JPS6223790B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides the water solubility of polymers containing unsaturated drying oil fatty acid hydroxyamides, carboxyl groups, carboxyester groups and, optionally, groups derived from the residues of other unsaturated polymerizable monomers. The present invention relates to a method of forming a coating using a composition comprising a salt. Similar polymers suitable for coatings and other applications such as coatings and putty-like compositions are known in the art. The putty-like composition is Kottke's U.S. Patent No. 3,759,915.
Coating compositions are found in Hapwood et al., US Pat. No. 3,590,016. The present invention is an improvement on this US patent. In that patent, as in the present application, the polymer in a preferred embodiment comprises an acrylic polymer having carboxyl groups that are subsequently reacted with an N-hydroxyalkylamide. In the US patent, the acid moieties of the hydroxyamides can be saturated or unsaturated, and the polymers disclosed in the examples are very brittle, have high glass transition temperatures (Tg), and the polymers are not soluble in water. Even in sex,
It may be water-insoluble. The carboxyl group-containing polymer salts disclosed in this patent include ammonia,
When certain amines or metal desiccant salts are used in the invention described in more detail below, they can be neutralized with bases, including those not available in the US patent. The problems with this polymer are that when it forms a gel and dries under high humidity conditions, it has poor gloss, slow development of anti-clumping properties, and poor dispersion. It has now been found that certain characteristics are essential for a polymer in order to use it as a water soluble, air hardening agent. The resulting coating should have a Tg of about 65°C or less, preferably 60°C or less. SUMMARY OF THE INVENTION It is an object of the present invention to provide a new and improved method for forming a water-soluble and air-oxidizable acrylic coating. The present invention provides a method for coating an object with a paint containing an alkaline aqueous solution of an addition polymer solubilized in an alkaline solution with a volatile amine or ammonium, wherein the polymer contains the following monomers in a total amount of 100: (a) (b) 10 to 50 parts by weight of a monomer selected from esters of acrylic or methacrylic acid which, when polymerized, yields a high molecular weight polymer having a Tg between about 0°C and -40°C; 20 to 70 parts by weight of monomers selected from esters of acrylic or methacrylic acid, vinyl aromatic hydrocarbons and unsaturated nitriles to yield a high molecular weight polymer with a Tg between 80°C (c) hydrophilic to the polymer; 5 to 15 parts of an ethylenically unsaturated carboxylic acid (the amount of ethylenically unsaturated carboxylic acid is: (d) 5 to 30 parts by weight of a monomer which provides monomer residues of the formula in the polymer; [In the formula, R ¹ is H, a lower alkyl group having 1 to 5 carbon atoms, halogen, -
CN, or -CH ₂ COOR, -COOR (where R is a lower alkyl group having 1 to 8 carbon atoms), R ² is (CR ⁷ ₂ )n, and R ⁷ is -H or -CH ₃
, n is 1 or 2, R ³ is H or a lower alkyl group having 1 to 8 carbon atoms, R ⁴ is an unsaturated, air-curable alkyl group, R ⁵ is H, -CONH ₂ or −COOR,
R is as described above] and is composed of a copolymer of the following, and v of the polymer is approximately
10000 to 100000, and the Tg of the cured polymer film
is about -20°C to 65°C, the hardness of the cured film is about 0.2 to 10, and if necessary, a metal compound desiccant of up to 0.5% metal based on the total amount of polymer in the composition. In addition, it is a method of forming a water-soluble and air-oxidizable acrylic coating, which is characterized by applying a solution coating onto an object, and drying and curing the coating in the presence of air. Further, in the present invention, the above polymer is preferably selected as follows. a is ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, 2-ethylhexyl acrylate
b is one or more of methyl methacrylate, styrene, ethyl methacrylate, acrylonitrile, butyl methacrylate, isobutyl methacrylate, and vinyltoluene. c is selected from one or more of acrylic acid, methacrylic acid, maleic acid and itaconic acid, optionally containing up to 20 parts of a hydrophilic monomer, hydroxyethyl (meth)acrylate or hydroxyl. Use with one or more propyl. d is about 5 parts to 30 parts. The polymer consists essentially of a), b), c) and d) and has a molecular weight of about 20,000 to 80,000, preferably about 30,000.
to 50,000 v. In the preferred polymer, n is 2,
R ³ is -H, -CH ₃ or -CH ₂ CH ₃ , and R ⁴
is one or more residues selected from tung oil acid, linseed oil acid, dehydrated castor oil acid, safflower oil acid, conjugated safflower oil acid, soybean oil acid and oiticica oil acid. Particularly preferred combinations of unsaturated drying oils include 50-90% dehydrated castor oil, safflower oil, conjugated safflower oil, soybean oil, 10-50%
(by weight) of tung oil acid. A single acrylic or methacrylic ester can be used, and there is no need to use a combination, provided the appropriate hardness and glass transition temperature are obtained. Examples of this type of polymer include those containing the following polymeric groups: e 45 to 90 parts by weight of butyl methacrylate f 5 to 15 parts of ethylenically unsaturated carboxylic acid (the amount of ethylenically unsaturated acid is about 0.6 to 2.5 meq/g of polymer) g 5 to 90 parts by weight 30 parts by weight of the group h of formula (); optionally up to 20 parts of different ethylenically unsaturated monomers which impart hydrophilicity to the polymer and increase its solubility in water. (The sum of e, f, g and h is 100.) The backbone polymer before esterification with hydroxyamide is a water-insoluble vinyl polymer containing the necessary carboxyl groups (-COOH), as described herein. The backbone polymer is well known in the art and does not form an essential part of the present invention. When R ⁶ is H, the proportion of said monomer (C) is at least 5% by weight, at most 20% by weight, preferably 15% by weight.
Up to % by weight of unsaturated carboxylic acid is present. Particularly preferred range is about 8% to 15%, optimal value is 10%
It is thought to be in the range of 12% to 12%. It is necessary to have a significant amount of free carboxyl groups in order to maintain adequate tack and flexibility for the longest time and to minimize the function of drying oils. Preferred backbone polymers have as essential components α,
It is of the vinyl addition polymer type containing a β-unsaturated carboxylic acid, preferably acrylic acid or methacrylic acid. Other useful copolymerizable acids are described in U.S. Pat. Unsaturated carboxylic acids are single monocarboxylic acids,
It may be a polycarboxylic acid, or a partial ester or half amide of an α,β-unsaturated polycarboxylic acid, or a volatile base such as ammonia, or dimethylamine, triethylamine, diethanolamine, triethanolamine, morpholin, N-methyl Salts of copolymer acids such as morpholine, pyricone, etc. and volatile monoamines that form water-soluble salts (polyamines are not good because they react with the metal of the desiccant) may also be used.
Examples of copolymerizable ethylenically unsaturated monocarboxylic acids or polycarboxylic acids are sorbic acid, acryloxyacetic acid, acryloxypropionic acid, cinnamic acid, vinylfuranic acid, α-chlorosorbic acid, methacryloxypropionic acid, methacryloxyacetic acid. , p-vinylbenzoic acid, acrylic acid, methacrylic acid, fumaric acid, aconitic acid, atropic acid, crotonic acid and itaconic acid or mixtures thereof (itaconic acid and α,β-unsaturated monocarboxylic acid,
A mixture of methacrylic acid and acrylic acid is particularly preferred. Other copolymerizable acid monomers include alkyl half esters or partial esters of unsaturated polycarboxylic acids, or partial amides thereof, such as itaconic acid, maleic acid and fumaric acid. Preferred half esters are lower alkyl (C ₁ to C ₆ ) esters such as methyl itaconate, butyl itaconate, methyl fumarate, butyl fumarate, methyl maleate and butyl maleate. Such partial esters, as well as partial amides, are considered "α,β-unsaturated monocarboxylic acids," and this term, as used herein, includes such esters and amides. The term "vinyl monomer" as used herein means a monomer containing at least one of the following groups. Vinylidene CH ₂ =C Vinyl CH ₂ =CH Vinylene -CH=CH- In this example, α,β-ethylenically unsaturated monocarboxylic acids and their esters and amides, α,β-ethylenically unsaturated aldehydes, α,β- Ethylenically unsaturated dicarboxylic acids and their esters, amides, half esters and half amides, α,β-ethylenically unsaturated nitriles, hydrocarbons such as α-olefins, conjugated diolefins, vinyl allyl compounds, vinyl alkyl ethers, vinyl halides , vinylidene halides, vinyl sulfides, vinyl acyloxy compounds (esters of saturated carboxylic acids and ethylenically unsaturated alkanols), vinyl amines and their salts, vinyl ureide monomers,
There are vinyl compounds having a group containing a ring nitrogen (HN<) and their halogen-, hydroxyalkyl- or aminoalkyl-substituted derivatives, which may be polymers or copolymers. Although this vinyl backbone polymer and its method of preparation are not a major part of the invention, it can be processed in accordance with the invention. Examples of known vinyl polymers and methods of making them can be found in Interscience, New York (1956).
See M. Schildkrecht, "Polymer Processes", pages 111-174. Mixtures of different polymers are useful. Water-insoluble polymers used according to the invention, in addition to unsaturated acid monomers and esters with alkanols having 1 to 20 carbon atoms, such as methanol, ethanol, butanol, pentadecanol, etc. Examples of suitable monomers to copolymerize to obtain are 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, vinyl pyridine,
primary amino compounds such as β-aminoethyl vinyl ether, aminopentyl vinyl ether,
Compounds containing secondary amines such as t-butylaminoethyl methacrylate, compounds containing tertiary amines such as dimethylaminoethyl methacrylate, and amine-salts such as chlorides or hydroxides and Scott U.S. Pat. No. 3,356,627. Included are copolymers and graft, bulk or segment polymers. Conventional methods are used to obtain the backbone polymer. As described below, these vinyl monomers are
It includes the acids mentioned above and their esters, as well as the known "soft" and "hard" monomers. Other essential monomers that are commonly used in significant amounts to add to acid monomers to make backbone polymers are elastomeric or soft monomers of the formula: where R is H or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ is a primary or secondary alkanol, alkoxyalkanol, or alkylthiaalkanol having up to about 14 carbon atoms. straight-chain or branched groups such as ethyl, propyl, n-butyl, 2-ethylhexyl, heptyl, hexyl, octyl, propyl, 2-methylbutyl, 1
-Methylbutyl, butoxybutyl, 2-methylpentyl, methoxymethyl, ethoxymethyl, cyclohexyl, n-hexyl, isobutyl, ethylthiaethyl, methylthiaethyl, ethylthiapropyl, n-octyl, 6-methynonyl, decyl,
dodecyl, etc., and the group R ¹¹ is an alkyl group having from 2 to about 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 has about 6 to about 14 carbons, and when R is H and R ¹¹ is alkyl, R ¹¹ is a soft monomer so that about 2 must have from 1 to about 12 carbon atoms. Other ethylenically unsaturated copolymerizable vinyl monomers whose polymers have high Tg may have an adverse effect on the desirable properties of the product (e.g., overall
They can be used with the soft monomers mentioned above, provided they do not cause an excessive increase in Tg. A "hard" acrylic compound is represented by the following formula. Here, R is as defined above, R ²² is preferably alkyl, and when R is H, it is methyl. and when R is methyl, it is alkyl of 1 to about 5 carbon atoms, or alkyl of about 15 to 20 carbon atoms. Examples of these and other hard monomers include:
Methyl acrylate, acrylamide, acrylonitrile, isobutyl methacrylate, vinyl acetate,
Tetradecyl acrylate, pentadecyl acrylate, methyl methacrylate, ethyl methacrylate,
Mention may be made of t-butyl acrylate, butyl methacrylate, styrene, pentadecyl methacrylate, vinyltoluene, methacrylamide and N-methylolacrylamide. As is well known, when the number of carbon atoms in the alcohol moiety is the same, the Tg is significantly affected by the degree and type of branching. That is, linear products exhibit low Tg. An important property of the backbone polymer is its Tg, so the monomers and their proportions are selected for their effect on the Tg. "Tg" is a common measure of polymer hardness and is found on pages 56 and 57 of "Principles of Polymer Chemistry" (Frawley, 1953), Cornell University Press. “Polymer Handbook” by Grand Lap and Inmargt
(Interscience, 1966), Chapter 3, 61-63
Please also refer to the page. While actually measuring Tg, the ``Journal of the American Physical Society''
1, 3, page 123 (1956), or the "Rohm and Haas Acrylic Glass Temperature Analyzer" (CM-24L/cb) manufactured by Rohm and Haas, Philadelphia. If the actual Tg of the prepolymer is significantly lower than the calculated Tg due to its low molecular weight, the calculated Tg
is related to the relative Tg of different polymers. The high molecular weight that can be calculated in this way (>
1000000) The Tg of the polymer and its specific Tg are as follows. Polymer Tg n-octyl acrylate -80℃ n-decyl methacrylate -60℃ 2-ethylhexyl acrylate -70℃ n-butyl acrylate -56℃ octyl methacrylate -20℃ n-tetradecyl methacrylate - 9℃ Acrylic Methyl acid 9°C n-tetradecyl acrylate 20°C t-butyl acrylate 43°C Methyl methacrylate 105°C Acrylic acid 106°C These or the monomers are mixed to form a copolymer of the preferred Tg. The backbone polymer preferably comprises one or more ethylenically unsaturated acids, more preferably vinyl monomers, acrylic acid or methacrylic acid and benzyl alcohol, phenol or saturated monohydric aliphatic alcohol, especially one Alkanols having from 18 carbons, such as cyclopentanol, cyclohexanol, methanol, ethanol, n-propanol, isopropanol, n-butanol, methoxyethanol, ethoxyethanol, methoxyethoxyethanol,
Ethoxyethoxyethanol, isobutanol,
Other unsaturated monomers including esters with secondary butanol, tertiary butanol, pentanol, hexanol, octanol, decanol, dodecanol, hexadecanol and octadecanol, taking into account the required Tg and acid monomers. However, it is produced by solution polymerization. Coverings according to the invention can be of any type, namely glass sheets, glass fiber cloth, asbestos sheets, asbestos cement products, concrete,
siliceous cladding such as stone, plaster, slate, sandstone, granite, ceramics and porcelain, fiber-reinforced plastic products such as canoes, boats, or made from glass-fiber reinforced polyester or other plastic materials Other molded articles, metals such as alumina, steel, iron, brass, wood and other structural materials, metal oxide films such as aluminum oxide and iron oxide, leather, cellulose fibers such as cotton, linen, silk. , wool, cellulose esters such as cellulose acetate, nylon, polyesters such as polyethylene glycone terephthalate, acrylonitrile polymers, vinylidene chloride polymers and other vinyl or acrylic ester polymers, films, membranes, sheets and hydroxyethyl cellulose, methyl cellulose. , cellulose acetate, cellulose ethers or esters such as cellulose acetate butyrate, polyesters such as polyethylene glycol terephthalate, nylon, vinyl chloride or vinyl chloride polymers and copolymers, methyl methacrylate polymers and copolymers, amino Includes plastic-based molded products such as plasto or phenoplast resin, organic polysiloxane resin, or rubber. The present invention is especially valuable in that it can be used directly on any coating without the need for priming costs. The solvents used in the polymerization are benzene, toluene, xylene, aliphatic, aromatic or naphthenic solvents such as mineral spirits, organic solvents such as naphtha, ethers, esters, acetone, dioxane etc. and mixtures thereof. . Preferred solvents are monoalkyl ( _C1 - _C4 ) ethers of ethylene glycol, diethylene glycol, or propylene glycol, commercially available under the tradenames "Carbitol", "Cellosolve" and "Propazole". Of course, other polymerization types can also be used. The amount of solvent in the polymer is from 0% to 80%, preferably from 10% to 65%, based on the solid polymer. Drying oils from which fatty acid amides are derived include:
Flaxseed oil, tung oil, tall oil, safflower oil, conjugated safflower oil, isan oil, soybean oil, dehydrated castor oil, oiticica oil, menhaden oil and similar oils, as well as those not derived from drying oils but synthesized Also included are acids having a carbon chain, preferably of about 20 or fewer carbon atoms, and unsaturation that can result in air curing, similar to linseed oil. Preferred oils are those that contain two or more olefinic unsaturations (conjugated or alternate) as a main component, and further include oiticica oil and dehydrated castor oil that contain linoleic acid and/or linoleic acid as a main component. . The synthesis of fatty acid hydroxyamides is carried out in a known manner, with the hydroxyamides esterifying the carboxyl groups of the backbone polymer. Examples of publications that describe this include:
Journal of the American Society of Oil and Fat Chemists, Volume 46 (published in 1969).
On pages 355-364, this describes the invention, German patent no. 1940471 and Belgian patent no. discloses the use of diethanolamine rather than the preferred monoethanolamine to synthesize fatty acid hydroxyamides. Although the American and Belgian patents generally relate to the same type of polymer, the products disclosed therein have several drawbacks that make them unsuitable for many applications. For example, all disclosed backbone polymers are brittle and hard polymers. Therefore, the softest backbone polymers of the patent examples are believed to be those consisting of styrene and/or methyl methacrylate with a glass transition temperature (Tg) of 100°C or higher. Desiccant materials include cobalt, zirconium, manganese, lead, cerium, chromium, iron, nickel,
All conventional desiccant agents such as uranium and zinc linoleates, naphthenates and resinates are suitable, and inorganic acid salts can also be used. The amount of desiccant used is 0.01% to 3% or more based on the weight of the hydroxyamide. Good results are often obtained using small amounts of desiccant combinations such as zinc naphthenate and cobalt naphthenate. For example, 0.1% or 0.5
The combination of 0.01% to 0.1% cobalt naphthenate with 0.01% to 0.1% zinc naphthenate is particularly effective.
Co ⁺⁺ as cobaltous acetate is also effective alone or in combination with compounds that supply Mn ⁺⁺ , Zn ⁺⁺ , Zr ⁺⁺ or Pb ⁺⁺ . The materials according to the invention are particularly effective as latex additives, as shown in Example 3.
Suitable latexes are aqueous addition polymer dispersions most commonly obtained by direct emulsion polymerization. The most important of these dispersions used to make water-based paints include the following polymers and copolymers: (1) Vinyl esters of aliphatic acids having 1 to 18 carbon atoms, especially vinyl acetate; (2) Acrylic and methacrylic esters of alcohols having 1 to 18 carbon atoms, especially acrylic acid. Methyl, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate, and (3) mono- and diethylenically unsaturated hydrocarbons such as ethylene, isobutylene, styrene and butadiene. ,
Aliphatic dienes such as isoprene and chloroprene. Polyvinyl acetate and copolymers of vinyl acetate and one or more of the following monomers are well known as film-forming components of water-based paints. The monomers mentioned above are one or two types of vinyl chloride, vinylidene chloride, styrene, vinyltoluene, acrylonitrile, methacrylonitrile, and the above-mentioned acrylic esters and methacrylic esters. Similarly, copolymers of one or more of the above-mentioned acrylic or methacrylic esters with one or more of the following monomers are also more or less commonly used in water-based paints. The monomers mentioned are vinyl acetate, vinyl chloride, vinylidene chloride, styrene, vinyltoluene, acrylonitrile and methacrylonitrile. Polymers of ethylene, isobutylene and styrene and one or more of these hydrocarbons with one or more esters, nitriles or amides of acrylic or methacrylic acid, or vinyl esters such as vinyl acetate and vinyl chloride; Copolymers with vinylidene chloride are also used. Diene polymers are usually used in water-based paints in the form of copolymers with one or more of the following monomers: styrene, vinyltoluene, acrylonitrile, methacrylonitrile and the above-mentioned esters of acrylic or methacrylic acid. . In order to make all three general types of copolymers mentioned above by emulsion polymerization,
1/2 acid monomer in the monomer mixture used
It is also very common for it to be present in small amounts of 5% to 5% or more. Acids used include acrylic acid, methacrylic acid, itaconic acid, aconic acid,
These include dimers of citraconic acid, crotonic acid, maleic acid, fumaric acid, and methacrylic acid. These aqueous dispersions are made using one or more anionic, cationic or nonionic emulsifiers. Mixtures of two or more types of emulsifiers can also be used, regardless of the type, except that mixing cationic and anionic types is usually undesirable because they neutralize each other. Furthermore, many cationic emulsifiers are incompatible with the polymers of this invention; the amount of emulsifier added is from about 0.1% to 5% by weight, and sometimes more, based on the weight of total monomer input. When using persulfate type initiators, the addition of emulsifiers is often required, but only in small amounts, e.g.
When less than 0.5% emulsifier is not used, it is desirable from a cost standpoint (because no expensive emulsifier is used), and the sensitivity of the dried film to humidity is reduced, thus making the coating less susceptible to humidity. For example, it forms a coating that is difficult to swell or soften, especially when exposed to high humidity atmospheres. The average particle size and diameter of these dispersed polymers may range from 0.03 microns to 3 microns or even larger. Here, the particle size refers to the weight average diameter. Here, the micron number is determined by the centrifugation method, and details of this method can be found in Colloid Science Journal 15
(1960), pp. 563-572 (J. Brodnyan). Generally, the molecular weight of these emulsion polymers is high, with an average viscosity of about 100,000 to 1,000,000, most commonly greater than 500,000. Suitable proportions include 10-70%, preferably 10-50% of the soluble polymer in the solid state, 30-90% of the latex polymer;
Preferably it is 50-90%. These have a pH of 3 to 11 and are insoluble in water. The following examples will direct those skilled in the art to carry out the invention, in which, unless otherwise indicated, parts and percentages are by weight and temperatures are expressed in °C. It can be done. In the examples, the following abbreviations are used for monomers: BA - Butyl acrylate MMA - Methyl methacrylate AA - St acrylate - Styrene AN - Acrylonitrile HEMA - Hydroxyethyl methacrylate MAA - BMA methacrylate - Butyl methacrylate EA - Ethyl acrylate iBMA - Isobutyl methacrylate The following abbreviations are: Certain fatty acid amines are used for the ester group of the formula N-methyl-N-hydroxyethylamide. MHELAE - Linseed oil acid MHESAE - Soybean oil acid MHESAFAE - Safflower oil acid MHEDCAE - Dehydrated castor oil acid MHETAE - Tung oil acid MHESTAE - Stearic acid - Non-drying acid The following abbreviations are also used in the examples. HELAE -N-hydroxyethyl linseed oil amide ester HESAFE -N-hydroxyethyl safflower oil amide ester group In the following table, prepolymers with a solids content of 85 to 90% are subjected to solution polymerization in Butyl Cellosolve®. The copolymerized unsaturated acid portion was then subjected to a post-polymerization esterification reaction with a drying oil N-methyl-N-(β-hydroxyethyl)amide. Synthesis details are shown in Table 1 and representative methods are shown in the following table.

Table: High levels of drying oil result in some increase in the molecular weight of the uncured polymer. A polymer with a v around 40,000 exhibits better curing characteristics at around 20% and requires less drying oil functionality than a polymer with a v of around 20,000, which cures well with around 40% drying oil functionality. . Cure speed is a function of the type of drying oil. Curing efficiency is also a function of the type and amount of drying oil. Some polymers containing styrene or acrylonitrile cure at slightly slower rates, while similar polymers containing hydroxyethyl methacrylate (HEMA) exhibit higher cure rates. The viscosity average molecular weights determined here are generally consistent with gel permeation chromatography (GPC) molecular weight determinations. In most cases, this gpc molecular weight is determined by a methylated prepolymer in which the copolymerized acid is reduced by methylation. A "prepolymer" is a polymer before esterification with drying oil hydroxyethylamide, and is also called a backbone polymer. The indicated molecular weight was calculated by adding the weight of the drying oil amide to the prepolymer molecular weight. In one example (F), gpc
Molecular weights were determined directly on the final methylated polymer. The good agreement between E and F indicates that almost no crosslinking occurs in the drying oil chain during the post-polymerization esterification reaction. The solution viscosity of water-soluble copolymers is significantly reduced by the addition of solvent. (a) Solubility coefficients and hydrogen bridges of solvents have no relation to the effect of solvents on reducing solution viscosity; and (b) among good solvents (acetonitrile, isopropanol, isobutanol, acetone, methyl ethyl ketone): The conclusion was reached that all have approximately equal effectiveness in reducing solution viscosity. Other useful solvents include butyl cellosolve, butyl carbitol, propazole B, propazole P and diacetone alcohol.

[Table] It is important to cool the bath quickly after the ester reaction is complete. The reason is that gelation will occur if the bath is not cooled quickly. The temperature is lowered by refluxing the water-xylene azeotrope during the ester reaction and then removing the azeotrope using a vacuum without further heating. Esterification temperature and time are also important. When a temperature of 165°C is used, the ester reaction has a significant non-gelation time compared to the ester reaction at 145°C and must be completed in a short time. At 145°C, sufficient non-gelation time is obtained even if the ester reaction is carried out over 45 minutes. Other factors related to the non-gelling time are the copolymerized acid content and the total solids content; the lower the acid content, the longer the non-gelling time, and the lower the total solids content, the longer the non-gelling time. Another factor is the nature of the drying oil acid. The order in which gelation is likely to occur is as follows. Dehydrated castor oil > tung oil > linseed oil = safflower oil soybean oil > stearic acid. Additives that reduce the gelling effect are also sometimes useful. These additives include carboxylic acids and anilines. Examples of acids are monochloroacetic acid and benzoic acid. The following examples will guide those skilled in the art in carrying out the invention, in which, unless otherwise indicated, parts and percentages are by weight and temperatures are in °C. . Next, a skeleton polymer containing carboxyl groups and N-
30BA/42MMA/20MHELAE/ by reacting methyl-N-hydroxyethyl linseed oil amide
A calculation example for the synthesis example of 8AA is shown. 35.86BA/50.19MMA/13.95AA (Tg calculation value =
A prepolymer having a composition of 8° C.) is reacted with 20.59% N-methyl-N-hydroxyethyl linseed oil amide (MHELA), based on the weight of the prepolymer. Therefore, 100 g of prepolymer are reacted with 20.59 g of N-methyl-N-hydroxyethyl linseed oil amide. 20.59/337 = 0.0611 mole amide 72 x 0.0611 = 4.40 g AA (in 0.0611 mole) 18 x 0.0611 = 1.10 g H ₂ O (in 0.0611 mole) Weight of formula MHELAE 220.59 + 4.40 - 1.10 = 23.89 g Final composition in grams % BA 35.86 30 MMA 50.19 42 AA 13.95−4.40=9.55 8 MHELAE 23.89 20 119.49 where the prepolymer composition is calculated in a similar manner. Example 1 40BA/30MMA/20MHELAE (linseed oil)/
Synthesis of 10AA (approximately 40,000 v) A monomer mixture with the following composition was prepared. Part Butyl acrylate 326.0 Methyl methacrylate 244.6 Acrylic acid 110.4 Mercaptoethanol 3.4 An initiator solution with the following composition was prepared. Part Butyl Cellosolve 35.4 Luperzole PMS 13.6 (tert-butyl, peroctoate) The following raw materials are charged to a reaction vessel equipped with a stirrer, condenser, nitrogen inlet and two addition devices. Butyl Cellosolve 88.0 Monomer Mixture 40.8 Heat the bath to 110°C and add the 6% initiator solution. After standing for 15 minutes, the remainder of the monomer mixture and initiator solution is added over a period of 4 hours while maintaining the temperature at 110±30°C. After addition, 1.8 parts of Lupanol 70 (t
- butyl peroctoate) and 5.8 parts of butyl cellosolve are added and the temperature is increased to 170°C.
The calculated Tg of the produced acrylic backbone polymer, ie, prepolymer (47.83BA/35.91MMA/16.21AA), is 7°C. At 170°C, N-methyl-N-
A mixture of 134.5 parts of hydroxyethyl linseed oil fatty acid amide and 65.0 parts of xylene is added. 76 parts of the biphasic clear solution are distilled from the bath under reduced pressure while the temperature is lowered to 153°C and maintained at 150-155°C for the next 45 minutes. Following distillation, the bath is cooled to 95° C. and 68.5 parts of a 28% aqueous ammonia solution and 600 parts of deionized water are added to the bath with good stirring. At 75°C, transfer the product from the reaction vessel to a glass vessel and reduce the temperature to room temperature. The product of this reaction is a clear aqueous solution with a solids content of 51.4% and a viscosity of 281,000 centipoise.
The viscosity average molecular weight is 42,300. Co ⁺⁺ 0.1%
Thin films (1-3 mils) of the above-mentioned polymer solutions containing (as cobalt acetate) do not lose their viscosity within 5 hours and harden to slightly yellow alkali-insoluble films in one week at room temperature. The glass transition temperature of this cured film is approximately +20°C. Example 2 40BA/30MMA/20MHELAE (linseed oil)/
Synthesis of 10AA (v, approx. 80000) The method of Example 1 is repeated except that the mercaptoethanol is reduced to 1.7 parts. The product of this reaction is a clear aqueous solution with a solids content of 50.7% and a viscosity of 342,000 centipoise. Viscosity average molecular weight is 80000
It is. A film cured from this material as described in Example 1 has a Tg of about 25°C. Example 3 20BA/42MMA/30MHELAE (linseed oil)/
Synthesis of 8AA (approximately 20,000 v) A monomer mixture with the following composition was prepared. Butyl acrylate 181.5 Methyl methacrylate 379.5 Acrylic acid 120.5 Mercaptoethanol 6.8 This monomer mixture (26.6BA/55.7MMA/
17.7AA), a prepolymer with a calculated Tg of approximately 43°C was produced. An initiator solution with the following composition was prepared. Part Butyl Cellosolve 35.4 Lupersol PMS 40.8 The following raw materials are charged to a reaction vessel equipped with a stirrer, condenser, nitrogen inlet and two dropwise addition devices. Butyl Cellosolve 88.0 Monomer Mixture 40.8 Heat the bath to 142°C and add the 6% initiator solution. The exothermic reaction raises the temperature to 151°C. After holding this temperature for 15 minutes, the monomer mixture and the remainder of the initiator solution are added over a period of 4 hours while maintaining the temperature at 150±3°C. Fifteen minutes after this addition is complete, 18 parts of Lupersol 70 and 5.8 parts of butyl cellosolve are added to the bath. Increase the temperature to 150±2 for another 15 minutes.
After keeping the temperature at 150±2℃,
224 parts of N-methyl-N-hydroxyethyl linseed oil amide and 69.0 parts of xylene are slowly added over a period of minutes. The temperature is then slowly raised to 155°C over 30 minutes, and 30.0 parts of a two-layer clear liquid is distilled from the bath at normal pressure. After distillation, the bath is cooled to 95° C. and a mixture of 50.3 parts of 28% aqueous ammonia solution and 587 parts of deionized water is added to the bath with good stirring. At about 70°C, the reactants are transferred from the reaction vessel to a glass vessel and the temperature is lowered to room temperature. The reaction product is a clear aqueous solution (labeled below as Copolymer 3 Solution) with a solids content of 53.1% and a viscosity of 11.230 centipoise. This viscosity average molecular weight is 22,500. Thin films of polymer solutions containing 0.1% Co ⁺⁺ (as cobalt acetate)
3 mil) does not lose its viscosity within 5 hours, becomes slightly yellow after 2 weeks at room temperature, and has a two-con hardness of approx.
1.5, hardens into an alkali-insoluble film with a glass transition temperature of approximately 25℃. A pigment pulverized body was made using Cowles' solvent and the following raw materials. Pigment pulverized body partial dispersant ^*1 25% TS ^*2 1.9 Copolymer 3 solution 53.6% TS 12.3 Ion-removed water 20.3 TiO ₂ R-900HG 65.5 *1 A combination of maleic anhydride and diisobutylene in a molar ratio of 1:1. Polymer *2 TS: TOTAL SOLID, same hereinafter. By adding TiO ₂ to the liquid component, a very smooth pigment pulverized body can be obtained. 3500~3500 mixture for 30 minutes
Mix with a Cowles mixer at 4000 feet/minute. The pulverized material is diluted as follows using a conventional stirrer. Part Grind A 34.5 Copolymer 3 solution at 25% TS to total solid polymer / 65.5 0.1% Co ⁺⁺ (as acetate) The resulting paint has a viscosity of 2700 cps, a PH of 8.5
and the test yoke has a slight yellow tinge.
Has a 60° gloss of 80. This desensitization time is much better than commercially available solvent alkyd paints with similar gloss properties. Removal of the dispersant results in a completely satisfactory pigment mill. The following mixing ratios were used: Pigment Grind Part B Copolymer 3 Solution 53.6% TS 12.5 Deionized Water 20.7 TiO ₂ R-900HG 66.8 To disperse the pigment as described above, use a Cowles disperser at a circumferential speed of 3500 to 4000 feet/minute. use. The resulting pulverized material is completely smooth,
It is easier to produce than ordinary semi-gloss pulverized bodies. The pulverized body is diluted with the following water-soluble polymer. Pigment Mill A 34.5 Copolymer containing 0.1% cobalt acetate based on total solids polymer 65.5 Coalescing 3 Solution 25% TS This paint is approximately 30% solids and 25% PVC
(% by volume), has a viscosity of 1750 and a pH of 8.5, has good flowability and leveling, good brushability, excellent gloss and a slightly yellow color. Conventional propylene glycol/polyelectrolyte dispersants can also be used. In this case, the soluble polymer is replaced with latex in the dilution stage. Typical compositions are as follows. Pigment grinding body C partial dispersant ^* 25%TS 3.1 Nopco NDW dispersant 5.6 Propylene glycol 19.5 TiO ₂ R-900HG 76.8 * Maleic anhydride-diisobutylene copolymer As in other cases, Cowles dispersion to make the grinding body machine is used. The dilution step is carried out using a conventional stirrer with the following composition: Pigment grind C 27.3 Deionized water 5.6 Copolymer 3 solution 30% TS 67.1 The metal desiccant in the Copolymer 3 solution is changed as shown below.

[Table] The resulting paint has very good gloss in the 20° gloss measurement, particularly in terms of gloss depth or image gloss. These are summarized along with 60° gloss and paint viscosity and PH.

[Table] In normal latex adjustment, 60° gloss is 65,
The typical value of 20° is 20 to 25. Other compositions with good gloss properties include regular acrylic latexes (EA/MMA/
MAA 57/42/1), the following composition is used: Part Pigment Grind C 33.2 Ion-removed water 6.8 Latex 46.5% TS 39.5 Copolymer 3 solution 30%TS W/0.1%Co ⁺⁺
20.5 This paint exhibits a 20°/60° gloss of 31/80, although not as high as the example above containing only the water-soluble polymer, which is better than the gloss of the following paint without Copolymer C: It's also pretty good. Pigment Grind C 36.1 Latex Total Solids 46.5% 57.3 Propylene Glycol 5.0 Texanol 1.6 It has a 60° gloss of 65 (this 20° gloss is not measured, but typical values observed for the same composition average 28) . Example 4 (20BA/42MMA/30MHESAE) (soybean oil)/
Polymer having a v of about 20,000 of 8AA The method of Example 3 was repeated using the same amount of N-methyl-N-hydroxyethyl soybean oil amide in place of N-methyl-N-hydroxyethyl linseed oil amide. return. The product of this method is a clear aqueous solution with a solids content of 53.4% and a viscosity of 19000 centipoise. The acid equivalent of the copolymer is 1.13 of the polymer
milliequivalent/g. Cured at 60℃ for two weeks
A thin film (1-3 mil) of the above polymer solution containing 0.1% Co ⁺⁺ (as cobalt acetate) results in a slightly yellow alkali-insoluble film with a Tucon hardness of about 2.0. Example 5 (40BA/20MMA/20MHELAE) (linseed oil)/20AA polymer with a v of about 20000 326 parts of butyl acrylate, 163 parts of methyl methacrylate, 191.5 parts of acrylic acid, 3.41 parts of mercaptoethanol , N-methyl-N-hydroxyethyl linseed oil amide to 134.5 parts, ammonia aqueous solution to 138 parts, and deionized water to 542 parts. The acrylic framework (47.9BA/24MMA/28.1AA) has a calculated Tg of 8°C. The product of this process is a clear aqueous solution with a solids content of 50.7%, a viscosity of 14,500 centipoise, and a viscosity average molecular weight of 21,000. Example 6 20BA/42MMA/30MHELAE (linseed oil)/
Polymer with a v of about 20000 of 8AA and neutralized with triethylamine Triethylamine instead of 28% ammonia solution
Repeat the method of Example 3 using 111.1 parts and reducing the deionized water to 526.6 parts. The product of this method is a slightly hazy aqueous solution with a solids content of 53.6% and a viscosity of 11650 centipoise. A thin film (1-3 mil) of this polymer is cured similarly to the polymer described in Example 3. Example 7 (5BA/42MMA/45MHELAE (linseed oil)/
Polymer with a v of about 20,000 of 8AA 53.8 parts of butyl acrylate, 456.0 parts of methyl methacrylate, 172.4 parts of acrylic acid, 403 parts of N-methyl-N-hydroxyethyl linseed oil amide
The method of Example 3 is repeated except that the amount of the 28% ammonia aqueous solution is changed to 66.7 parts, and the deionized water is changed to 571 parts. Acrylic skeleton (7.9BA/66.8MMA/
25.3AA) has a calculated Tg of 84°C. The product of this process is a hazy aqueous solution with a solids content of 56.7% and a viscosity of 100.000 centipoise, hereinafter referred to as Copolymer 7 solution. A thin film (1-3 mil) of this polymer solution containing 0.1% Co ⁺⁺
After two weeks at ℃, it is cured to form a yellow alkali-insoluble film with a Tucon hardness of about 3.0 and a Tg of about 50℃. The Copolymer 7 solution is a mixture of pigment, polymer, and water only in the form of a preferred pulverized body, mixed with these water-soluble vehicles eliminating the need for flocculants, humidification aids, and dispersants as follows: be done. Pigment Grind Part D Copolymer 7 Solution 25% TS 49.2 Deionized Water 1.6 TiO ₂ , R-900HG 49.2 A standard method using a Cowles disperser is then performed. The ground material is diluted by adding various amounts of a water-soluble polymer mixed with a metal desiccant. The complete formula for this series is as follows:

[Table] These paints have PH, viscosity, gloss, (82~
94 range) and other properties specific to the aforementioned paint rows. Additionally, alkaline scratch resistance was measured by passing 1% Tide (detergent) solution 500 times using a Gardner scratcher equipped with a 1 pound boat. The specimens were coated on black vinyl chart at a thickness of 7 mils. Paint number 7-1 (does not contain desiccant) is
After three days of air drying, it will completely peel off from the panel.
After one week, 30% of the membrane peels off. After air drying for 1 day, the gloss of No. 7-4 paint (0.5% Co ⁺⁺ ) decreased from 92 to 81 after 500 strokes, and after 7 days air drying the gloss decreased from 89 to 82 or -8% becomes. A drying time of 2 days is sufficient for 90% gloss retention with 1.25Co ⁺⁺ . Example 8 (305BA/42MMA/20MHELAE) Polymer having a v of approximately 40,000 of (305BA/42MMA/20MHELAE) linseed oil/10AA. In addition, the method of Example 1 was used.
This monomer mixture (35.9BA/47.9MMA/
16.2AA) has a calculated Tg of 26°C. After adding the monomer mixture, heat the bath to 150°C and maintain the temperature by adding 1.8 parts Lupasol 70 and 5.8 parts Butyl Cellosolve. After 15 minutes, 134.5 parts of N-methyl-N
- Gradually add hydroxyethyl linseed oil amide and 63 parts of xylene. For the next 30 minutes,
The temperature is slowly increased to 155°C and 24 parts of a two-layer clear liquid are distilled from the bath at atmospheric pressure. Following distillation, the bath is cooled to 98° C. and 68.5 parts of a 28% aqueous ammonia solution and 600 parts of deionized water are added to the bath with good stirring. At 690°C, the reactants are removed from the reaction vessel, placed in a glass vessel, and the temperature is lowered to room temperature. The product from this method has a solids content of 47.9%,
It is a clear aqueous solution with a viscosity of 67.500 centipoise.
The equivalent weight of this copolymerized acid is 1.34 milliequivalent of polymer/
g, and the viscosity average molecular weight is 58,000. 0.1%
A thin film of this polymer solution (copolymer 8 solution) containing Co ⁺⁺ (as cobaltous acetate) has a Tuccon hardness of 2.5 and a glass transition temperature of about + in two weeks.
Cures to a slightly yellow alkali-insoluble film with 40°C. Excellent pigment grinds and paints are made from this polymer. A standard Cowles grinding body is constructed as follows. Copolymer 8 solution 47.9% 25.1 Ion-removed water 26.7 TiO ₂ , R-900HG 48.2 Copolymer 8 solution was further added to dilute the pulverized body,
Carefully add water until the consistency is just right for brushing. Pigment dispersant 66.5 Copolymer 8 solution 23.5% 26.8 Deionized water 6.7 This paint has better brushability, gloss, and fluidity/leveling than the previously described paints made from copolymers 3 and 7. It is excellent. Example 9 Synthesis of a polymer with a v of about 40000 of (30BA/40MMA/20MHESAEAE) (Safflower)/10AA The method of Example 8 was followed except that oil amide was used. The product from this method has a solids content of 51.7%,
It is a clear aqueous solution with a viscosity of 176,000 centipoise. A thin film of this material cured in the manner described in Example 8 exhibits similar film properties, except that the cured film exhibits a lighter color. Example 10 Synthesis of a polymer with a v of about 40000 of 30BA/40MMA/15MHEDCAE (dehydrated castor oil)/5MHETAE (tung oil) 10AA 168 parts of N-methyl-N-hydroxyethyl dehydrated castor oil amide and 56 parts of N - 224 parts of N-methyl-N-hydroxyethyl tung oil amide mixture
The procedure of Example 8 was repeated except that methyl-N-hydroxyethyl linseed oil amide was used instead. The product from this method has a solids content of 48.7
%, a clear aqueous solution with a viscosity of 257,500 centipoise. The copolymer acid equivalent weight is 1.37 meq/g of polymer. Thin films (1-3 mils) of this polymer containing 0.1% Co ⁺⁺ (as cobaltous acetate) lose their viscosity within 5 hours and turn into slightly yellow, alkali-insoluble films with a Tucon hardness of approximately 3.4 in 6 days. harden. Example 11 Synthesis of 30BA/40 styrene/20MHELAE (linseed oil)/10AA polymer (approximately 40,000 v) Calculated Tg at 26°C by the method of Example 8 except that styrene was used instead of methyl methacrylate. Acrylic prepolymer (35.9BA/47.9S/
16.2AA). The product from this method has a solids content of 49.7%,
It is a clear aqueous solution with a viscosity of 304,000 centipoise. The copolymer acid equivalent weight is 1.44 meq/g of polymer. Thin films (1-3 mils) of this polymer containing 0.1% Co ⁺⁺ (as cobaltous acetate) are
It cures for weeks to form a slightly yellow, alkali-insoluble film with a hardness of about 7.5. Example 12 43BA/27AN/20MHELAE (linseed oil)/
10AA Polymer (approximately 40,000 v) The procedure of Example 8 was followed, increasing the amount of butyl acrylate to 350 parts and replacing methyl methacrylate with 221 parts of acrylonitrile. This acrylic backbone polymer (51.4BA/32.4AN/16.3AA) has a calculated Tg of 0°C. The product from this method has a solids content of 49.4%,
It is a clear aqueous solution with a viscosity of 490,000 centipoise. Thin films (1-3 mils) of this polymer are cured at 25 DEG C. for 6 weeks to form a slightly yellow, alkali-insoluble film with a Tucon hardness of about 5.0. Example 13 27BA/34MMA/20MHELAE (linseed oil)/
14HEMA/5AA polymer (approximately 40,000 v) 200 parts of butyl acrylate, methyl methacrylate
277 parts, hydroxyethyl methacrylate, 114.7
part, acrylic acid 69.5 parts, mercaptoethanol
Example 8 except using monomer mixture from 3.4 parts
I went in the same way. The aqueous ammonia solution is reduced to 34.4 parts and the deionized water is increased to 634 parts. The skeleton (32.3BA/40.7MMA/16.8HEMA/10.2AA) is
It has a calculated Tg value of 27°C. The product from this method has a solids content of 49.2%,
It is a clear aqueous solution with a viscosity of 465,000 centipoise.
The copolymer acid equivalent weight is 0.83 meq/g of polymer. A thin film (1-3 mil) of this polymer containing 0.1% Co ⁺⁺ (as cobaltous acetate)
It cures for two weeks at 25°C to form a slightly yellow, alkali-insoluble film with a Tucon hardness of approximately 2.5. Example 14 70BMA/20MHELAE (tung oil)/10MMA polymer (Mv approx. 40000) 1) A monomer mixture (83.4BMA/16.6MAA) with a calculated Tg of 38°C consists of: i.e. 568 parts of butyl methacrylate, 113 parts of methacrylic acid
3.4 parts of mercaptoethanol, 2) 129.9 parts of N-methyl-N-hydroxyethyl tung oil amide is used instead of N-methyl-N-hydroxyethyl linseed oil amide. 3) The ammonia aqueous solution and deionized water are changed to 57.1 parts and 630 parts, respectively. and 4) according to the method of Example 8, except that an additional 500 parts of butyl cellosolve was added to the final polymer solution. The product from this method has a solids content of 40.2%,
It is a clear solution with a viscosity of 3370 centipoise. The equivalent weight of this copolymer acid is 1.14 milliequivalents per gram of polymer. Thin films (1-3 mils) of this polymer containing 0.1% Co ⁺⁺ (cobaltous acetate) are cured for 2 weeks at 25°C to form a slightly yellow, alkali-insoluble product with a Tucon hardness of approximately 10 and a glass transition temperature of 60°C. Forms a film. Example 15 40BA/40MMA/10MHETAE (tung oil)/
Polymer of 10AA (v approx. 40000) 1) The following monomer mixture: 297 parts of butyl acrylate, 297 parts of methyl methacrylate, acrylic acid
87.2 parts of mercaptoethanol, 3.4 parts of mercaptoethanol, 2) 61.2 parts of N-methyl-N-hydroxyethyl tung oil amide are used in place of N-methyl-N-hydroxyethyl linseed oil amide. and 3) Example 8 except that the ammonia aqueous solution and deionized water were replaced with 62.5 parts and 548 parts, respectively. This 43.6BA/
43.6MMA/12.8AA acrylic prepolymer
It has a calculated Tg value of 14℃. The product from this method has a solids content of 48.8%,
It is a clear solution with a viscosity of 308,000 centipoise. 0.1
Thin films (1-3 mils) of this polymer containing % Co ⁺⁺ (as cobaltous acetate) are cured for two weeks at room temperature to form a slightly yellow alkali-insoluble film with a Tucon hardness of about 1.5. 10BA/
The 27.5BMA/40iBMA/10MHETAE/12.5AA polymers have similar properties. Comparative Example A Polymer of 20BA/42MMA/30MHESTAE (Stearate) 8AA (v approx. 20000) This is a saturated fatty acid disclosed in Patent No. 3590016. The procedure of Example 3 is repeated using 456 g of a 49.2% xylene solution of N-methyl-N-hydroxyethyl stearylamide in place of the xylene solution of N-methyl-N-hydroxyethyl linseed oil amide. The product of this reaction is a hazy solution that becomes clear when heated to 60°C. Solid content is 53.4%,
The viscosity at room temperature is 37200 centipoise. 0.1%
Thin films (1-3 mils) of this polymer containing Co ⁺⁺ (as cobaltous acetate) are soft, sticky, and indefinitely soluble in alkali. Comparative Example B This corresponds to Example 16 of US Pat. No. 3,590,016. An acrylic prepolymer (89.4MMA/10.6MMA) with a calculated Tg of approximately 105°C or higher reacts with hydroxyethylamide of safflower oil fatty acids to form a polymer with a composition of 79.2MMA/14.5HESAFE/6.3MMA. arise. This example is reproduced as described in the patent, except that the bath is separated into two parts before the final dilution with water and KOH. A portion is neutralized with KOH/H ₂ O as described in the patent and the other portion is neutralized with equivalent amounts of ammonia/water. According to this patent, the prepolymer is obtained as a solution (column 12, line 45), but in experiments repeating this example a heterogeneous mixture was obtained. The mixture becomes homogeneous until the amide and solvent are added.

[Table] Comparative example C Final composition 35.80S/56.65HELAE/7.54AA
(HELAE/Hydroxyethyl Linseed Amide Ester) Example 17 is repeated as described in the US patent, except that the bath is separated into three parts before final dilution with water (column 13, line 30). Part A is neutralized and diluted with KOH (~0.25 equivalents relative to the polymeric acid) and water with stirring as described in that patent to yield a polymer dispersion. Part B is the KOH
The procedure is the same as the first, except that an equivalent amount of ammonia is used instead of 1 to form a polymer dispersion. Part C is diluted with sufficient equivalents of ammonia (relative to the polymeric acid) and enough water to obtain a clear solution of about 47% TS. Both dispersions are very unstable. Sedimentation is observed within 18 hours. Also, all three samples have a very strong odor. This odor has a characteristic mercaptan odor and is thought to be due to t-dodecyl mercaptan used during polymerization.

【table】

Table Cure Study Data regarding the cure of the polymers made according to Comparative Examples B and C are shown in the table. The final product is a representative polymer of the invention. Conclusion Example B: The samples made according to this example were unsatisfactory for the following reasons. 1 The membrane is very hard and brittle. 2. Does not exhibit satisfactory alkali resistance because it is not sufficiently cured. 3. Samples neutralized with KOH have poor electrolyte stability as indicated by an increase in acid equivalents upon heat aging. Example C: Dispersed sample is insufficient due to poor sedimentation stability. In fact, the sample settles so quickly that its evaluation cannot be carried out completely. Although the change in solubility in this example shows adequate cure and electrolyte stability, the odor of the solution as well as the excessive hardness and color of the cured film make this polymer unacceptable.

【table】

Claims (1)

[Scope of Claims] 1. In a method for coating an object with a paint containing an alkaline solution of an addition polymer solubilized in an alkaline aqueous solution with a volatile amine or ammonium, the polymer has the following monomers in a total amount of 100: (a) 10 to 50 parts by weight of a monomer selected from esters of acrylic acid or methacrylic acid, which when polymerized yield a high molecular weight polymer having a Tg between about 0°C and -40°C; 20 to 70 parts by weight of monomers selected from esters of acrylic or methacrylic acid, vinyl aromatic hydrocarbons, and unsaturated nitrites to yield high molecular weight polymers with Tg between about 20°C and 80°C. 5 to 15 parts of an ethylenically unsaturated carboxylic acid (ethylenically unsaturated carboxylic acid (d) 5 to 30 parts by weight of a monomer which provides monomer residues of the formula in the polymer; [In the formula, R ¹ is H, a lower alkyl group having 1 to 5 carbon atoms, halogen, -
CN, or -CH ₂ COOR, -COOR (where R is a lower alkyl group having 1 to 8 carbon atoms), R ² is (CR ⁷ ₂ )n, and R ⁷ is -H or -CH ₃
, n is 1 or 2, R ³ is H or a lower alkyl group having 1 to 8 carbon atoms, R ⁴ is an unsaturated, air-curable alkyl group, R ⁵ is H, -CONH ₂ or −COOR,
R is as described above] and is composed of a copolymer of the following, and v of the polymer is approximately
10000 to 100000, and the Tg of the cured polymer film
is about -20°C to 65°C, the hardness of the cured film is about 0.2 to 10, and if necessary, a metal compound desiccant of up to 0.5% metal based on the total amount of polymer in the composition. Additionally, a method for forming a water-soluble and air-oxidizable acrylic coating, which comprises applying a solution coating onto an object, drying and curing the coating in the presence of air. 2. The method for forming an acrylic coating according to item 1, wherein (a) to (d) in the preceding item consist of the following. (a) is ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid,
(b) is one or more of methyl methacrylate, styrene, ethyl methacrylate, acrylonitrile, butyl methacrylate, isobutyl methacrylate and vinyltoluene; (c) is selected from one or more of acrylic acid, methacrylic acid, maleic acid and itaconic acid and is present in an amount of 8 parts to 15 parts; (d) is selected from about 10 parts to 30 parts; and the polymer consists exclusively of (a), (b), (c) and (d) above;
v is about 20,000 to 80,000, and 10 to 40 parts by weight of the group of formula ( ) is present. 3 In the group of the above formula (), n is 2, R ³ is -H, -
CH ₃ or CH ₃ CH ₂ −, and R ⁴ is one of the drying oil acids selected from tung oil acid, linseed oil acid, dehydrated castor oil acid, safflower and conjugated safflower oil acid, soybean oil acid and oiticica oil acid. 3. The method for forming an acrylic coating according to item 2, wherein the acrylic coating has one or more residues. 4. The drying oil acid mixture containing 50% to 90% by weight of dehydrated castor oil, safflower oil, conjugated safflower oil or soybean oil or a mixture thereof and 10% to 50% by weight of tung oil acid. 4. The method of claim 3, wherein the cured polymer film has a Tg of about 60° C. or less and a backbone polymer has a calculated Tg of about 50° C. or less. 5. The method for forming an acrylic coating according to item 1, wherein the polymer contains a group consisting exclusively of the following. (e) 45 parts to 90 parts by weight of butyl methacrylate (f) 5 parts to 15 parts of an ethylenically unsaturated carboxylic acid (the amount of ethylenically unsaturated acid being about 0.6 to 2.5 milliequivalents per gram of polymer) (g) from 5 parts by weight to 30 parts by weight of groups of formula (h) and (h) up to 20 parts of different ethylenically unsaturated monomers which impart hydrophilic properties to the polymer and increase its solubility in aqueous solution. Add as necessary (total of (e), (f), (g) and (h) is 100). 6 (b) is selected from one or more of acrylic acid, methacrylic acid, maleic acid and itaconic acid, and (c) is present in an amount of about 10 to 30 parts;
6. The method of forming an acrylic coating according to claim 5, wherein v is about 20,000 to 80,000. 7 Group of formula (), n is 2, R ³ is -H, -
CH ₂ CH ₃ , or CH ₃ and R ⁴ are one of the drying oil acids selected from tung oil acid, linseed oil acid, dehydrated castor oil acid, safflower and conjugated safflower oil acid, soybean oil acid and oiticica oil acid. 7. The method for forming an acrylic coating according to item 6, wherein the acrylic coating has one or more residues. 8 50% to 90% by weight dehydrated castor oil acid,
8. A method for forming an acrylic coating according to claim 7, characterized in that a mixture of safflower or conjugated safflower acid or a mixture thereof and the drying oil acid containing 10% to 50% by weight of tung oil acid is used.