which results from the addition of a drying agent, to develop. With a view to suppressing pollution, reducing the risk of flammability as well as the toxicity to the personnel who use the compositions according to the invention, the most preferred compositions according to the invention consist of at least 70 and preferably 80 to 100% Solids. Also within the scope of the invention are compositions in which a certain amount of a volatile solvent is combined with the liquid monomeric component, as described above has been described, can be used to facilitate the adjustment of the viscosity for brushing, spraying or the like. The amount of the volatile solvent is not above 30% by weight and preferably not above 20% by weight, based on the total weight of the coating composition.

The inventive coating compositions can therefore according to a

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preferred embodiment "consist of the following components:

(a) a non-volatile reactive monomeric material found in essentially consists of the following components:

(1) In the case of the masses of type A, dxcyclopentenyl acrylate (DCPA) or methacrylate (DCPMA) or a mixture thereof or

(2) (in the case of masses of type B) DCP (M) A in a predominant Amount in a mixture with up to 40% by weight, based on component (a), of a non-volatile ethylenically unsaturated monomers, for example one saturated or unsaturated aliphatic ester of acrylic acid or methacrylic acid, the alcohol content Has 10 to 20 carbon atoms,

(b) a polyester or an alkyd with at least one unsaturated Component selected from residues or proportions of (1) maleic acid or maleic anhydride or fumaric acid, and (2) Residues or parts of drying or semi-drying oils, preferably an oil-modified polyester (or alkyd) made of:

(1) (In the case of masses A) an alkyd in which the dicarboxylic acid component Mainly or exclusively an aliphatic dicarboxylic acid (or an anhydrite thereof) having a hydrocarbon group or chain having 2 to 40 or more carbon atoms, which are the carboxyl groups separates, and 0 to 29% by weight of phthalic acid or phthalic anhydride or

(2) (in the case of masses B) an alkyd as under (b) (1) or an alkyd in which the dicarboxylic acid component

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may have predominantly or exclusively aromatic character,

(c) one of a polyvalent metal-containing desiccant and optionally

(d) a volatile stabilizer to inhibit the Oxidizing effect of the drying agent,

(e) a polyethylenically unsaturated monomer with low volatility and at least 2 groups of the formula H ₃ C = C ^, which makes up to 25% by weight and preferably not more than 2% by weight, based on the total binder weight, to improve the water resistance , solvent resistance, abrasion resistance, blocking resistance, or the like. Examples are glycol or polyol (meth) acrylates, for example ethylene glycol di (meth) acrylates, trimethylolpropane trimethacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri- and tetra ( meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate and allyl (meth) acrylate,

(f) a volatile solvent in an amount of up to about 30% by weight, preferably not more than 20% by weight, based on the total weight of the formulated coating composition which is ready for application,

(g) a pigment and / or filler, a dispersant therefor and / or other materials that are conventionally used in paints, varnishes and such coating compositions will.

In addition to the essential components mentioned above, you can also add various addition or condensation polymers of the thermoplastic type to such an extent as to which

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it with component (a) 'in the presence of component (b), optionally in the presence of a small amount of the organic solvent (f), are compatible. Instead of the thermoplastic addition polymers, thermosetting condensates such as Aminoplasts or phenoplasts, also to such an extent as to which they are compatible, are added. in the in general, the amounts of such additional polymers and / or condensation products can be from about 1/2 to 25% by weight, based on the weight of (a) + (b), vary.

The binder of the preparations described above consists of components (a) and (b) (plus (d) and any Addition and / or condensation polymers, which are explained in the previous section, if such polymers are added), while the binder is made up of these three components and the solvent (f), if such is used. If you take these components into account, then the preferred relative proportions are as follows:

Type A masses

Per every 100 parts by weight of the alkyd (b), the amount of monomeric component (a), which in this case consists essentially of DCP (M) A, vary between 15 and 300 parts by weight, preferably between 25 and 150 parts by weight.

Type B masses

For every 100 parts by weight of the alkyd resin, in particular one Resin of the hard type, i.e. an alkyd in which the polycarboxylic acid component is predominantly or exclusively aromatic is, especially in the case of alkyds from phthalic acid or phthalic anhydride, you can 17 to 300 parts by weight of the reactive

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Use monomer component (a) which consists of 60 to 90% by weight of DCP (M) A and the remaining 40 to 10% by weight of another non-volatile monomer, for example one or more (C ₁ QC ₂₀ ) -alkyl acrylates and / or methacrylates.

In preferred measures, special attention is given to the component (a) given, which determines the desired viscosity for the application of the top coat, for example by dipping, Brush, spray or roll on, leaving only a small amount of the volatile solvent (f) or none at all Solvent is used to prepare the coating composition, with 70 to 100% solids being obtained in which the entire binder of the mass is hardened to produce the solid coating, without the There is a need to remove a significant amount of volatile solvent during curing. By avoidance volatile organic solvents avoids fire and toxicity problems and eliminates the need the creation of solvent recovery systems.

According to a further embodiment of the invention, a liquid mixture with a reactive and essentially non-volatile character that acts as a whole binder (Vehicle) of coating compositions can be used which contain such common solid binding materials, for example Polyester (including alkyd and oil modified Alkyd resins) or polyisocyanate prepolymers that are cured and can be chemically combined with the reactive component of the binder if the films obtained during coating dried or otherwise hardened and / or solidified at ambient temperatures. This non-volatile reactive liquid consists of a mixture of DCP (M) A and at least one non-volatile monomer selected from the group those of (I) esters of (C. q-C-q) -aliphatic alcohols with

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2710Q32

Acrylic acid or methacrylic acid, such as the above-mentioned (C ₁ QC ₂₀ ) -alkyl and (C ₁₀ -C ₂₀ ) -alkenyl esters, (II) vinyl esters of higher (C. QC ₃₀ ) -aliphatic acids, such as those specifically mentioned above, and (III) non-volatile dialkyl fumarates, maleates and itaconates with (C _n -C ₂ -) - alkyl groups. These alkyl groups can be, for example, methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, myristyl, palmityl or stearyl. Such a mixture of non-volatile monomers can make up the entire binder, or it can be the predominant component of a binder containing some amount of a volatile non-reactive solvent in a minor amount.

The non-volatile reactive liquid binder as above can be made by blending and sold as a blend ready to be used as a formulation ingredient and serves as a binder or an important part of the same for the production of topcoat materials. Besides manufacturing the non-volatile reactive diluent or binder mixture in the specified relative proportions, for example 51 to 99% and preferably 60 to 90%, based based on the weight of the DCP (M) A, and 49 to 1%, preferably 40 to 10%, based on the weight of the other non-volatile monomer, the DCP (M) A can be supplied in the form of two or more mixtures with different proportions of DCP (M) A, including a mixture that contains only 1% by weight DCP (M) A and 99% of the other non-volatile reactive component, and a mixture containing 99% DCP (M) A. When pulling on you can then use the two liquids to adjust the Mix the relative amounts required for the respective coating compound are. For example, the amount of DCP (M) A in the non-volatile binder medium can depend on the desired hardness and Toughness also depend on the contribution made by the other components of the mass, including the one in question

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coming binder, for example one of the discussed Alkyds.

So far only masses have been discussed in which the alkyd or the polyester and the reactive monomer from DCP (M) A in one non-aqueous system are included. The invention also provides aqueous systems in which the alkyd or polyester is water-soluble or is water dispersible. In the latter case, an emulsifying agent can be used in a small amount sufficient to disperse the alkyd as well as the reactive monomer in the aqueous system. Often used in such Systems use the emulsifying agent for emulsifying a solution of the alkyd in a reactive monomer or the latter in the alkyd. In some cases, depending on the partition coefficient in question of alkyd, water and reactive monomers including DCP (M) A »the alkyd can be partially or completely be dissolved in the aqueous phase and be present in negligible manner or in partially dissolved form in the DCP (M) A phase. Examples of emulsifiers that can be used in such dispersed systems are nonionic Types such as tert-octylphenoxy-poly (10-40) -ethoxyethanol, anionic Types such as the sulfate of the nonionic type just mentioned, sodium lauryl sulfate or dioctyl sodium sulfosuccinate, or cationic Types such as dodecylbenzyltrimethylammonium chloride.

The masses, which contain the two main components (a) and (b), can be manufactured and stored before use. Even compounds containing the three components (a), (b) and (c), can be manufactured and stored if certain precautionary measures are observed. Usually the Masses, especially those which contain component (c), are stored in closed containers to air or Exclude oxygen. However, the two components (a)

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and (b) any other auxiliary components included in the Bulk can be used, mixed and without desiccant or volatile polymerization inhibitor or stabilizer be stored until the consumer has finished with the upper pull mass used, at which time component (c) is added with or without inhibitor or stabilizing agent (d) will.

The inventive polymerization or curing of the components (a) and (b) with each other and with other materials that react with them differs significantly from hardening, that by free radical polymerization of the type made using polymerization initiators such as Benzoyl peroxide, or by the methods carried out using a photosensitizer (photoinitiator) , the polymerization being effected by radiation, for example UV light, electron beams or x-rays. In the case of conventional polymerization by radiation using a photosensitizer the polymerization product obtained generally lacks durability. In contrast to the products that are obtainable using radiation and a photosensitizer is, in the case of the cured products, according to the invention using a desiccant will result in a significant amount of oxygen in the finished cured Products built in. It is believed that the desiccant is associated with the presence of oxygen, for example the oxygen in the atmosphere, a reaction of the drying oil component of the alkyd with an 8 double bond in the ring of DCP (M) A as well as in the (meth) acryloxy substituent causes a common reaction throughout the body each of these reactants occurs, which means that there is no appreciable amount of DCP (M) A that is not covalent in the hardened Product is bound. However, the invention is not intended to

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this theory of joint action may be limited. If the composition contains medium oil or long oil alkyds, the use of the drying agent results in a very effective hardening of components (a) and (b), optionally with other added components, this hardening during the action of the Atmosphere takes place even at normal temperature. Curing can of course be accelerated by heating, for example during a firing step in an oven, it being possible to maintain a temperature of 40 to 150 ^° C. or above, for example. Similarly, short oil alkyd resins in conjunction with the desiccant may take longer to air dry at normal room temperatures. In the case of these systems, it can be useful to provide a firing stage. Firing stages of this type can be carried out at temperatures of approximately 50 to 150 ^° C., it also being possible, if appropriate, to maintain lower or higher temperatures. The firing time depends on the mass used and can vary from a few seconds, depending on the thickness of the film, to 1/2 hour or more.

In the compositions according to the invention, the component containing DCP (M) A has the advantage that it is able to form solutions of the alkyd and of the drying agent and of other resinous or polymeric materials which can be incorporated into the composition. Will the use of volatile solvents by using the DCP (M) A with or without additional non-volatile monomers Avoided as the only solvent or diluent in the mass, then you actually get one that is 100% solids existing covering mass, the hardening of this mass no longer the necessity of having to release a volatile organic solvent into the air or the environment. Further eliminates the need to provide a facility for recovering a volatile solvent from the system or a To use the plant in which the hardening is carried out.

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In the various compositions mentioned above, the drying oil modified alkyds are preferred due to their characteristic air dry curing which is accelerated by the drying agent or agents which are added. The DCP (M) A is similarly cured simultaneously by air drying. The coatings obtained from compounds in which the alkyd is predominantly or exclusively derived from aliphatic components are characterized by excellent resistance to discoloration or yellowing when exposed to UV light, while the coatings made from such compounds in which the alkyd consists to a considerable extent of aromatic components, have excellent hardnesses without being too brittle and without a tendency to discolour under the influence of weather, but with excellent air-drying properties being retained. This combination of properties makes the compounds mentioned in addition suitable for a large number of purposes. This versatility is accomplished through the use of a reactive monomer component in the compositions, which is a predominant amount (60 to 90% by weight) of DCP (M) A with a smaller but substantial amount (10 to 40% by weight) of a non-volatile aliphatic Monoethylenically unsaturated monomers with a terminal group of the formula HC = CC ^, with (C ₁₀ -C ₂₀ ) alkyl acrylates or methacrylates being mentioned as examples, is achieved. The compositions according to the invention in which the alkyd is unsaturated as a result of the use of an unsaturated dicarboxylic acid, for example dimer acid (from linoleic acid polymerization), maleic acid or fumaric acid (or an anhydride of this acid) without modification by a drying oil, are suitable for the production of paints Oil-based, enamels, which are suitable for the surface treatment of household and industrial objects, wall coverings, shingles or other building elements. In such masses, in which the drying oil component is missing, the hardening depends on the

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Developing a high flow of free radicals which cause the alkyd and DCP (M) A to overflow the unsaturated Functionally copolymerize acrylate or methacrylate before the oxidative effect on the allyl type of unsaturation in the ring of DCP (M) A takes place. A hardening of such masses can by Introduction of a free radical initiator, such as benzoyl peroxide, in the inventive compositions, which an alkyd with contain both types of unsaturation, namely that which goes back to a 26, ß-ethylenically unsaturated dicarboxylic acid, as well as that which can be traced back to a drying oil can be accelerated, whereby a joint hardening with the DCP (M) A is not only runs according to the mechanism just described, but rather, autoxidation also takes place, which of course can be traced back to effective air drying or curing of the films that can be obtained from upper layers that are made from the masses exposed to the atmosphere at ambient temperature conditions. However, it is not 'intended that To limit invention to any of the theories discussed.

Some preferred embodiments of the invention are given below explained in more detail using the examples. All parts and percentages relate unless otherwise stated is on weight. Unless otherwise stated, all temperature data are in "Celsius".

Example A: Preparation of a "long" linseed oil / phthalic acid alkyd resin

In a flask equipped with a stirrer, thermometer, nitrogen inlet and a Vigreaux distillation column is provided with a head, 430 parts of linseed oil and 118 parts of glycerine are made filled. The flask is heated to 250-255 ° C and held at that temperature. The reaction follows one Dilution of a sample with ethanol (1 volume sample / 1 volume ethanol). The reaction is over when this dilution is a

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homogeneous solution results. The reaction time at 25O ⁰ C is about 6 hours. The batch is then cooled to 16O ⁰ C, whereupon 213 parts of phthalic anhydride and 5 parts of maleic anhydride are introduced. The temperature is allowed to rise slowly and water is distilled off from the batch. First of all, the water distillation is fast. Foaming can be problematic, so that a slow heating rate from 160 to 210 ° C may be necessary. The batch is then ^{heated to 235 to 240 °} C. and kept at this temperature. The reaction is followed by a measurement of the viscosity and an acid titration. The reaction is stopped when a Gardner-Holdt viscosity of BC of a 60% resin solution in xylene at 25 ° C and an acid titration value of 0.60 mXq / g (acid number = 34) have been determined. After completion (1 to 3 hours at 240 ⁰ C), the batch is cooled to 100 to 125 ° C, with a nitrogen atmosphere is maintained, before the resin (about 700 parts.) Is removed from the reactor.

Examples B to F: Production of further alkyd resins using aliphatic dibasic acids

The method described in Example A is used to prepare Solvent-free alkyd resins are used, with all or part of the phthalic anhydride by equivalent amounts is replaced on various aliphatic dibasic acids. In addition, to carry out Example F, flaxseed oil is used replaced by soybean oil. The components of the approach are shown in Table I, where the characteristic values of the Products are listed.

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430 430 430 430 - - - - - 430 - - 107 - - 5 5 5 5 5 210 - - - 210 - 268 135 - - - - - 806 - 118 118 118 118 118

Table I (Examples B-F) Example BCD

Components

Flaxseed oil soybean oil

Phthalic anhydride Maleic anhydride Adipic acid Azelaic acid Dimer acid * Glycerine

Characterization of the resin

Acid number 32 35 22 22 30

Gardner-Holdt viscosity

(60% in xylene)) D-E C B-C B-C B-C

Brookfield viscosity 10,000 5,000 20,000 15,500 (100%)

♦ Emery Industries, Empol 1014

Examples 1 to 6: Solvent-free clear coatings on the

Based on DCPA or DCPMA and alkyd resins

The solvent-free alkyd resins described in Examples A to F are used in DCPMA or DCPA in various proportions dissolved. In the fourth column of Table II, MA refers to DCPMA and A to DCPA. 100 parts of each 1 part of cobalt naphthenate (6% metal) and 0.25 part of methyl ethyl ketone oxime are added to the mixture. After thorough mixing the topcoats are applied to aluminum test panels and for a period of 2 weeks at ambient temperature Allowed to harden and then examined for their basic mechanical properties. The results are shown in Table II. the

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Use of alkyd resins based on aliphatic dicarboxylic acids has a marked improvement in the combination of viscosity reduction and hardness balance and flexibility. The flexibility test consists of bending a hardened film around mandrels with various Diameters to determine the smallest diameter that the film can be bent without cracking or tearing.

Alkyd
resin
according to
Ex. Parts
Alkyd DCP (M) A 40 employees
60 employees Tabel lead
Pen
hardness II Mandrel flexibility
(mm) at
game A. 60
40 40 A Visco
sity 2 B
F. Button
Hardness,
No. 76
•? 152 1 60 40 employees
50 employees
60 employees Z-2
P. B. 3.6
13.7 51 B. 60
50
40 40 A
50 A
60 A Z-1 6B
4B
F. 1.8 <3
51
76 2 60
50
40 40 employees
50 employees
60 employees Y
V
Q 5B
PE
F. 1.0
2.5
2.0 < 3
<3
<3 C. 60
50
40 40 A
50 A
60 A X
V
R. 4B
HB
F. 0.6
5.5
3.7 <7 ³ 6
> 76 3 60
50
40 40 employees
50 employees
60 employees U
O
H F.
4B
H 1.6
1.6
3.0 < ³
<2 ³ 5 D. 60
50
40 40 A
50 A
60 A U
O
I. 3B
F.
F. 4.8
2.8
4.1 38
76
127 4th 60
50
40 40 employees
50 employees
60 employees VW
N
HI B.
HB
2H 2.3
4.1
9.1 U E. 60
50
40 40 A
50 A
60 A UV
O
I. HB
H
B. 1.8
4.1
5.8 51
76
127 5 60
50
40 W.
S.
JK 3B
F.
H 1.4
3.6
9.1 < ₃ l
76 VW
R.
KJ 1.0
3.5
5.8

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40 employees
50 employees
60 employees -31 - 6B
5B
F. 4.1
1.5 2710032 40 A
50 A
60 A S.
J
E-F F.
F.
HB 3.0
1.3
1.8 60
50
40 S.
K
E-F 13th
13th
76 60
50
40 A.
U) U) U)

Example 7: Solvent-free clear coatings based on DCP (M) A and a phthalic acid alkyd resin

The alkyd resin according to Example A is in DCPma or DCPA or Mixtures of these with cetyl methacrylate (CEMA) * dissolved. To 100 parts of each mixture add 1 part of cobalt naphthenate (6% metal) and 0.25 part of methyl ethyl ketone oxime. The top coats are applied, cured and as in the case of the examples 1 to 6 examined. A modification with the long-chain methacrylate monomer enables the formation of top layers on the Basis of the phthalic acid alkyd resin and DCP (M) A, which avoids excessive hardening and excessive brittleness (Table III).

Table III

Pencil Knoop mandrel flexibility t hardness hardness (mm)

4.5 B 76

3.3 F 51

1.2 HB 38

1.1 HB 38

♦ A crude mixture of methacrylates of aliphatic alcohols with the following number of carbon atoms:

Parts - iskosj Alkyd Z-1 60 DCP (M) A CEMA V 8th X 60 40 employees 8th Z 60 40 A X 60 32 employees 32 A

fewer as C. ₁₆ (side chain) 2% C. 16 51 C. 18th 31 C. 20th 12th more than ^C 20 1

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TA

Examples 8 to 12: TiO ₂ -pigmented paints on the

Based on alkyd resins and DCPMA

A. Solvent-diluted alkyd paints are prepared from the resins of Examples A, B, C, D as described below and E made:

Components kg liter Alkyd resin (100%) 183.96 177.84 Rutile TiO ₂ 167.85 91.42 Zinc oxide 8.59 1.52 White spirit 60.39 77.90

60.39 77.90 1.84 1.06 3.82 1.59 0.48 0.53

The ingredients described above are mixed and placed on a three roll dispersion mill to a Hegman fineness of 7 wed. The paste is then mixed with the following ingredients:

White spirit cobalt naphthenate (6%) lead naphthenate (24%) methyl ketone oxime

487.32 * 379.76

B. 100% convertible paints are used of the alkyd resins of Examples A to E and of DCPMA as reactive diluents:

Components

Alkyd resin (100%) rutile TiO ₂

Zinc oxide

DCPMA

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kg liter 157.72 152.00 292.99 72.20 14.85 2.66 74.25 75.24

74, 25th 75 24 3, 08 1, 75 Of 38 Of 42

The above-described 'ingredients are ground as described under A, whereupon the paste with the following ingredients is mixed:

Components kg liter

DCPMA

Cobalt naphthenate (6%) methyl ethyl ketone oxxm

617.52 379.51

Both paints A and B have the same pigment volume concentration in the dried and cured film (20 parts by volume). However, the paint diluted with solvent has 25% by weight volatile constituents (41% by volume). All paints have a viscosity of 135 to 140 Krebs units.

Films of the paints are placed on Alodine treated aluminum panels as well as on clean cold rolled steel test panels produced, the films having a thickness of 63 μ in the dry state. All paints dry to a tack free Condition in about 16 hours. After air drying for 2 weeks at ambient temperature conditions the following physical properties are determined:

Example: 8 9 10 11 12 alkyd according to _ _ _p η ρ Example: ^ABC DE paint-. "". "" .. '.

_ty ρ. ABA, BABAB AB

properties

Knoop hardness, No. 0.75 12.5 0.57 4.1 0.44 3.2 0.67 2.8 0.92 7.3

Pencil hardness 6B F 5B F 5B F 6B HB 5B HB

Mandrel flexibility, mm3.2 168 3 13 3 9 3 63

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- 34 -

Solvent resistance (on aluminum)

(rated as film deterioration, with 10 having no effect means and 0 represents a complete failure)

a) 74 ⁰ C, 1%
"Tide"
(Detergent),
3 hours 0 10 0 10 1 10 2 10 5 10 b) Methylethyl
ketone, 3 hours 1 1 5 5 3 5 10 10 10 10 c) Toluene, 3 hours 1 1 5 3 5 5 10 10 10 10 d) Isooctane,
3 hours. 10 10 10 10 10 10 10 10 10 10 e) NH.OH (28%)
3 hours. 2 5 2 6th 2 6th 5 10 5 10 f) KOH (10%)
15 minutes. 1 10 1 10 1 10 1 10 1 10 G) HCl (10%)
3 hours. 1 8th 1 5 1 8th - 10 10 10 10

Anti-corrosion properties (on steel) - salt spray (500 hours)

a) general
Roast 10 10 6th 10 8th 10 0 5 8th 10 b) corrosion
under the
Upper pull 10 10 6th 10 8th 10 0 3 6th 10 c) blow 10 10 6th 10 7th 10 0 7th 7th 10

Whereas the conventional alkyd (Example A) is overly soft (Paint type A according to example (8), has a modification with DCPMA, excessive hardening and embrittlement (paint type B according to Example 8) result. The partially or fully aliphatic alkyds have an excellent balance for the same level of DCPMA modification between upper tensile strength and flexibility. DCPMA also significantly improves chemical resistance as well the corrosion resistance of alkyd resins.

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Example 13: Solvent-free paints based on phthalic acid alkyd resins and mixtures of DCPMA and a long chain alkyl methacrylate

Solvent-free paints are made according to method B of the examples 8 to 12, the alkyd resin described in Example A being used. The DCPMA is being used by increasing amounts of cetyl methacrylate, which is described in Example 7, the total amount of DCPMA and cetyl methacrylate being constant at 74.25 kg amounts to. Films are produced, cured and examined according to the method described in Examples 8 to 12, with the following Results obtained are:

% Cetyl methacrylate in the diluent monomer part of the paint:

0 10 20 30 40

Knoop hardness, No. 16.8 13.8 11.2 2.8 0.7 0.6 Pencil hardness F. F. F. B. 6B 6B Mandrel flexibility, mm 165 127 101 50 9 3

Example 14: Aqueous coating of a water-dispersed coating Alkyd resin and DCPMA

The base alkyd resin consists of Aroion 585 (Ashland Chemicals), a short safflower oil alkyd resin, which has a solids content of 42 parts in 57 parts of water and 1 part of triethylamine in Commercially, in the following ways, are paints manufactured:

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Components ■ paint A, paint B,

kg kg

Aroion 585 (42%) 121.03 121.03

Rutile TiO ₂ 102.33 102.33

The above ingredients are mixed and placed on a three roll mill to a Hegman reading of 7 grind and then mixed with the following ingredients:

Aroion 585 204.79 107.05 DCPMA - 41.04 Butyl carbitol 9.71 0.71 Triton-X-405 2.86 2.86 Cobalt naphthenate (6%) 1.04 1.04 Lead naphthenate (24%) 0.19 0.19 water 32.86 89.57

The pigment volume concentration of both paints is approximately 15% (Triton is a registered trademark).

The paints are produced on aluminum test panels applied by films with a thickness of 50 μ. After drying for 2 weeks at room temperature, the following film properties are found:

Paint A Paint B Knoop hardness, No. 1.0 8.0 Pencil hardness 3B HB

Example 15: Aqueous coating of an emulsified, solvent-free alkyd / DCPMA paint

Two parts of dioctyl sodium sulfosuccinate as a surfactant Agent is mixed with 100 parts of type B paint from

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Example 12 mixed. This mixture is then poured into 100 parts of water stirred in to achieve a coarse dispersion. A stable paint emulsion with low viscosity is obtained, by passing the coarse dispersion through a hand-operated Logeman mulsifier five times. The emulsified paint after application and curing, as in the case of Examples 8 to 12, provides a coating with essentially the the same film properties as have been described for the paint of type B according to Example 12.

Example 16: Aqueous coating of a water-soluble alkyd resin and DCPMA

The base alkyd resin consists of Aroion 376 (Ashland Chemicals), a medium to short safflower oil alkyd resin that contains 50 parts in a mixture of tert-butanol, butoxyethanol, water and Triethylamine (12.5, 12.5, 21.7 and 3 parts) brought to market will. Paints are made in the following way:

Components paint A paint B

Aroion 376 (50%) 55.70 55.70

RUtU-TiO ₂ 77.13 77.13

The ingredients described above are processed on a three roll mill ground to a Hegman reading of 7 and then mixed with the following ingredients:

Aroion 376 (50%) 137.47 79.49

DCPMA - 28.96

Mineral diluent 1.54 1.54

Cobalt naphthenate (6%) 0.81 0.81

Lead naphthenate (24%) 0.18 0.18

Water 170.29 199.26

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The pigment volume concentration of both paints is approximately 17%.

The paints are produced on aluminum test panels applied by dry films with a thickness of 50 μ. After drying for 2 weeks at room temperature the following film properties are determined:

Alistain A Paint B

Knoop hardness, No. 0.7 3.6

Pencil hardness 4B HB

Example 17: Solvent-free coating made from an oil-free one Maleic anhydride polyester and DCPMA

An unsaturated polyester resin is made by condensing 1 mole of maleic anhydride with 1.05 moles of dipropylene glycol to achieve a weight average molecular weight of 2500. 50 parts of the polyester resin are first divided into 50 parts DCPMA dissolved, whereupon 1 part cobalt naphthenate (6% cobalt) is added to the mixture. A film with a thickness of 40 μ will be potted on an aluminum test plate and allowed to dry at room temperature. Drying until it is tack-free Surface takes approximately 12 to 18 hours. After a Hardening over a period of 2 weeks is the pencil hardness F and the Knoop hardness number 11.6.

Example 18: Solvent-free coating compositions on the basis

of a phthalic acid alkyd resin and mixtures of DCPMA and a fumarate diester

The alkyd resin of Example A is made in DCPMA or mixtures thereof using

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«U

Dibutyl fumarate dissolved, to 100 parts of each mixture 1 part of cobalt naphthenate (6% metal) is added. The overalls are applied, cured and examined as in Examples 1 to 6. A partial modification of the dilution part of the coating with the fumarate ester means that excessive Hardening and embrittlement can be avoided while maintaining a low viscosity for application (Table IIIA). Compare example 7.

Table IIIA

Parts

Alkyd DCPMA Dibutyl
fumarate viscosity pencil
hardness Button
Hardness, Gardner
No. Duration
blow
strength,
m-kg 50 50 - N B. 7.6 <0.276 50 40 10 J B. 1.9 <0.276 50 30th 20th J HB 0.3 0.552 50 - 50 G / 6B * «0.1 * -

♦ sticky, poor curing

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Claims (21)

Claims 1. Autoxidizable coating and / or impregnation compound, characterized by (a) a reactive non-volatile monomeric material is selected the end (1) a monomeric material consisting essentially of dicyclopentenyl acrylate or methacrylate or a mixture thereof exists, and (2) a monomeric material composed of a predominant amount Dicyclopentenyl acrylate and / or methacrylate and a minor amount of at least one other non-volatile liquid monoethylenically unsaturated monomers, and, dissolved or dispersed in it, (b) an unsaturated polyol-polycarboxylic acid-alkyd or polyester resin, the alkyd or resin at least one unsaturated Has component selected from (I) maleic acid or anhydride or fumaric acid type fractions and (II) drying or semi-drying oil type fractions, the resins consisting of a polycarboxylic acid or an anhydride are formed, and the alkyd is selected from the following components: (1) Alkyds in which the polycarboxylic acid precursor component consists of a dicarboxylic acid which is 30 to 100% by weight consists of an aliphatic dicarboxylic acid or anhydride having 4 to 40 or more carbon atoms, and (2) Alkyds in which the polycarboxylic acid precursor component consists of a dicarboxylic acid which is 30 to 100% by weight is an aromatic dicarboxylic acid or anhydride, and where (a) (1) is used with (b) (1), 709837/0884 ORIGINAL or (a) (1) with (b) (2) in a weight ratio of less than 25 to 75 is used, or (a) (2) with (b) (1) and / or (b) (2) is used in such a way that when component (b) (2) is in bulk is used, either a sufficient amount of the other non-volatile monomer or a sufficiently low ratio of (a) (1) to (b) (2) is maintained so that the obtained film obtained by the mass is not excessively hard. 2. Composition according to claim 1, characterized by (a) a reactive non-volatile monomeric material is selected the end (1) a monomeric material consisting of dicyclopentenyl acrylate or methacrylate or a mixture thereof, and (2) a monomeric material consisting of more than 50% by weight of dicyclopentenyl acrylate and / or methacrylate and less than 50% by weight of at least one other non-volatile liquid monoethylenically unsaturated monomer and, dissolved or dispersed in it, (b) an unsaturated polyol-polycarboxylic acid-alkyd- or Polyester resin, the alkyd or resin having at least one unsaturated component which can be traced back to the following constituents: (I) maleic acid or anhydride or Fumaric acid type fractions or (II) drying or semi-drying type fractions, wherein the resin consists of a polycarboxylic acid or is formed from an anhydride, and the alkyd is selected from the following components: 709837/0884 (1) Alkyds in which the polycarboxylic acid precursor component consists of a dicarboxylic acid, 30 to 100% by weight of an aliphatic dicarboxylic acid or a Anhydride with 4 to 40 carbon atoms, and (2) Alkyds in which the polycarboxylic acid precursor component consists of a dicarboxylic acid, 30 to 100% by weight of an aromatic dicarboxylic acid or a Composed of anhydride, where (a) (1) is used with (b) (1), or (a) (1) is used with (b) (2) in a weight ratio of less than 25 to 75, or (a) (2) is used with (b) (1) and / or (b) (2). 3. Composition according to claim 1 or 2, characterized in that in component (a) (2) the other non-volatile monomer consists of one or more of the following constituents: (I) an ester of a Cc ₁₀ -C ₂ Q> - aliphatic alcohol with acrylic acid or methacrylic acid, (II) a vinyl ester of a (C ₁ qCq) aliphatic acid and (III) a dialkyl ester of maleic acid, fumaric acid or itaconic acid, each alkyl group containing 1 to 20 carbon atoms. 4. Mass according to one of claims 1 to 3, characterized in that that component (a) (2) consists of 60 to 90% by weight of dicyclopentenyl acrylate and / or methacrylate and 10 to 40% by weight of the other non-volatile monomer. 5. Composition according to one of claims 1 to 4, characterized in that that component (b) (1) or (b) (2) is based on a polycarboxylic acid component, more than 50% by weight of a 709837/0884 aliphatic dicarboxylic acid or an anhydride or an aromatic dicarboxylic acid or an anhydride. 6. Mass according to one of the preceding claims, characterized by (a) a non-volatile monomeric material consisting of more than 50 to% by weight of dicyclopentenyl acrylate and / or methacrylate and, dissolved or dispersed therein, (b) a drying oil-modified polyol / polycarboxylic acid polyester resin derived from a polycarboxylic acid or anhydride which is greater than 50 to 100% by weight at least one aliphatic dicarboxylic acid or an anhydride having 4 to 40 carbon atoms, the carboxyl groups being replaced by a hydrocarbon group in the case of a dicarboxylic acid separated by at least 2 carbon atoms. 7. Composition according to one of claims 1 to 5, characterized by (a) a non-volatile monomeric material of more than 50 to 100% by weight of dicyclopentenyl acrylate and / or methacrylate and, dissolved or dispersed in it, (b) an unsaturated polyol / polycarboxylic acid polyester resin which is based on a polycarboxylic acid, more than 50 to 100% by weight of at least one unsaturated aliphatic dicarboxylic acid or an anhydride having 4 to 40 carbon atoms exists, wherein in the case of a dicarboxylic acid, the carboxyl groups are separated by a hydrocarbon group having at least 2 carbon atoms in such a way that, when used, the Unsaturation of the aliphatic dicarboxylic acid or the anhydride increases contributes to the hardening of the mass, 709837/0884 8. Composition according to claim 7, characterized in that the polyester resin is due to maleic acid or maleic anhydride. 9. Composition according to claim 7, characterized in that the polyester resin goes back to linoleic acid dimer. 10. Composition according to claim 7, characterized in that the polyester resin modified by reaction with a drying oil is. 11. Composition according to one of claims 1 to 5, characterized by (A) a non-volatile monomeric material composed of more than 50% by weight of dicyclopentenyl acrylate and / or methacrylate and less than 50% by weight of an ester of a (c ₁₀ -C ₂ ^ -aliphatic alcohol with acrylic acid or methacrylic acid or a dialkyl maleate, -fuma - rat or itaconate, each alkyl group containing 1 to 8 carbon atoms, and, dissolved or dispersed therein, (b) an oil-modified polyol / polycarboxylic acid-alkyd or a Polyester, which is based on a polycarboxylic acid or an anhydride, the or more than 50 to 100% by weight of at least an aromatic dicarboxylic acid or an anhydride. 12. Mass according to one of the preceding claims, characterized in that that it consists of 15 to 75% by weight of component (a) and 85 to 25% by weight of component (b). 13. Composition according to one of the preceding claims, characterized in that that it also contains (c) a metal salt or a complex as a drying agent. 14. Composition according to claim 13, characterized in that it is 0.0005 709837/0884 up to 2% by weight of component (c), based on the total weight of components (a) and (b). 15. Composition according to one of the preceding claims, characterized in that that they also (d) 0.1 to 2% by weight of a volatile oxime stabilizer based on the total weight of components (a) and (b). , 16. Composition according to one of claims 1 to 12, characterized in that that components (a) and (b) are dissolved or dispersed in an aqueous medium. 17. Use of a composition according to any one of claims 1 to 16 for Impregnation or for coating a substrate. 18. Liquid mass which is suitable for use in a mass according to claim 1, characterized by a liquid mixture from the following non-volatile reactive monomers: (1) Dxcyclopentenyl acrylate and / or methacrylate and (2) at least one of the following: (A) an ester of a (C ₁₀ -C ₂₀ ) aliphatic alcohol with acrylic acid or methacrylic acid, (b) a vinyl ester of a (C ₁ q-C_ ₀ ) -aliphatic acid and (c) a dialkyl ester of maleic acid, fumaric acid or itaconic acid, each alkyl group containing 1 to 20 carbon atoms. 19. Mixture according to claim 18, characterized in that it, consists of at least 51% by weight of component (1) and up to 49% by weight of component (2). 709837/0884 20. Mixture according to claim 18 'or 19, characterized in that that it is in the form of two or more component mixtures that contain at least 1% by weight (1) and up to 99% by weight (2) included. 21. Mixture according to claim 20, characterized in that the Component ini mixtures 40 to 90% by weight (1) and 10 to 60% by weight (2) contain. 709837/0884