NO774136L - POLYMER, ESPECIALLY FOR USE AS COATING MATERIAL - Google Patents

Description

Polymer, especially for use as a coating

material,.

The present invention relates to a method for coating using polymer substances, as well as certain polymers. The polymer substances contain a water-soluble salt of a polymer containing pendant groups derived from a hydroxyamide of a fatty acid with drying oil, carboxy groups, carboxy ester groups and possibly residues from other unsaturated addition polymerizable monomers. The polymers have certain critical properties, such as carboxy unit content, glass transition temperature and molecular weight.

Similar polymers are known for coatings and other uses, such as putty-like sealants. Such sealants are known from US patent 3,759,915, while coating substances are known from US patent 3,590,016. The present invention relates to an improvement in relation to said US patent document 3,590. 016. In this patent document and in the present application, the polymers contain an acrylic backbone with pendant carboxy units, which in the preferred embodiment are post-reacted with N-hydroxyalkylamides. According to the patent document, the acid part of the hydroxyamide can be saturated or unsaturated, and the polymers described in the examples are very brittle as they have a high glass transition temperature (Tg). The polymers according to the patent can be water-soluble or water-insoluble. The salts of the polymers containing carboxyl groups described in the patents can be neutralized with ammonia, certain amines or other bases including those that were unsuitable for use according to the present invention,

when a metal siccative salt is used. Problems encountered with the known polymers include gelling, low gloss if dried under high humidity conditions, slow development of blocking resistance and unstable dispersions.

According to the invention, a water-soluble, air-curing, polymeric material has been produced where certain parameters and features of the polymer are critical for such use. E.g. finished coatings must have a T of less than 65°C, preferably less than 60°C. The calculated T of the prepolymer or backbone polymer, prior to esterification with the hydroxyamide, should preferably be below 50°C, although it may be as high as 85°C, if large amounts of the amide units are present.

The method according to the invention is characterized by

a polymeric substance is placed on a substrate and brought to or allowed to dry and harden in the presence of air, where the substance contains

(A) an aqueous, alkaline solution of an addition polymer that has been rendered soluble in the solution by means of ammonia

or a volatile amine, the polymer containing

(i) 5-60, preferably 10-40, e.g. 10-30, parts by weight of units with the formula

(ii) 20-90 parts by weight of units of the formula (iii) 5-20, preferably 8-15, parts by weight of units of one or more unsaturated carboxylic acids, where preferred units

as well as (iv) the possible remainder, which is necessary for there to be 100 parts by weight, are units of one or more other ethylenically unsaturated addition polymerizable monomers, where R<1> is H, (C1~C5)-alkyl, halogen, - CN, -CHjCOOR, -COOR or

-CH COOH, where R is (C 1 -C 8 )-alkyl,

2 7 7

R is (cR2)n'where R is H or -CH^ and n is 1 or 2, preferably 2,

R 3 is H or (C 1 -C 8 )-alkyl, preferably H, -CH 3 or

—CH^CH-,

R is an unsaturated, air-curable alkyl radical,

R 5 is K, -COOH, -CONH 2 or -COOR, where R is (C 1 -C 8 )-alkyl,

R6 is an aliphatic or cycloaliphatic radical containing from 1 to 20 carbon atoms,

the amount of units (iii) being sufficient to give the polymer a carboxy content of from 0.5 to 3 meky/g, preferably from 0.6 to 2.5 meky/g, and the amount of carboxy groups in the form of salt groups with the amine or the ammonia is sufficient to render the polymer water soluble, and the units (ii) are derived from monomers whose polymers have a T of from -80 to 120°C,

wherein the polymer has a viscosity average molecular weight of from 10,000 to 100,000, preferably from 20,000 to 80,000 and a cured film of the polymer has a T now: from -20 to 65°C and a Tukon hardness of from 0.2 to 10, and optionally

(B) a metal siccative in an amount of up to 0.5 percent by weight, on a metal basis, of the total weight of the polymer in

the substance.

The polymers used according to the invention and which contain the units (i) above can be produced by esterification of a backbone or base polymer with a hydroxyamide.

The base polymer contains units with the formula

where X is the units (iv), the optional other ethylenically unsaturated monomers, and R 1 is H and R 1 , R 1 , R 5 and R 5 are as indicated above. Hvdroksvamidet. a fat svreamide. has the formula

2 3 4

where R , R , and R are as indicated above.

The production of the fatty acid hydroxyamide is carried out in a known manner, which also applies to the esterification of the carboxyl groups in the polymer backbone with hydroxyamide. Examples of publications that describe these are The Journal of the American Oil Chemists' Society, 4_6, 355-364 (1969), where the use of diethanolamine for the production of the fatty acid hydroxyamide is described instead of mono-ethanolamine which is preferred according to the present invention, German patent document 1940 .471 and Belgian patent specification 757,271 and the corresponding US patent specification 3,590,016 as indicated above, where the two. the latter relates to hard coatings, such as paints. The US patent document and the Belgian patent document generally relate to the same type of polymers, although the products according to said patent documents have several disadvantages which make them unsuitable for many purposes. E.g. are all the described backbone polymers brittle or hard polymers. Thus, according to the examples in the patent documents, the softest polymer backbone seems to be of styrene and/or methyl methacrylate, which will have an alase temperature, T<J, of 100 C or more.

The fatty acid amide, and thus R 4 in formula I, is derived from one or more drying oils, such as linseed oil, tree oil, tall oil, safflower oil, conjugated safflower oil, isano oil, soybean oil, dehydrated castor oil, oiticica oil, menhaden oil and similar oils , also of synthetic origin, which has a carbon chain with preferably approx. 20 carbon atoms or less and which is unsaturated and which can air dry in a similar way to linseed oil. The preferred oils are those where the main component contains two or more olefinically unsaturated groups which can be either conjugated or alternating, including in addition to oiticica oil and dehydrated castor oil those which predominantly contain linoleic acid and/or linolenic acid.

According to a preferred embodiment, R<4> is derived

from a mixture of drying oils containing 50-90% by weight of one or more of the oils dehydrated castor oil, safflower oil, conjugated safflower oil or soybean oil, while 10-50% by weight is wood oil.

Formula IV thus represents the part of the addition-polymerized polymer backbone that has both free carboxyl groups and carboxyl groups that are esterified with the various alcohols that are usually used. Moiety X is derived from any of the well-known unsaturated addition polymerizable vinyl monomers as set forth below.

etc. 5

It should be understood that when R and/or R contain free carboxyl groups, -COOH, the hydroxyamide will react with these to form basic ester groups with a formula I.

Examples of R 1 and R 5 are:

Before the esterification with the hydroxyamide, the basic polymer is a water-insoluble vinyl polymer which contains the required proportion of carboxyl groups as described. The backbone polymers as such are known in the field and form no part of the present invention.

The proportions of the monomers in the backbone are such that there is at least 5% and never more than 20%, preferably less than 15% unsaturated carboxylic acid as units of formula IV where R gives H. A particularly preferred range is from 8 to 15%, and the optimal is considered to be in the range of 10-12%. It is most desirable to have a significant proportion of free carboxyl groups for good adhesion, and for the greatest possible elasticity over a long period of time the least drying oils.

The preferred base polymers are vinyl addition polymers, which contain as an essential component the α,3-unsaturated carboxylic acid, preferably acrylic acid or methacrylic acid.

Other useful copolymerizable acids are disclosed in US Patents 3,098,760 and 3,261,796 while additional examples are provided below.

By "unsaturated carboxylic acid" in the units (iii) is meant a simple monocarboxylic acid, a polycarboxylic acid or a partial ester or hemamide of α,3-unsaturated. polycarboxylic acids, as well as salts thereof with a volatile base such as ammonia, or with a volatile amine, which form water-soluble salts with the copolymerized acid. Examples of such amines are dimethylamine, triethylamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine and picoline.

When a desiccant is present and the acid is in salt form with an amine, it is preferred that the amine is a monoamine and not a polyamine, the latter being able to react with the metal in the silica. Examples of copolymerizable ethylenically unsaturated monocarboxylic or polycarboxylic acids are sorbic acid, acryloxyacetic acid, acryloxypropionic acid, vinylfuronic acid, α-chlorosorbic acid, methacryloxypropionic acid, methacryloxyacetic acid, p-vinylbenzoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, aconitic acid, atropic acid , crotonic acid and itaconic acids or mixtures of these acids. Itaconic acid and the α,8-unsaturated monocarboxylic acids, especially methacrylic acid and acrylic acid, are preferred. Other copolymerizable acid monomers are alkyl half-esters or the partial esters of unsaturated polycarboxylic acids, such as of itaconic acid, maleic acid and fumaric acid, or the partial amides thereof. Preferred half-esters are the lower alkesters (C,-CV),

16 such as methyl acid itaconate, butyl acid itaconate, methyl acid fumarate, butyl acid fumarate, methyl acid maleate and butyl acid maleate. Such partial esters and partial amides are considered to be "a, 8-unsaturated monocarboxylic acids", and this term includes such esters and amides in the sense used herein.

The term "vinyl monomer" means a monomer containing at least one of the following groups:

whether they are homopolymerizable or not, and give units corresponding to X, when this is present. Examples are a,g-ethylenically unsaturated monocarboxylic acid amides, a,g<->ethylenically unsaturated aldehydes, a,g-ethylenically unsaturated dicarboxylic acid amides, a,6-ethylenically unsaturated nitriles, hydrocarbons such as a-olefins, conjugated diolefins, vinyl aryl compounds, vinyl alkyl ethers, vinyl halides , vinylidene halides, vinyl sulfides, vinyl acyloxy compounds

(esters of saturated carboxylic acids and ethylenically unsaturated alkanols), vinylamines and their salts, vinylurea monomers, vinyl compounds with heterocyclic, nitrogen-containing groups (HN<) as well as halogen-, hydroxyalkyl- or aminoalkyl-substituted derivatives thereof, both as homopolymers or copolymers.

For examples of well-known vinyl polymers that can be used in the present invention, as well as methods for preparing the same, see "Polymer Processes", Schildknecht, Interscience, N.Y. 111-174 (1956). Blends of different polymers are useful.

Special examples of suitable monomers that can be copolymerized for the production of the water-insoluble base polymer for use according to the present invention in addition to the unsaturated acid monomers and their esters with alkanols having from 1 to 20 carbon atoms, such as methanol, ethanol, butanol and pentadecanol, is acrolein, methacrolein, ethylene, propylene, isobutene, butadiene, isoprene, chloroprene, styrene, vinyltoluene, vinyl methyl ether, vinyl isobutyl ether, vinyl chloride, vinyl bromide, vinylidene chloride, vinyl sulfide, vinyl acetate, vinyl propionate, the vinyl pyridines, primary amino compounds such as 3-aminoethyl vinyl ether, aminopentyl vinyl ether, secondary amine-containing compounds such as tert-butylaminoethyl methacrylate, tertiary amine-containing compounds such as dimethylaminoethyl methacrylate, and the related amine salts, such as chloride and hydroxide, as well as ureidomonomers which are described in US Patent 3.3 56,627. Copolymers and polytapolymers, block polymers or segmented polymers are included. Conventional methods for producing the backbone polymers are used.

Another of the essential monomers, in addition to the acid monomer, which is usually used in a significant amount in the production of the base polymer, is an elasticity-providing or soft monomer which can be indicated by the following formula:

where R is H or alkyl with 1-4 carbon atoms and is an unbranched or branched chain in a primary or secondary alkanol, alkoxyalkanol or alkylthialkanol and has up to approx. 14 carbon atoms, e.g. ethyl, propyl, n-butyl, 2-ethylhexyl, heptyl, hexyl, octyl, propyl, 2-methylbutyl, 1-methylbutyl, butoxy-

butyl, 2-methylpentyl, methoxymethyl, ethoxymethyl, cyclohexyl, n-hexyl, isobutyl, ethylthiaethyl, methylthiaethyl, ethylthiapropyl, n-octyl, 6-methylnonyl, decyl, dodecyl and the like, the radicals R when they are alkyl having from 2 to approx. 14 carbon atoms, preferably from 3 to 12 carbon atoms when R is H or methyl. When R is alkyl and R<11> is alkyl, R<11> should have from approx. 6 to approx. 14 carbon atoms, and when R is H and R<11>is alkyl, R<11> should have from approx. 2 to approx. 12 carbon atoms to be a soft monomer.

Other ethylenically unsaturated copolymerizable vinyl monomers whose homopolymers have a much higher glass transition temperature are preferably used in combinations with the above-mentioned soft monomers provided that they do not adversely affect the desired properties of the product, e.g. increases the total T^ unreasonably. These^"hard" monomers can be represented by the following formula:

22

where R is as indicated above and R is preferably alkyl and is methyl when R is H, and is alkyl with from 1 to approx. 5 carbon atoms or alkyl with from approx. 15 to approx. 20 carbon atoms when R is methyl. Examples of these hard ester monomers and other hard monomers include methyl acrylate, acrylamide, acrylonitrile, isobutyl methacrylate, vinyl acetate, tetradecyl acrylate, pentadecyl acrylate, methyl methacrylate, ethyl methacrylate, tert-butyl acrylate, butyl methacrylate, styrene, pentadecyl methacrylate, vinyltoluene, methacrylamide and N-methylolacrylamide.

For a given number of carbon atoms in the alkyl part, as is known, the degree and type of branching has a marked effect on T, since compounds with straight chains have a lower T g.

As can be seen, an important property of the backbone polymer is its T , and consequently the choice of monomers and their properties depends on their effect on T . T is a common criterion of polymer hardness and is described by Flory, "Principles of Polymer Chemistry", 56-57 (1953), Cornell University Press. See also "Polymer Handbook", Brandrup and Immergut, Section III, 61-63, Interscience (1966). Although actual measurement of T can be performed, it can be calculated as described by Fox, Bull., Am. Physics Soc., 1, 3, 123 (1956), or using the "Rohm and Haas Acrylic Glass Temperature Analyzer", Publication CM-24 L/cb, Rohm and Haas Company, Philadelphia, Pa., 19105. Although the prepolymers actual T is much lower than the calculated T due to low molecular weights, the calculated T^ is a very different characteristic of the relative glass transition temperatures for different polymers. Examples of T for homopolymers with a high molecular weight (< 1,000,000) and their glass transition temperature that enable such calculations are the following:

These or other monomers are mixed to achieve the desired

T n for the copolymer.

The base polymer is preferably produced by solution polymerization of one or more of the ethylenically unsaturated acids with other unsaturated monomers which include, among the more preferred vinyl monomers, the esters of acrylic acid and/or acrylic acid with benzyl alcohol, phenol or a saturated, aliphatic monoalcohol, in particular an alkanol with 1 -18 carbon atoms, such as cyclopentanol, cyclohexanol, methanol, ethanol, n-propanol, isopropanol, n-butanol, methoxyethanol, ethoxyethanol, methoxy-ethoxyethanol, ethoxyethoxyethanol, isobutanol, sec-butanol, tert-butanol and pentanol, hexanol, octanol, decanol, dode-carol, hexadecanol or octadecanol, taking into account the required T^ and the acid monomer. Preferred vinyl monomers in addition to the acid include one or more of an ester of an α,3-unsaturated carboxylic acid, or when these optional vinyl monomers are used, an unsaturated nitrile, a vinyl halide, a vinylidene halide, a vinyl aromatic, a vinyl alcohol ester or an unsaturated hydrocarbon, in particular acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyltoluene (o, m or p), vinyl chloride or vinylidene chloride, to form the unit X of the formula

above. Mixtures of copolymers can be used.

The solvent used in the polymerization can be organic solvents and mixtures thereof, such as benzene, toluene, xylene, solvent naphtha of aliphatic, aromatic or naphthenic type, such as white spirit, ether, esters, acetone, dioxane, etc. Preferred solvents are the monoalkyl esters (C^ -C^) of ethylene glycol, diethylene glycol or propylene glycol, "Carbitol", "Cellosolve" and "Propasol". Of course, other types of polymerization can be used. The amount of solvent in the polymer is from 0 to 80%, calculated from the polymer dry matter, preferably from 10 to 65%.

Any of the conventional drying agents or siccatives, such as the linoleates, naphthenates or resinates of cobalt, zirconium, manganese, lead, cerium, chromium, iron, nickel, uranium and zinc are suitable. Inorganic salts can also be used.

If desiccant is used, the amount of this calculated by the weight of the hydroxyamide of formula V may be as low as 0.01% and as high as 3% or more. Good results are often achieved with combinations of drying agents, such as zinc naphthenate and cobalt naphthenate in fairly small amounts, e.g. from 0.01 to 0.5% zinc naphthenate together with from 0.01 to 0.1% cobalt naphthenate is particularly favorable. Co 2+ as cobalt acetate is also usable, alone or together with compounds containing Mn , Zn , Zr Pb 2+ .

A preferred polymer for use in the method according to the invention contains: (a) 5-30, preferably 10-30, parts by weight of units of formula I, (b) 10-50 parts by weight of one or more esters of acrylic acid and/or methacrylic acid as in homopolymerization gives a polymer having a T of from 0 to -80°C, preferably below -10°C,

g

(c) 20-70 parts by weight of one or more esters of acrylic acid and/or methacrylic acid, vinyl aromatic hydrocarbons and unsaturated nitriles which upon homo<p>olymerization give a polymer having a Tg of from 20 to 120°C, preferably from 50 to 120°C, (d) 5-15, preferably 3-15, parts by weight of an ethylenic unsaturated carboxylic acid, as well as optionally (e) up to 20 parts by weight of one or more different ethylenic unsaturated monomers which impart hydrophilicity to the polymer and increase its solubility in aqueous liquids, the sum of (a), (b), (c), (d) and (e) when used being 100 parts by weight.

Preferably, in this polymer, the amount of ethylenically unsaturated acid units is such that they amount to from 0.6 to 2.5 meq/g of the polymer.

It is particularly preferred that the polymer is a polymer where (b) is one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate or isopropyl acrylate,

(c) is one or more of methyl methacrylate, styrene, ethyl methacrylate, acrylonitrile, butyl methacrylate, isobutyl methacrylate and vinyltoluene, and (d) is one or more of acrylic acid, methacrylic acid, maleic acid and itaconic acid, and (e) when this is used is one or more of hydrophilic monomers, hydroxyethyl or hydroxypropyl-(meth)acrylate.

The preferred viscosity average molecular weight is from 20,000 to 80,000, especially from 30,000 to 50,000.

or -I C^en CHfo^r, eotrg ukR k4 ert epsoteln ymefr ra meéd n efolrlmer el flIe, re er syn re2^ , R of 3 Htø, rk-CeHndJ,e oils in the form of tree oil, linseed oil, dehydrated castor oil, safflower oil , conjugated safflower oil, soybean oil and oiticica oil. A particularly preferred combination of unsaturated, drying oleic acids is 50-90% of the acids from dehydrated castor oil, safflower oil, conjugated safflower oil or soybean oil, mixed with 10-50% by weight of the acids from wood oil.

It is possible to use only an acrylate or methacrylate ester, as it is not necessary to use a combination if the suitable hardness and glass transition temperature can be achieved in another way. An example of a polymer of this type is a polymer which

.contains polymerized units consisting mainly of

(a) 5-30 parts by weight of units of formula I,

(b) 4 5-90 parts by weight butyl acrylate,

(d) 5-15 parts by weight of an ethylenically unsaturated carboxylic acid

in an amount of from 0.6 to 2.5 meq/g of the polymer, as well as optionally (e) up to 20 parts by weight of another ethylenically unsaturated monomer which imparts hydrophilicity to the polymer and increases its solubility in aqueous liquids, the sum of (a) , (b), (d) and (e) are 100 parts by weight.

The substrates on which the polymers are to be applied are of all types, such as silicon-containing substrates in the form of glass sheets, glass fiber textiles, asbestos sheets, asbestos cement products, concrete, stone, plaster, slate, sandstone, granite, ceramics, porcelain as well as fibre-reinforced plastic objects such as canoes, ship hulls or other shaped objects made of glass fiber reinforced polyester or other plastic material, metals such as aluminium, steel, iron and brass, wood and other construction materials, metal oxide layers such as aluminum oxide and iron oxide, leather, cellulose textiles such as cotton, linen, silk, wool, rayon, cellulose esters such as cellulose acetate, nylon, polyesters such as polyethylene glycol terephthalate, acrylonitrile polymers, vinylidene chloride polymers and other vinyl or acrylic ester polymers, films, films, sheets and other shaped articles of plastic systems, such as of cellulose ethers or esters including hydroxyethyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, polyesters such as polyethylene glycol terephthalate, nylon, vinyl chloride or vinylidene chloride polymers and copolymers, methyl methacrylate polymers and copolymers, aminoplast or phenoplast resins, organo<p>oly-siloxane resins or rubber.

Preferably, the coatings have a thickness of from 2.5 to 250 µm when dry.

The products according to the present invention are particularly valuable in that they can usually be used directly on any of the substrates without the need for a primer coating.

The polymers are particularly suitable as additives to latexes as shown in example 3. Suitable latexes are aqueous addition polymer dispersions, which are usually prepared most conveniently by direct emulsion polymerisation. The most important of these dispersions used in the production of water-based paints are polymers containing homopolymers and copolymers of (a) vinyl esters of an aliphatic acid with from 1 to 18 carbon atoms, especially vinyl acetate, (b) acrylic acid esters and methacrylic acid esters of an alcohol having from 1 to 18 carbon atoms, in particular methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate,

and (c) mono- and diethylenically unsaturated hydrocarbons, such as ethylene, isobutylene, styrene and aliphatic dienes such as butadiene, isoprene and chloroprene.

Polyvinyl acetate and copolymers of vinyl acetate with one or more of the following monomers: vinyl chloride, vinylidene chloride, styrene, vinyl toluene, acrylonitrile, methacrylonitrile, one or two of the above-mentioned acrylic and methacrylic acid esters are known as the film-forming component in water-based paints. Similar copolymers of one or more of the above-mentioned acrylic or methacrylic acid esters with one or more of the following monomers: vinyl acetate, vinyl chloride, vinylidene chloride, styrene, vinyl toluene, are also used more or less commonly in water-based paints. Homopolymers of ethylene, isobutylene and styrene, and copolymers of one or more of these hydrocarbons with one or more esters, nitriles or amides of acrylic acid or of methacrylic acid with vinyl esters such as vinyl acetate and vinyl chloride, or with vinylidene chloride are also used. The diene polymers are usually used in water-based paints in the form of copolymers with one or more of the monomers styrene, vinyltoluene, acrylonitrile, methacrylonitrile and the above-mentioned esters of acrylic acid or methacrylic acid. It is also quite common to add a small amount, such as from h to 5% or more, of an acid monomer in the monomer mixture used for the preparation of the copolymers of all the above three general types by emulsion polymerization. These acids include acrylic acid, methacrylic acid, itaconic acid, aconitic acid, citraconic acid, crotonic acid, maleic acid, fumaric acid, dime of methacrylic acid, etc.

These aqueous dispersions can be prepared using one or more emulsifiers of anionic, cationic or non-ionic type. Mixtures of two or more emulsifiers can be used regardless of the type, with the exception that it is usually undesirable to mix a cationic with an anionic type in any particular amount, as these tend to neutralize each other. Moreover, many cationic types of emulsifiers are not combinable with the polymers according to the invention. The amount of emulsifier can be from 0.1 to 5% by weight or sometimes even more, calculated by the weight of the total monomer charge. When a persulphate is used as initiator, the addition of an emulsifier is often unnecessary, and this omission of even the small amount, i.e. less than approx. 0.5% emulsifier, may occasionally be desirable from a cost point of view (omission of expensive emulsifier) and due to less sensitivity of the dried coating or impregnation to moisture, and consequently less tendency of the coated substrate to be affected by humidity, such as would produce coatings that are less prone to swelling or softening, particularly when exposed to moist atmospheres. The average particle size or diameter of these dispersed polymers can be from approx. 0.03 to 3 microns or more. By particle size is meant here the "weight average diameter". This number, expressed in microns, is determined using an ultracentrifuge. A description of the method can be found in The Journal of Colloid Science 1_5, 563-572 (1960). In general, the molecular weight of these emulsion polymers is high, e.g. from approx. 100,000 to 10,000,000 viscosity average molecular weight, most commonly above 500,000. A suitable weight ratio is 10-70, preferably 10-50 of the soluble polymer with 30-90%, preferably 50-90% latex polymer, on a solids basis. They are insoluble in aqueous media at a pH of 3-11.

According to the invention, a polymer has also been produced which is oxidatively curable with air and which contains:

(a) 5-60 parts by weight of units of the formula

(b) 10-50 parts by weight of one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate and isopropyl acrylate, 0 (c) 20-70 parts by weight of one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, sec-butyl methacrylate , tert.-butyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, acrylonitrile, isobutyl methacrylate, styrene and vinyltoluene, (d) 8-15 parts by weight of one or more of acrylic acid, methacrylic acid, maleic acid and itaconic acid,

where R<1> is H, (C 1 -C 8 )-alkyl, halogen, -CN, -CH 2 COOH, -CH 2 COOR or -COOR, where R is (C 1 -C 6 )-alkvl,

3 18-

R is H or (C1-CQ)-alkvl,

4 18-

R is an unsaturated, air-curable radical and

R 5 is H, -COOH, -CONH 2 or -COOR, where R is (C 1 -C 8 )-alkyl,

while the rest

is a cutting residue from a drying oil i

form of one or more of treoleic acid, linoleic acid, dehydrated castor oleic acid, safflower oleic acid, conjugated safflower oleic acid, soya oleic acid and oiticica oleic acid,

wherein the sum of (a), (b), (c) and (d) is 100 parts by weight, the amount of (d) is from 0.5 to .3 meq/g of the polymer and is sufficient when in the form of salt groups with a volatile amine or ammonia, to impart water solubility to the polymer whose viscosity average molecular weight is from 20,000 to 80,000 oa T for a cured film of the polymer from 10 to 65°C.

Preferably, R is derived from a mixture of acid of drying oils as described above.

Some preferred embodiments of the invention will be described in more detail in the following examples where all parts and percentages are by weight and the temperature in °C

unless otherwise specifically stated.

In the examples, the abbreviations for the monomers have the following meanings:

BA - butyl acrylate HEMA - hydroxyethyl methacrylate

MMA - methyl methacrylate MMA - methacrylic acid

AA - acrylic acid BMA - butyl methacrylate

S - styrene EA - ethyl acrylate

AN - acrylonitrile iBMA - isobutyl methacrylate MHELAE■- linoleic acids

MHESAE - soybean oleic acids

MHESAFAE - safflower oleic acids

MHEDCAE - dehydrated castor oil acids

MHETAE - wood oleic acids

MHESTAE - stearic acid, a non-drying acid

HELAE - N-hydroxyethyl linoleic acid amide esters

HESAFE - N-hydroxyethyl safflower oleic acid amide esters •

In the following table, the prepolymers with a solids content of 85-90% were prepared by solution polymerization in "butyl-Cellosolve", followed by post-polymerization esterification with the drying oil N-methyl-N-(8-hydroxyethyl)-amide of a portion of the copolymerized, unsaturated acid. Details of the preparation are given in table I while a typical method is given in table ill.

At the higher levels of drying oil, the molecular weight of the uncured polymer increases somewhat.

The polymers which have a viscosity average molecular weight of approx. 40,000 requires significantly less content of drying oil, approx. 20% for good curing properties, than polymers with a viscosity average molecular weight of approx. 20,000 do, which exhibits effective curing at approx. 4 0% content of drying oil.

The cure rate is a function of the type of drying oil. Curing efficiency is also a function of the type of drying oil and its amount. It has been shown that some polymers containing styrene or acrylonitrile cure at a slightly lower rate, while analogous polymers containing hydroxyethyl methacrylate (HEMA) show an increased rate of cure.

The viscosity average molecular weights as determined here generally agree with molecular weight determinations by gel chromatography. In most cases, molecular weights by gel chromatography were determined on methylated prepolymers that were methylated to reduce the copolymer acid for more reliable measurements. "Prepolymers" are polymers before esterification with the drying oil hydroxyethyl amides, also referred to as backbone or base polymers. The molecular weights listed were calculated from the prepolymer molecular weights plus the weight of the amide of the drying oil. In an example (F), the gel chromatography molecular weight was determined directly on the methylated final polymer. The good agreement between E and F indicates that few cross-links are formed between the chains of drying oils during the post-polymerisation esterification.

The solution viscosities of the water-soluble copolymers can be greatly lowered by the addition of a co-solvent. It is concluded that (a) the solubility parameter and hydrogen bond class of a carbon solvent have no connection with the effectiveness of the carbon solvent's ability to lower the solution's viscosity and (b) among the better carbon solvents (acetonitrile, isopropanol, isobutanol, acetone, methyl ethyl ketone) are all about equally effective when it comes to lowering the viscosity of the solution. Other usable carbon solvents are butyl "Cellosolve", butyl "Carbitol", "Propasol" B, "Propasol" P and diacetone alcohol.

It is important to cool the batch quickly after the esterification is complete, otherwise gelatinization may occur. Temperature reductions can be achieved by recooling an azeotropic mixture of water and xylene during the esterification and by subsequent removal of the azeotropic mixture under vacuum without the addition of additional heat. Esterification temperature and time are also important. When a temperature of 16 5°C is used, the esterification must be completed in a much shorter period of time, e.g. 10 minutes, to have a reasonable gel-free time compared to esterification at 145°C, where mostly gel-free time is achieved even when the esterification is carried out over a period of 45 minutes. Other factors that contribute to gel-free time are the content of copolymerized acid, as a lower acid content gives a longer gel-free time, and the total solids content, as products with a lower solids content have a longer gel-free time. Another factor is the nature of the drying oleic acid. The order of sensitivity to gelatinization is as follows: dehydrated castorwood > wood > flax = saf f lov/er ^. soy stearin. Additives that will suppress the gelatinization effect are

occasionally usable. These additives include carboxylic acids and aniline. Examples of the acids are monochloroacetic acid and benzoic acid.

In what follows, a trial calculation is given for determining the mutual weight ratio for the units with the formula IV,

I and X when these are present in the final polymer.

The sample calculations illustrate the production of 30BA/42MMA/20MHELAE/8AA polymer by reacting the carboxy-containing base polymer with N-methyl-N-hydroxyethyllinoleic acid amide. A prepolymer with the composition 35.86BA/50.19MMA/13.95AA (calculated T = 8°C) converts with 20.59%, calculated from the weight of the prepolymer, N-methyl-N-hydroxyethyl linoleic acid amide (MHELA). Thus, 100 g of prepolymer is reacted with 20.59 g of N-methyl-N-hydroxyethyl linoleic amide.

20, 59 = 0.0611 mol amide.

337 72 x 0.0611 = 4.40 g. AA in 0.0611 mol. 18 x 0.0611 = 1.10 g. H2/in 0.0611 mol.

Weight of MHELAE units with the formula V 2 20.59 +

4.40 = 1.10 = 23.89 g.

Final composition

The polymer compositions have been calculated here in a similar way.

Example 1

Production of 40BA/3 0MMA/20MHELAE (linseed oil)/10AA with

a MV of approx. 4 0.000.

A monomer mixture was prepared with the following substances:

view

An initiator solution with the following substances was prepared:

The following substances were placed in a reaction vessel equipped with a stirrer, condenser, nitrogen purge and two gradual addition devices:

The batch was heated to 110°C and 6% of the initiator solution was added. After a residence time of 15 minutes, the remainder of the monomer mixture and the initiator were added proportionally over the course of 4 hours while the temperature was maintained at 110 + 30°C. After these additions, a mixture of 1.8 parts "Lupersol" 70 (tert.-butyl peracetate) and 5.8 parts butyl "Cellosolve" was added to the batch and the temperature increased to 170°C. The resulting acrylic base polymer or prepolymer (47.87BA/35.91MMA/16.21AA) had a calculated T of 7°C. At 170°C, a mixture of 134.5 parts of II-methyl-N-hydroxyethyl linoleic acid amide and 65.0 parts of xylene was added. The temperature dropped to 153°C. During the next 45 minutes, while maintaining the temperature at 150-155°C, 76 parts of a two-phase, clear solution were distilled from the batch under partial vacuum. After the distillation, the batch was cooled to 95°C, and a mixture of 68.5 parts of 28 percent aqueous ammonia and 600 parts of deionized water was added to the batch with good stirring. At 75°C, the batch was removed from the reaction container and placed in a glass container where the temperature was allowed to drop to room temperature.

The product of this process was a clear, aqueous solution

with a solids content of 51.4% and a viscosity of 281,000 cP. The viscosity average molecular weight was determined to be 42,300. A thin film (25-75 microns) of this<p>polymer solution, which contained

2+

0.1% CO (as cobalt acetate) detacked within five hours and cured in one week at room temperature to a faint yellow, alkali-insoluble film. The glass transition temperature of the hardened film was approx. 20°C.

Example 2

Production of 4OBA/3OMMA/2OMHELAE (linseed oil)/10AA

with a Mv of 8 0,000.

The procedure in Example 1 was repeated, but mercaptoethanol was reduced to 1.7 parts. The product from this process was a clear, aqueous solution with a solids content of 50.7% and a viscosity of 342,000 cP. The viscosity average molecular weight was determined to be 80,000. A thin film of this material was cured similarly to the film described in example 1 and had a T g of approx. 2 5°C in hardened form.

Example 3

Production of 2OBA/42MMA/3OMHELAE (linseed oil)/8AA

with a Mv of approx. 2 0.000.

A monomer mixture of the following substances was produced:

This monomer mixture (26.6BA/55.7MMA/17.7AA) gives a prepolymer which has a calculated Ta of approx. 4 3°C.

An initiator solution of the following substances was prepared:

The following substances were placed in a reaction vessel equipped with a stirrer, nitrogen purge, condenser and two gradual addition devices:

The batch was heated to 142°C, and 6% of the initiator solution was added. An exothermic reaction to 151 C was observed.

This temperature was maintained for 15 minutes, after which the rest of the monomer mixture and the initiator solution were added over 4 hours while the temperature was maintained at 150+ 3°C. 15 minutes after the completion of these additions, a mixture of 1.8 parts "Lupersol" 70 and 5.8 parts butyl "Cellosolve" was added to the batch. The temperature was held at 150 + 2°C for a further 15 minutes, after which a mixture of 224 parts of N-methyl-N-hydroxyethyl linoleic amide and 69 parts of xylene was added gradually over 15 minutes while the temperature was still held at 150 + 2°C. The temperature was then allowed to rise slowly to 155°C over 30 minutes, and 30 parts of a biphasic, clear liquid was distilled from the batch at atmospheric pressure. After the distillation, the batch was cooled to 95°C, and a mixture of 50.3 parts of 28 percent ammonia and 587 parts of deionized water was added to the batch with good stirring. At approx. 7°C, the batch was removed from the reaction container and placed in a glass container where the temperature was allowed to drop to room temperature.

The product from this process was a clear aqueous solution (referred to below as copolymer-3 solution) with a solids content of 53.1% and a viscosity of 11,230 cP. The viscosity average molecular weight was determined to be 22,500. A thin film (25-75 microns) of this polymer solution containing 0.1% Co2 +

(as cobalt acetate) became tack-free within 4 hours and cured in two weeks at room temperature to a slightly yellow, alkali-insoluble film with a Tukon hardness of approx. 1.5 oa at a glass temperature of approx. 25°C.

A pigment coating was prepared using Cowles dissolver and the following substances:

<x>) A copolymer of maleic anhydride and diisobutylene in the molar ratio 1:1. 0

A very even pigment coating was achieved by adding TiO2 to the liquid components. The mixture was stirred on the Cowles mixer at 1067-1219 m/min for 30 minutes. The coating was thinned in the following way using a normal pipework:

The resulting paint had a viscosity of 2700 cP, a pH of 8.5 and, when drained, had a 60° gloss of 80 with a slight yellowish tint. Its tack-free time was significantly better than that of commercially available solvent alkyd paints with similar gloss properties.

Removal of the dispersant resulted in completely satisfactory pigment grinding. The ratio used was:

As above, a Cowles dissolver was used at a peripheral speed of 1067-1219 m/min to disperse the pigment. The resulting finish was fairly even and was much easier to produce than conventional semi-gloss finishes. The coating was thinned with additional water-soluble polymer as follows:

At an approximate solids content of 30% by volume and a PVK of 25% with a viscosity of 1750 cP at a pH of 8.5, this paint had good ironability and leveling, excellent gloss and a slight yellowish tint.

Common propylene glycol/polyelectrolyte dispersant coatings can also be used. In this case, the soluble polymer replaces the latex in the thinning step. A typical paint job:

x)

<x>) Maleic anhydride-diisobutylene copolymer.

As in the other cases, a Cowles dissolver was used for the preparation of the coating.

The thinning step, which was carried out with a normal pipework, consisted of the following:

The metal-containing desiccant in the copolymer-3 solution was varied as indicated below:

<1>) % metal of total solids content in copolymer-3.

The resulting paints had very high gloss, particularly gloss depth or image gloss according to 20° gloss measurements. These are listed below along with 60° gloss and paint viscosity and pH.

A normal latex control sample had a 60° gloss of 65 while the 20°^ value would typically be 20-25.

A further variant with good gloss properties is a mixture of the water-soluble polymer with a regular acrylic latex (EA/MMA/MAA 57/42/1) on a 20/80 basis. The following conditions were used:

This paint had a 20°/60° gloss of 31/80, not as good as the above examples containing only the water-soluble polymer, but significantly better than the gloss of a paint formulated without copolymer-3 as follows.

which had a 60° gloss of 65 (its 20° gloss was not measured, but typical values observed for similar formulations averaged 28).

Example 4

Production of (20BA/4 2MMA/3 0MHESAE) (soy) /8AA polymer with an Mv of approx. 20,000.

The procedure in example 3 was repeated with an equal amount by weight of N-methyl-N-hydroxyethyl soya oleic acid amide instead of N-methyl-N-hydroxyethyl linoleic acid amide. The product from this process was a clear, aqueous solution with a solids content of 53.4% and a viscosity of 19,000 cP. The copolymer acid titer was 1.13 meq/g polymer. A 25-7 6 micron thin film of poly-2+

the additional solution containing 0.1% Co (in the form of cobalt acetate) was cured for two weeks at 60°C to a slightly yellow, alkali-insoluble film with a Tukon hardness of approx. 2.0.

Example 5

Production of (40BA/20MMA/2OMHELAE) (linseed oil/20AA polymer with a Mv now approx. 20,000.

*• - ■u- -- — ■■■ - - -i .. —

The procedure in Example 3 was repeated with the butyl acrylate changed to 326 parts, the methyl methacrylate to 163 parts, the acrylic acid to 191.5 parts, the mercaptoethanol to 3.41 parts, the N-methyl-N-hydroxyethyl linoleic amide to 134.5 parts, the aqueous ammonia to 138 parts and the deionized water to 542 parts. The acrylic backbone (47.9BA/24MMA/28.1AA) had a calculated T now 8°C. 9"

The product obtained was a clear aqueous solution with a solids content of 50.7% and a viscosity of 14,500 cP. The viscosity average molecular weight was determined to be 21,000.

Example 6

Production of 20BA/42MI1A/3OMHELAE (linseed oil)/8AA polymer with an Mv of approx. 20,000, neutralization with triethylamine.

The procedure in example 3 was repeated with 111.1 parts of triethylamine instead of 28 percent ammonia solution, and deionized water increased to 526.6 parts. The product obtained was a slightly cloudy aqueous solution with a solids content of 53.6%

and a viscosity of 11,650 cP. A thin film of 25-75 microns of this polymer cured correspondingly to the polymer as described in example 3.

Example 7

Preparation of (5BA/42MMA/45MHELAE)(linseed oil)/8AA polymer with an Mv of 20,000.

The procedure in Example 3 was repeated with the butyl acrylate changed to 53.8 parts, the methyl methacrylate to 4 56.0 parts, the acrylic acid to 172.4 parts, the N-methyl-N-hydroxyethyl linoleic amide to 403 parts, the 28 percent aqueous ammonia to 66, 7 parts and the deionized water to 571 parts. The acrylic backbone (7.9BA/66.8MMA/25.3AA) had a calculated T" of 84°C.

The product obtained was a cloudy aqueous solution with a solids content of 56.7% and a viscosity of more than 100,000 cP, hereafter referred to as copolymer-7 solution. A 25-75 micron thin film of this polymer solution with 0.1% Co 2+ (as cobalt acetate) cured to a yellow, alkali insoluble film with a Tukon hardness of approx. 3.0 and y a T g -now approx. 50°C after two weeks at 25°C.

The Co<p>olymer-7 solution was mixed into the preferred grinding of these water-soluble binder solutions, which contained only pigment, polymer and water and which eliminated the need for film formers, wetting agents, dispersing agents,

in the following way:

Standard technique using Cowles dissolver was used. The coating was thinned with additional water-soluble polymer containing varying amounts of metal-containing desiccant. The total prescription for this series includes:

The desiccant levels in paint no. 7-1, -2, -3 and -4 were 0, 0.1,

2+

0.25 and 0.5% Co of the polymer solids, in the form of cobalt acetate.

These "paints had pH values, viscosities, gloss (range 82-94) and other properties of the previous paint series. In addition, alkali scrubbing resistance was measured with a Gardner scrubbing machine with 4 54 g porcelain bowl, detergent in the form of 1 percent" Tide" solution for 500 cycles. 60° gloss was examined before and after scrubbing. Substrates were 17 5 micron films on black vinyl sheets. Paint No. 7-1, which was desiccant-free, was completely removed from the panel after three days of air drying . After a week, 30% of the film had been removed. After one day of air drying, the gloss went from paint no. 7-4,

2+

which contained 0.5% Co from 92 to 81 after 500 cycle scrubbing, while after seven days of air drying the gloss changed from 89 to 82, or -8%. Two days' drying time was sufficient for 90% gloss retention at 0.25% Co<2+>.

Example 8

Preparation of (3OBA/4OMMA/2OMHELAE), (linseed oil)/10AA polymer with an Mv of approx. 4 0.000.

The procedure in Example 1, with the exception that the butyl acrylate was changed to 245 parts and the methyl methacrylate to 327 parts, was used throughout the completion and addition of the monomer mixture to the reaction vessel. This monomer mixture (3 5.9BA/47.9MMA/16.2AA) gives a calculated Tg of 26°C. After the monomer mixture addition, the batch was heated to 150°C and a mixture of 1.8 parts "Lupersol" 70 and 50.8 parts butyl "Cellosolve" was added and the temperature maintained. After 15 minutes, a mixture of 134.5 parts of N-methyl-N-hydroxyethyl linoleic amide and 63 parts of xylene was added gradually over approx. 10 minutes while the temperature was maintained at 150 +2°c. The temperature was then allowed to rise slowly to 155°C over 30 minutes, and 24 parts of a two-phase, clear liquid was distilled from the batch at atmospheric pressure. After the distillation, the batch was cooled to 98°C, and a mixture of 68.5 parts:28 percent aqueous ammonia and 600 parts deionized water was added to the batch with good stirring. At 69°C, the batch was removed from the reaction container and placed in a glass container where the temperature was allowed to drop to room temperature.

The product obtained was a clear aqueous solution with a solids content of 47.9% and a viscosity of 67,500 cP. The copolymer acid titer was determined to be 1.34 meq/g polymer and the viscosity average molecular weight to 58,000. A thin film of this

2+

polymer solution, which contained 0.1% Co as cobalt acetate (copolymer-8 solution) cured within two weeks to a slightly yellow, alkali-insoluble film with a Tukon hardness of approx. 2.5 and a glass temperature of approx. 40°C.

Excellent pigment overlays and paints were produced

of this polymer. A standard Cowles painting was prepared as follows:

The paint-up was thinned with additional copolymer-8 solution and water carefully added until the consistency was thinned properly for ironing. The final mix contained:

This paint had good spreadability, good gloss and good flow/levelling, compared to paints made from copolymers 3 and 7.

Example 9

Production of 3 0BA/4 0MMA/2 0MHESAFAE (saf f lov/s)/10AA polymer with Mv of approx. 4 0.000.

The procedure in example 8 was used with the exception that N-methyl-N-hydroxyethyl safflower oil amide was used instead of N-methyl-N-hydroxyethyl linoleic amide.

The product obtained was a clear aqueous solution with a solids content of 51.7% and a viscosity of 176,000 cP. A thin film of this material cured in the manner described in Example 8 had similar film behavior with the exception that the cured film had a lighter colour.

Example 10

Preparation of (3OEA/40MMA/15MHEDCAE) (dehydrated castor)/5MHETAE(wood)/lOAA nolymers with a Mv now approx. 40,000.

The procedure in example 8 was used with the exception that a mixture of 168 parts of N-methyl-N-hydroxyethyl-dehydrated castor oil amide and 56 parts of N-methyl-N-hydroxyethyl tree oil amide was used instead of 224 parts of N-methyl-N-hydroxyethyl linoleic acid. eamide .

The product obtained was a clear aqueous solution with a solids content of 48.7% and a viscosity of 257,000 cP. The copolymer acid titer was determined to be 1.37 meq/g polymer.

A thin film of 25-75 microns of this polymer which contained

2+

0.1% Co as cobalt acetate became tack-free in (4 hours) and cured in 6 days to a slightly yellow, alkali-insoluble film with a Tukon hardness of about 3.4.

Example 11

Production of 30BA/4Ostyrene/2OMHELAE (linen)/10AA polymer with Mv of approx. 40,000.

The procedure in example 3 was used with the exception that styrene was used instead of methyl methacrylate, which gave a calculated T for the acrylic prepolymer (35.9BA/47.9S/16.2AA) of 26 C.

The product obtained was a clear aqueous solution with a solids content of 49.7% and a viscosity of 304,000 cP. The copolymer acid titer was 1.44 meq/g polymer. A 25-75 micron thin film of this polymer containing 0.1% Co<2+>as cobalt acetate cured in 6 weeks at 25°C to a faint yellow, alkali insoluble film with a Tukon hardness of approx. 7.5.

Example 12

Production of 43BA/27AN/2OMHELAE (linseed oil)/10AA

with Mv of approx. 4 0.000.

The procedure in example 8 was used with exception

of the amount of butyl acrylate being increased to 350 parts and acrylonitrile used instead of methyl methacrylate in an amount of 2,021 parts. The backbone acrylic polymer (51.4BA/32.4AN/16.2AA) had a calculated Tg of 0°C.

The product obtained was a clear aqueous solution with a solids content of 49.4% and a viscosity of 490,000 cP. A thin film of 25-75 microns of this polymer cured in 6 weeks at 25°C to a slightly yellow, alkali-insoluble film with a Tukon hardness of approx. 5.0.

Example 13

Polymer of 27BA/34MMA/2OMHELAE (linen)/14HEMA/5AA

with Mv on' approx. 40,000.

The procedure in example 8 was used with the exception that the monomer mixture consisted of the following: butyl acrylate 200 parts, methyl methacrylate 277 parts, hydroxyethyl methacrylate 114.7 parts, acrylic acid 69.5 parts, mercatoethanol 3.4 parts. The amount of aqueous ammonia was lowered to 34.4 parts and the deionized water increased to 63 4 parts. The backbone (32.3BA/40.7MMA/16.8HEMA/10.2AA) had a bare T of 27°C. •

The product obtained was a clear aqueous solution with a solids content of 49.2% and a viscosity of 465,000 cP. The copolymer acid titer was 0.83 meq/g polymer. A 25-75 micron thin film of this polymer containing 0.1% Co as cobalt acetate cured in 2 weeks at 25°C to a faint yellow, alkali insoluble film with a Tukon hardness of approx. 2.5.

Example 14

Polymer of 7OBMA/ 2OMHETAE ( wood)/ TOMMA, with Mv of approx. 4 0.000.

The procedure in example 8 was used with exception

of that: 1) the monomer mixture (83.4BMA/16.6MAA), which gives a calculated Tg of 38°C, consisted of the following: butyl methacrylate 568 parts,

methacrylic acid 113 parts, mercaptoethanol 3.4 parts, 2) 129.9 parts of N-methyl-N-hydroxyethyl treoleylamide was used instead of N-methyl-N-hydroxyethyllinoleic amide, 3) the aqueous ammonia and the deionized water were changed to 57, respectively, 1 part and 630 parts and 4) another 500 parts of butyl "Cellosolve" were added to the solution of the final polymer.

The product obtained was a clear solution with a solids content of 40.2% and a viscosity of 3.370 cP. The copolymer acid titer was 1.14 meq/g polymer.

A 25-75 micron thin film of this polymer containing 0.1% Co<2+> as cobalt acetate cured in 2 weeks at 25°C to a faint yellow, alkali insoluble film with a Tukon hardness of approx. 10

and a glass temperature of approx. 60°C.

Example 15

Polymer of 4OBA/ 4OMMA/ IOMketAE ( wood)/ 10AA with Mv of approx. 40 . 00(

The procedure in example 8 was used with exception

of the fact that 1) the monomer mixture consisted of the following: butyl acrylate 297 parts, methyl methacrylate 297 parts, acrylic acid 87.2 parts, mercaptoethanol 3.4 parts, and 2) 61.2 parts N-methyl-N-hydroxyethyl treoleamide was used instead of N -methyl-N-hydroxyethyl linoleic amide, and 3) aqueous ammonia and deionized water were changed to 62.5 parts and 548 parts, respectively. The acrylic prepolymer consisting of 43.6BA/43.6MMA/12.8AA had a calculated Tg of 14°C .

The product obtained was a clear aqueous solution with a solids content of 48.8% and a viscosity of 308,000 cP. A 25-75 micron thin film of this polymer containing 0.1% Co<2+>as cobalt acetate cured in 2 weeks at room temperature to a slightly yellow, alkali insoluble film with a Tukon hardness of approx. 1.5.

A polymer of 10BA/27.5BMA/40iBMA/10MHETAE/12.5AA had similar properties.

Comparison example A

Polymer of 20BA/4 2MMA/3 0MHESTAE (stearate)/8AA with

Etc. of approx. 20,000.

This is a saturated fatty acid which is described in US patent 3,590,016.

The procedure in example 3 was repeated with 4 56 g of

a 4 9.2 percent solution of N-methyl-N-hydroxyethyl stearamide in xylene instead of N-methyl-N-hydroxyethyl linoleic amide in xylene. The product obtained was a cloudy solution which clarified by

heating to 60°C. The dry matter content was 53.4%. The viscosity at room temperature was 37.200 cP. A thin film of 2 5-7 5 microns

2+

of this polymer solution containing 0.1% Co as cobalt acetate remained soft, sticky and alkali soluble indefinitely.

Comparison example B

This example is example 16 in US patent 3,590,016. The acrylic prepolymer (89.4MMA/10.6MAA), which had a calculated T

o O ^

of above 105 C, was reacted with the hydroxyamide of safflower oil fatty acids, whereby a polymer with the composition 7 9.2MMA/14.5HESAFE/6.3MMA was obtained.

This example was repeated as described in the patent, with the exception that before the final dilution with water and KOH, the batch was divided into two parts. One part was neutralized with KOH/H20 as described in the patent and the other with an equivalent amount of ammonia/water.

According to the patent, the prepolymer is obtained as a solution (column 12, line 45), but in this attempt to repeat the example, a heterogeneous mixture was obtained. The mixture eventually becomes homogeneous by adding the amide and solvent.

Comparison example C

Final composition 35.8OS/56.65HELAE/7.54AA.

HELAE - hydroxyethyl linoleic amide esters.

Example 17 in US patent 3,590,016 was repeated as described in the patent with the exception that before the final dilution with water (column 13, line 30) the batch was divided into three parts. Part A was neutralized and diluted with KOH

(approx. 0.25 equivalents of polymeric acid) and water with stirring as described in the patent document. This gave a polymer dispersion. Part B was treated as the first except that an equimolar amount of ammonia was used instead of KOH. This also gave a polymer dispersion. Part C was diluted with one full equivalent of ammonia (of polymeric acid) and just enough water to give a clear solution with a solids content of approx. 47%.

Both dispersions were very unstable. Strong sedimentation was observed within 18 hours. The smell from all these samples was also very strong. This odor was a typical mercaptan odor and was probably washed away by the tert.-dodecyl mercaptan used in the polymerization. Oven stability (10 days/ 60°C)

Data regarding the curing of the polymers prepared according to comparative examples B and C are given in Table IV. The last product is a typical polymer according to the present invention.

Conclusions:

Example B: The samples prepared according to this example were unsatisfactory for the following reasons:

1) the films were too hard and crazy,

2) insufficient curing to develop satisfactory alkali resistance, 3) the sample that was neutralized with KOH had poor hydrolytic stability, which is indicated by the increased acid titers upon heat ageing.

Example C: The dispersed samples were unsatisfactory due to the poor sedimentation stability. In fact, the samples sedimented so quickly that it was not possible to complete their assessment. The solubilized variant in this example showed adequate curing and hydrolytic stability, but the unpleasant odor of the solution plus the very strong hardness and color of the cured film make this polymer unacceptable.

Claims (18)

1. Procedure for coating, characterized in that a polymer substance is placed on a substrate and brought to or allowed to harden in the presence of air, where the substance contains (A) an aqueous alkaline solution of an addition polymer rendered soluble in the op <p> solution by means of ammonia or a volatile amine, the polymer containing (i) 5-60 parts by weight of units of the formula (ii) 20-90 parts by weight of units of the formula (iii) 5-20 parts by weight of units of one or more unsaturated carboxylic acids, as well as (iv) the remainder, if any, necessary to make 100 parts by weight, in the form of units of one or more other ethylenically unsaturated addition polymerizable monomers, where R is H, (C, -Cc) -alkvl, halocrene, -CN, -CH-COOR, Ib- • 2 . -COOR or -CH-COOH, where R is (C1-CR)-alkyl, R is (CRn), where R is H or -CH-, and n is 1 or 2, 3 R is H or (C 1 -C 0 )-alkvl, 4 H or 18- R is an unsaturated, air-curable alkyl radical, R 5 is H, -COOH, -CONH 2 or -COOR, where R is {Q^-- Q.^)-alkyl, R is an aliphatic or cycloaliphatic radical containing from 1 to 20 carbon atoms, the amount of the units (iii) being sufficient to give the polymer a carboxy content of from 0.5 to 3 meq/g polymer and the amount of carboxy groups in the form of salt groups with the amine or the ammonia being sufficient to make the polymer water-soluble, and the units (ii) are derived from monomers whose polymers have a T of from -8 0 to 12 0 o C, where the polymer has a viscosity average molecular weight of from 10,000 to 100,000 and a cured film of the polymer has a T g of from -20 to 65°C and a Tukon hardness -oå from 0.2 to 10, as well as optionally (B) a metal siccative in an amount of up to 0.5 percent by weight, on a metal basis, of the total weight of the polymer in the substance. 2. Method in accordance with claim 1, characterized in that the units (iii) have the formula 1 5 where R and R are as stated in claim 1. 3. Method in accordance with claim 1 or 2, characterized in that the polymer contains from 10 to 40 parts by weight of the units (i). 4. Method according to one of claims 1-3, characterized in that the amount of ethylenically unsaturated acid units in the polymer is sufficient to give a carboxy content of from 0.6 to 2.5 meq/g polymer. 5. Method according to one of claims 1-4, characterized in that the polymer's viscosity average molecular weight is from 20,000 to 80,000. 6. Process in accordance with one of claims 1-5, characterized in that the polymer contains a) 5-30 parts by weight of the units (i), b) 10-50 parts by weight of units of one or more esters of acrylic and/ or methacrylic acid, which upon homopolymerisation gives a polymer which has a T of from 0 to -80°C, c) 20-70 parts by weight of units of one or more esters of acrylic and/or methacrylic acid, vinyl aromatic hydrocarbons and unsaturated nitriles, which by homopolymerization, a polymer having a T of from 20 to 120°C gives d) 5-15 parts by weight of units of at least one ethylenically unsaturated carboxylic acid, as well as optionally e) up to 20 parts by weight of units of one or more different ethylenically unsaturated monomers which imparts hydrophilicity to the polymer and increases its solubility in aqueous liquids, as the sum of a), b), c), d) and e) when this is used, is 100 parts by weight. 7. Method in accordance with claim 6, characterized in that b) comprises units of one or more of acrylic acrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate and isopropyl acrylate, c) comprises units of one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, styrene, vinyltoluene and acrylonitrile, d) includes units of one or more of acrylic acid, methacrylic acid, maleic acid and itaconic acid, as well as e) when this is used, includes units of one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. 8. Method according to one of claims 1-5, characterized in that the polymer contains a) 5-30 parts by weight of the units (i), b) 45-90 parts by weight of butyl methacrylate, c) 5-15 parts by weight of units of one or more ethylenically unsaturated carboxylic acids in an amount which means that the carboxy content in the polymer is 0.6-2.5 meq/g polymer, as well as possibly d) up to 4 parts by weight of units of at least one different ethylenically unsaturated monomer which imparts hydrophilicity to the <p> polymer and increases its solubility in aqueous liquids, where the sum of a), b), c) and d) is applied, 9. Method according to one of the preceding claims, characterized in that R 4 is the residue of one or more of the drying oils wood oil, linseed oil, dehydrated castor oil, safflower oil, conjugated safflower oil, soya oil and oiticica oil. 10. Method in accordance with claim 9, characterized in that R 4 is derived from a mixture of drying oils containing 50-90 weight percent of one or more of dehydrated castor oil, safflower oil, conjugated safflower oil and soybean oil and 10-50 weight percent trioleic acid. 11. Method in accordance with one of the preceding claims, characterized in that the substance contains, on a dry matter basis, 10-70% by weight of water-soluble polymer (A) and 30-90% by weight of a water-insoluble latex polymer. 12. Polymer which is oxidatively curable using air, characterized in that it contains a) 5-60 parts by weight of units with the formula b) 10-50 parts by weight of units of one or more of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, isobutyl acrylate and isopropyl acrylate, c) 20-70 parts by weight of units of one or more of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, acrylonitrile, isobutyl methacrylate, styrene and vinyltoluene, and d) 8-15 parts by weight of units of one or more of acrylic acid, methacrylic acid, maleic acid and itaconic acid, the sum of a), b), c) and d) being 100 parts by weight, where R <1> is H, (C 1 -C 2 )-alkyl, halogen, -CN, -CH 2 COOR, -COOR or -CH„COOH, where R is (C 1 -C 2 )-alkvl, 3 R is H or (C 1 -C 0 )-alkyl, 4 18 R is an unsaturated, air-curable radical, and R<5> is H, -COOH, -CONH2 or -COOR, where R is (C1-C8)-alkyl, the amount of units d) being sufficient to impart to the polymer a carboxy content of 0.5-3 meq/g polymer, and in the form of salt groups with ammonia or a volatile amine, to make the polymer water-soluble, the polymer having a viscosity average molecular weight of from 20,000 to 80,000 and a cured film of the polymer having a T g of from 10 to 75 C, while the rest is a drying oleic acid residue in the form of one or more of treoleic acid, linoleic acid, dehydrated castor oleic acid, safflower oleic acid, conjugated safflower oleic acid, soya oleic acid and oiticica oil acid. 13. Polymer in accordance with claim 12, characterized in that the remainder is derived from a mixture of 50-90% by weight of one or more of dehydrated castor oleic acid, safflower oleic acid, conjugated safflower oleic acid or soya oleic acid, and 10-50% by weight treoleic acid. 14. Polymer substance, characterized in that it contains an aqueous solution of the polymer according to claim 12 or 13 mixed with a polymer latex which is insoluble in the aqueous solution, the ratio between soluble polymer and latex polymer being 10-70 parts by weight soluble polymer to 30-90 parts latex polymer on a solids basis. 15. Method for coating a substrate, characterized in that the substance according to claim 14 is applied to the substrate, and that the substance is cured or allowed to cure. 16. Object, characterized in that it has been processed by the method according to claim 1. 17. Object, characterized in that it has been processed by the method in accordance with one of claims 2-11 or 15. 18. Object, characterized in that it is coated with a coating of hardened polymer according to one of claims 12-14.