JPH07157524A - Vinyl copolymer containing macromonomer - Google Patents

Abstract

PURPOSE: To provide a vinyl copolymer which is economical, is useful for a water-dispersible coating compsn., and is prepd. from a vinyl monomer, a monoethylenically unsatd. monomer, and a specific macromonomer in a specified ratio.

CONSTITUTION: This vinyl copolymer is obtd. from (A) about 1-99.9 wt.% at least one vinyl monomer, (B) about 0-98.9 wt.% at least one monoethylenically unsatd. monomer other than monomer A, and (C) about 0.1-99 wt.% monomer component comprising (i) a monoethylenically unsatd. macromonomer obtd. by hydrolyzing a reaction product of a styrene/maleic anhydride copolymer with hydroxyethyl acrylate or (ii) a mixture thereof with a macromonomer obtd. by reacting trimellitic anhydride with hydroxyethyl acrylate. Vinyl chloride or vinyl acetate is pref. as monomer A; and a hydroxyalkyl (meth)acrylate, as monomer B.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

The present invention relates to (1) a vinyl copolymer containing a giant monomer, and a method for producing the same,
(2) A water-dispersible vinyl copolymer coating composition, a method for producing the same, and (3) a giant monomer, a giant monomer mixture, and a method for producing the same.

[0002]

The use of organic polymers dissolved or dispersed in various organic solvents to form coatings is well known in the art. The formation of coatings using solvents or dispersion media involves the removal of large amounts of organic solvents, and in particular in recent years the removal of such solvents has become considered undesirable due to ecological and environmental considerations. Therefore, there is increasing interest in coating compositions that dissolve or disperse organic polymers in a medium that is primarily water.

[0003]

Some water-dispersible vinyl copolymers have a hydroxyl group-containing vinyl resin dissolved in acetone, to which is added some styrene / maleic anhydride oligomer, and the latter It can be made by the method of grafting on the former. Sufficient to react the excess acid anhydride groups with water and neutralize them with amines, thereby forming pendant polar charged groups away from the vinyl backbone and making the vinyl copolymer water dispersible. It creates a very hydrophilic property. Unfortunately, this method is very expensive and therefore the final product is too expensive in price for many applications. Incorporating a monomer containing a suitable polar group into the vinyl copolymer during polymerization would be one of the good and low cost ways to obtain the same.

Many attempts to find the right monomer to achieve this have been unsuccessful. Vinyl copolymers that precipitate or agglomerate and gel when water is added, or vinyl copolymers that dissolve in water to give viscous solutions and produce water-sensitive useless coatings. Often a problem. Proving the right balance has proven to be extremely difficult.

[0005]

As part of this invention, the present invention comprises reaction components of the following composition: a) one or more vinyl group-containing monomers, typically vinyl chloride and vinyl acetate, about 1 to 99.9 parts by weight. %, Preferably about 10-90% by weight, b) one or more monoethylenically unsaturated monomers different from component a) above, typically about 0 to 98.9% by weight hydroxyalkyl (meth) acrylate. %, Preferably about 0-25% by weight, and c) one or more monoethylenically unsaturated macromonomers,
Typically a monoethylenically unsaturated macromonomer consisting of the reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product, or i) trimellitic anhydride and hydroxy. Monoethylenic including macromonomers consisting of reaction products with ethyl acrylate and ii) reaction products of styrene / maleic anhydride copolymers with hydroxyethyl acrylate or hydrolytic derivatives of these reaction products It relates to vinyl copolymers which consist of about 0.1 to 99% by weight, preferably about 5 to 60% by weight, of the reaction product of a mixture of unsaturated macromonomers.

The present invention also relates as part thereof to a process for preparing various vinyl copolymers, which comprises a) 1) about 1 to 99.9% by weight, preferably about 10%.
To 90% by weight of one or more vinyl group-containing monomers,
Typically vinyl chloride and vinyl acetate, 2) about 0 to 98.9% by weight, preferably about 0 to 2
5% by weight of one or more monoethylenically unsaturated monomers different from component 1) above, typically a hydroxyalkyl (meth) acrylate, and 3) about 0.1 to 99% by weight, preferably about 5 to 6
0% by weight of one or more monoethylenically unsaturated macromonomers, typically a reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product. An ethylenically unsaturated macromonomer, or i) a macromonomer comprising a reaction product of trimellitic anhydride and hydroxyethyl acrylate, and ii) a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or Forming a reaction mixture comprising a mixture of monoethylenically unsaturated macromonomers, including macromonomers consisting of hydrolyzed derivatives of the reaction products, and b) adding the reaction mixture of a) above to the manufacture of the vinyl copolymer The reaction is carried out under sufficient polymerization conditions.

The invention further relates, in part, to a water dispersible coating composition comprising a vinyl copolymer of the invention, in which each reaction component a), b) and c).
The weight ratio of each is about 50-95%, 0-20% and 5 respectively.
It can range from -40%, and the vinyl copolymer can be dispersed in an essentially aqueous medium after neutralizing at least some of the carboxylic acid groups with a base. is there.

The present invention still further in part relates to a method of making a water dispersible coating composition comprising: a) 1) about 50 to 95% by weight, preferably about 60%.
To 90% by weight of one or more vinyl group-containing monomers,
Typically vinyl chloride and vinyl acetate, 2) about 0 to 20% by weight, preferably about 5 to 15
% By weight of one or more monoethylenically unsaturated monomers different from component 1) above, typically a hydroxyalkyl (meth) acrylate, and 3) about 5 to 40% by weight, preferably about 10 to 2
5% by weight of one or more monoethylenically unsaturated macromonomers, typically a reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product. An ethylenically unsaturated macromonomer, or i) a macromonomer comprising a reaction product of trimellitic anhydride and hydroxyethyl acrylate, and ii) a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or Forming a reaction mixture comprising a mixture of monoethylenically unsaturated macromonomers including macromonomers consisting of hydrolyzed derivatives of the reaction products, and b) reacting the reaction mixture of a) above, in which case this reaction In an essentially aqueous medium after at least some of the carboxylic acid groups have been neutralized with a base. It consists in causing to the extent necessary to produce a film forming composition that allows dispersion.

The invention comprises, in part, the reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate, or a monoethylenically unsaturated macromonomer consisting of a hydrolyzed derivative of this reaction product, or i)
A giant monomer consisting of the reaction product of trimellitic anhydride and hydroxyethyl acrylate and ii) styrene /
It also relates to a mixture of monoethylenically unsaturated macromonomers, including macromonomers consisting of the reaction product of a maleic anhydride copolymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product.

The invention also relates, as part thereof, to a process for preparing a mixture of macromonomers, which comprises: a) reacting trimellitic anhydride dissolved in a solvent with a molar excess of hydroxyethyl acrylate; b) styrene / maleic anhydride dissolved in a solvent,
Reacting with a molar excess of hydroxyethyl acrylate from step a) above, c) optionally incorporating into the reaction water capable of reacting with acid anhydride groups, and d) i) with trimellitic anhydride. Giant monomers consisting of reaction products with hydroxyethyl acrylate and ii)
It consists in obtaining a macromonomer mixture containing a macromonomer consisting of the reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product.

[0011]

DETAILED DESCRIPTION The present invention provides economical vinyl copolymer resins suitable for use in water dispersible coating compositions.
The vinyl copolymer resin provided by the present invention comprises i) about 1-99.9% by weight, preferably about 10-90% by weight of 1%.
One or more vinyl group-containing monomers, typically vinyl chloride and vinyl acetate, and ii) about 0-98.9% by weight, preferably about 0-25% by weight, of one or more of the above components i). Different monoethylenically unsaturated monomers, typically hydroxyalkyl (meth) acrylates, and iii) about
0.1-99% by weight, preferably about 5-60% by weight, of one or more monoethylenically unsaturated macromonomers, typically a styrene / maleic anhydride copolymer, formed by reaction with hydroxyethyl acrylate. Monoethylenically unsaturated giant monomer consisting of a product or a hydrolyzed derivative of this reaction product, or 1) a giant monomer consisting of a reaction product of trimellitic anhydride and hydroxyethyl acrylate, and 2) styrene / maleic anhydride copolymer It is made by copolymerization with a monomer mixture containing a mixture of monoethylenically unsaturated macromonomers containing macromonomers consisting of the reaction product of a polymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product.

These vinyl copolymer resins are i)-CH ₂ --CH
A first monomeric moiety of vinyl chloride of the formula Cl-, ii)-
_{CH 2 -CH (O-CO-} CH 3) - wherein the second monomeric moiety of vinyl acetate of, iii) a third hydroxypropyl acrylate
And iv) a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or a monoethylenically unsaturated macromonomer comprising a hydrolysis derivative of this reaction product, or 1) tri-anhydride It contains a macromonomer composed of a reaction product of meritic acid and hydroxyethyl acrylate, and 2) a macromonomer composed of a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or a hydrolysis derivative of this reaction product. It is preferably composed of each monomeric moiety consisting of a fourth monomeric moiety of the mixture of monoethylenically unsaturated macromonomers. The weight ratios of these preferred monomeric moieties are in the range 1 to 99.9% for i) and ii), 0 to 98.9% for iii), and 0.1 to 99 for iv), respectively.
It can range up to%. It is also preferred that the copolymer has an average intrinsic viscosity in methyl ethyl ketone ranging from 0.1 to 0.5.

The copolymerization reaction of each comonomer is emulsion polymerization,
It can be carried out by any known method including a method such as solution polymerization. The vinyl acetate moieties in the copolymer can be replaced with vinyl propionate or other vinyl esters of lower carboxylic acids if desired. The vinyl copolymer of the present invention is prepared by copolymerizing each of the above-mentioned monomers as a mixture to obtain 0.1 to 0.5 in methyl ethyl ketone.
It is obtained by making a copolymer having an average intrinsic viscosity of.

Conventional solution polymerization methods can be preferably used to form the vinyl copolymers of the present invention as described below. Similarly, other polymerization methods can be used, such as conventional emulsion polymerization. Therefore, the method used to make the vinyl copolymers of the present invention is not critical, and such methods are well understood by those skilled in the art.

In general, the vinyl copolymers of the present invention, described by way of illustrative example, are made using solution polymerization using solvents for the resulting copolymer and for the various components used. be able to. Suitable solvents are conventional ketone solvents such as acetone, methyl ethyl ketone, methyl-n-butyl ketone, methyl isopropyl ketone and the like, as well as mixtures of such ketone solvents with alcohols such as methanol, ethanol and isopropanol. including. Exemplary polymerizations of the vinyl copolymers of the present invention are described in detail in Examples 5-7 below.

The polymerization can be carried out batchwise or continuously. Typically, the solvent / monomer ratio will vary from about 0.3 / 1 to about 4/1 depending on the desired molecular weight. The selected temperature can vary from about 35 ° C to about 80 ° C depending on the reaction rate and the desired molecular weight of the copolymer. Any oil-soluble free radical catalyst can be used in amounts varying from about 0.01 to about 3.0% by weight of the monomer. Suitable catalysts include, by way of illustrative example, dibenzoyl peroxide, dilauroyl peroxide, azobisbutyronitrile and diisopropyl peroxydicarbonate. Any pressure above the vapor pressure of each component of the reaction system can be employed, with pressures of about 30 psi to 100 psi being typical. Note that psi is 0.
It is roughly converted to 07 kg / cm ² .

The relative amounts of each of the components a), b) and c) present in the vinyl copolymer of the present invention are narrow and not limiting. Components a) and b) are present in an amount sufficient to ensure that the vinyl copolymer can form a satisfactory coating on the substrate, and component c) is the vinyl copolymer. It is present in an amount sufficient to ensure that the coalesce can be dispersed in the essentially aqueous medium after neutralizing at least some of the carboxylic acid groups with a base. Preferably the vinyl copolymer comprises components a) + b): component c) in a weight ratio of about 1: 0.01 to 1: 1 and more preferably about 1: 0.15 to 1: 0.4. Included in the weight ratio. Corresponding amounts of each of the components a), b) and c) are used in the process according to the invention for producing these vinyl copolymers.

The vinyl copolymer of the present invention is film-forming. As used herein, a "film-forming substance" means a substance that can be coated on a solid substrate to form a continuous dry film. Such overcoating is usually accomplished by forming a coating from a solution of the material in a suitable solvent and drying the coating. Membrane-forming substances should be distinguished from substances that form liquid films or discontinuous solid particles under conditions where the film-forming substance forms a dry film.

The vinyl copolymers made from components a) and b) are not dispersible in water. Components a), b) and c)
The vinyl copolymer made from is dispersible in water after conversion to the salt form. The vinyl copolymers of this invention are dispersible in an essentially aqueous medium after neutralizing at least some of the carboxylic acid groups with a base.

Exemplary ethylenically unsaturated monomers which can be used as components a) and b) in the vinyl copolymers according to the invention contain hydroxyl groups or groups which can be converted into hydroxyl groups. One or more vinyl group-containing monomers and one or more ethylenically unsaturated monomers. Typical of such monomers are hydrolyzed vinyl acetate, hydroxyalkyl acrylates or methacrylates having from 2 to about 6 carbon atoms in the alkyl group (eg hydroxyethyl acrylate, hydroxyethyl methacrylate, Hydroxypropyl acrylate and hydroxypropyl methacrylate), alkanols (eg allyl alcohol), alkenyl acetals (eg vinyl formal) and the like. Typical other monomers are vinyl halides (eg vinyl chloride), vinyl esters (eg vinyl acetate), α-olefins having 2 to 4 carbon atoms (eg ethylene and propylene), among alkyl groups. Alkyl acrylates and methacrylates thereof having 1 to 18 carbon atoms (eg methyl and ethyl acrylates and methacrylates), acrylic acid and methacrylic acid, alkenyl-substituted aromatic compounds (eg styrene and α-methylstyrene), Alkenyl alkyl ethers (for example, methyl vinyl ether and octadecyl vinyl ether) and the like. Preferred monomers which can be used as components a) and b) are 2
Is a terpolymer of vinyl chloride / vinyl acetate / hydroxyalkyl acrylate or methacrylate having from 1 to about 6 carbon atoms in its hydroxyalkyl group. Most preferred in this group are vinyl chloride / vinyl acetate / hydroxypropyl acrylate copolymers.

Component a) in the vinyl copolymer of the present invention
And other monoethylenically unsaturated monomers which can be used as b) are, for example, vinyl propionate,
And Union Carbide Chemicals and Plastics Company I
vinyl esters of various carboxylic acids such as VYNATE® vinyl ester monomers available from nc., vinyl ethers such as methyl vinyl ether, isobutyl vinyl ether and cetyl vinyl ether, eg vinylidene chloride and fluorinated. Vinylidene halides such as vinylidene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, anhydrous unsaturated carboxylic acids such as maleic anhydride, such as diethyl maleate, butylbenzyl maleate. Esters of unsaturated carboxylic acids such as ates, dimethyl itaconate, β-carboxyethyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate and lauryl (meth) acrylate, eg ( Data) including unsaturated nitriles such as acrylonitrile, and for example, styrene, an aromatic vinyl compound such as α- methylstyrene and p- methylstyrene.

Component c) in the vinyl copolymer of the present invention
Suitable macromonomers that can be used as
Derived from ethylenically unsaturated monomers containing acid anhydride groups such as maleic anhydride, trimellitic anhydride, phenylmaleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, itaconic anhydride and aconitic anhydride. . The acid anhydride group-containing monomers are usually copolymerized with, for example, the other ethylenically unsaturated monomers listed above. Preferably component c) is a monoethylenically unsaturated macromonomer consisting of the reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product, or i) trimellitic anhydride. A macromonomer consisting of a reaction product of an acid and hydroxyethyl acrylate, and ii) a monomer containing a macromonomer consisting of a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product. It is a mixture of ethylenically unsaturated macromonomers.

For the water-dispersible coating compositions of the present invention containing a hydroxyalkyl (meth) acrylate as component b), component c) is i) reaction of styrene / maleic anhydride copolymer with hydroxyethyl acrylate. A product, or ii) a mixture of a reaction product 1) of trimellitic anhydride and hydroxyethyl acrylate and a hydrolyzed derivative 2) of a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate. Is preferred. For the water-dispersible coating compositions of the invention which do not contain hydroxyalkyl (meth) acrylate as component b), component c) is the reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate or A monoethylenically unsaturated macromonomer consisting of a hydrolyzed derivative of the reaction product, or i) a macromonomer consisting of the reaction product of trimellitic anhydride and hydroxyethyl acrylate, and ii) a styrene / maleic anhydride copolymer It is preferably a mixture of monoethylenically unsaturated macromonomers, including macromonomers consisting of the reaction product of a polymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product.

The reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product has a hydroxyethyl acrylate: styrene / maleic anhydride copolymer molar ratio of about 0.1.
Includes 4: 1 to 1.4: 1. The reaction product of trimellitic anhydride and hydroxyethyl acrylate comprises hydroxyethyl acrylate: trimellitic anhydride in a molar ratio of about 0.8: 1 to 1: 1. When component c) is a mixture, the reaction product of the styrene / maleic anhydride copolymer with hydroxyethyl acrylate or the reaction product of the hydrolyzed derivative of this reaction product with trimellitic anhydride and hydroxyethyl acrylate. The weight ratio to can range from about 1:10 to 99: 1, or even higher. Exemplary methods for making the macromonomers of the present invention are described in detail in Examples 1, 3 and 4 below.

An organic reaction solvent is preferably present in the reaction mixture used in the process of the present invention. Suitable solvents include ketones, alcohols,
Includes esters and chlorinated hydrocarbons. The preferred reaction solvent is a saturated aliphatic ketone having from 2 to about 4 carbon atoms in each aliphatic moiety. Exemplary ketones include acetone, methyl ethyl ketone, ethyl propyl ketone and methyl butyl ketone, ethyl butyl ketone, and the like. The solvent used is preferably acetone or another solvent having the following properties: 1) Boiling at low temperature, thus minimizing thermal decomposition of each reaction component 2) Easily removed from the composition of the invention 3) Not reactive in the reaction mixture used in the process of the invention (other than as a chain transfer agent) and 4) Water-soluble.

The preferred amount of reaction solvent is from 75 to 500 parts by weight per 100 parts by weight of each component a), b) and c). When a reaction solvent is used in the method of the present invention, the product is a solution of the composition of the present invention in an organic solvent. These solutions (varnishes) are new and form part of the invention.

As mentioned above, the vinyl copolymer produced by the reaction of each of the components a), b) and c) is such that a sufficient proportion of the carboxylic acid groups in this vinyl copolymer is more hydrophilic. It is dispersible in water only by being converted to a group (eg, by reacting those carboxylic acid groups with a base to form a salt group). The formation of such salts can be carried out by using an excess of base after the polymerization reaction.
Preferably, the amount of base added is sufficient to render the composition water dispersible. Suitable bases include, for example, triethylamine, ammonia, dimethylethanolamine and the like. This neutralized composition is the novel salt of the present invention.

The vinyl copolymers of the present invention can be dispersed together with various other polymers and can be used as such or in combination with alkyd polymers, polyurethanes, epoxy polymers or latex polymers (alloying) in coatings,
Mixtures can be formed that can be used as inks and adhesives.

The vinyl copolymers according to the invention can also be used to advantage in coatings, essentially in the form of salts in aqueous dispersions (for example dispersions in which the continuous phase is largely water).
Such dispersions are preferably 15 to 55% by weight
(More preferably 20 to 45% by weight) salt of the vinyl copolymer of the present invention, 40 to 84% by weight (more preferably 50 to 70% by weight) water and 0 to 35% by weight (more preferably 0 to 50% by weight). 10% by weight) of an organic solvent (for example, the reaction solvent described above). Typically these aqueous dispersions are formed by adding a base, then water, and then driving off the solvent. This base neutralizes the carboxylic acid groups in the vinyl copolymer to form a water dispersible salt.

The aqueous dispersion of the present invention can typically be prepared as follows. The copolymer varnish dissolved in acetone and isopropanol is placed in a container with a stirrer. Add triethylamine in an amount equal to about half the stoichiometric amount for the carboxylic acid in the polymer,
Then deionized water is added. The triethylamine and water are slowly added and mixed with good stirring to form a good dispersion. The solvent is driven out of this dispersion under vacuum at a warm jacket temperature of up to about 100 ° C., thereby producing an essentially solvent-free dispersion having a nonvolatile content of about 36 to 40% by weight. The pH of the solvent driven dispersion is typically about 6.0 to 7.0. The solvent-excited dispersion is typically washed with ammonium hydroxide to a pH of about 8.5 to 9.0.
Neutralize until. Optionally, an antifoaming agent can be added prior to solvent displacement. An exemplary method of making an aqueous dispersion is described in detail in Examples 8-10 below.

Aqueous dispersions made by the process of the present invention generally have a liquid state and homogeneity, ie, no gels, aggregates, sediments or particles, at least 2 at 50 ° C. unless the pH is too low. Keep for months. The aqueous dispersion of the present invention can be used as a component of industrial coatings, inks, binders and the like. The aqueous dispersions of the invention are shear stable. Therefore, various pigments can be directly ground and mixed into the water-retaining (water-retaining: waterborne) dispersion liquid to prepare a pigment-containing paint or ink.

In some cases, a coalescing solution
t) can be added to aid the film formation.
Typical cosolvents are, for example, monobutylethylene glycol, monopropylethylene glycol, monoethylethylene glycol, monomethylethylene glycol, monomethyldiethylene glycol, monoethyldiethylene glycol, monopropyldiethylene glycol, monobutyldiethylene glycol, etc. (and the corresponding propylene oxide-based Solvent system). When sufficient cosolvent is added, the coated aqueous dispersion will dry to a clear, glossy coating. The unmodified membrane is thermoplastic.

Optionally, a crosslinker capable of reacting with hydroxyl or carboxyl groups can be added to the aqueous dispersion to create a thermosetting binder or coating. Polyaziridines and polycarbodiimides are typical carboxyl group-reactive crosslinkers. Amino formaldehyde resins and polyfunctional isocyanates are typical hydroxyl functional crosslinkers.

The aqueous dispersions of this invention can be blended with other water-retaining vehicles to form polymer alloys (blends). These include, for example, water-reducing alkyds, alkali-soluble or dispersible acrylic and styrene-acrylic copolymers, polyurethane dispersions, conventional latices and the like. This aqueous dispersion can optionally be modified with a plasticizer to improve the flexibility of the coating.

Coatings made from the vinyl copolymers of the present invention generally exhibit a good balance of chemical resistance with flexibility and hardness, similar to coatings made from vinyl copolymers. The properties of the cured coatings of various aqueous dispersions of the vinyl copolymer salts of the present invention were in the same range as solvent-based vinyl chloride / vinyl acetate / hydroxypropyl acrylate terpolymers. A clear cured coating of an aqueous dispersion of a salt of a vinyl copolymer of the present invention onto various solid substrates, such as a metal substrate such as aluminum or steel, provides a salt-containing vinyl copolymer of the present invention and It is made from the curable mixture of the invention consisting of a crosslinker. The curable mixture comprises a relatively small amount of crosslinker than that of the salt-containing composition of the present invention. Preferably, the curable mixture comprises about 10 to 20 parts by weight curing agent per 100 parts by weight of the salt-containing composition of the present invention. Preferably the curable mixture is made by mixing a crosslinker with one of the aqueous dispersions of the invention described above, and in such cases the curable mixture comprises a major amount of water and a minor amount of water. A curable aqueous dispersion comprising a stipulated amount of the salt-containing vinyl copolymer of the present invention, a stipulated amount of a crosslinking agent, and optionally a stipulated amount of an organic solvent. The curable composition of the present invention produces a cured coating on solid substrates by known crosslinking and coating methods. If desired, the substrate can be primed by known methods prior to coating the curable composition thereon. Preferably the crosslinker is a melamine-formaldehyde resin (eg hexamethoxymethylmelamine), a urea formaldehyde resin, a polyaziridine resin or a polycarbodiimide resin. The curable mixture of the vinyl copolymer coating composition (or salt thereof) of the present invention and a cross-linking agent is new, and a method for coating a substrate using the same and the coated coating thus formed. It forms part of the invention as well as the substrate.

For the purposes of this invention, the hydrolyzed derivative of the reaction product of a styrene / maleic anhydride copolymer with hydroxyethyl acrylate is defined as at least some of the unreacted maleic anhydride groups in the reaction product. It means that the amount, preferably substantially all, and most preferably all is hydrolyzed.

[0037]

The present invention will be described with reference to the following examples. Abbreviations used The following abbreviations are used in the following examples.

[Table 1]

Description of Properties in Table 1 Gel-Free Varnish "Good" means that the solvent-based varnish contained substantially no gel particles larger than about 1 micron particle size. The copolymer solution was diluted with acetone and poured onto a glass plate before conversion to a dispersion in water. The dried coating was examined microscopically. O Storage life "Good" indicates that the aqueous dispersion was stable at 50 ° C for at least 2 months. The dispersions rated good have an objective shelf life of at least 1 year at 25 ° C. By "stable" is meant that the dispersions remain liquid and are essentially free of sediments and agglomerates. ○ Initial stability of dispersion "Good" means that the amine-modified reactor varnish was easily dispersed in water under mild agitation to form a uniform dispersion with an average particle size of about 0.3 microns or less. Means The resulting dispersion was substantially free of precipitates, agglomerates or particles and remained stable during the drive of the solvent. ○ Solid content / viscosity "Good" is about 3 for the final aqueous dispersion that has driven off the solvent.
It has a solid content of 35% by weight or more at a viscosity of 00 cPs or less. ○ Final practical performance "Good" means that the final aqueous dispersion that has driven out the solvent is
This means that a transparent, grain-free coating is formed when modified with a suitable flocculating solvent such as EGME and dropped onto glass. The dispersions were stable under high shear mixing conditions and could be formulated into inks, topcoats and the like.

[0039]

Example 1 Preparation of SMA / HEA Giant Monomer A 2 liter flask equipped with a heating mantle, condenser, stirrer and air inlet tube was charged with 550 g of MIBK and 1.6 g of methoxyphenol. To this mixture was added 450 g of SMA and the resulting reaction mixture was added to 80-10.
The SMA was dissolved by heating to 0 ° C. The mixture is then cooled to 75 ° C. and 33 g HEA and 33 g MI.
The mixture with BK was added dropwise. The mixture is heated to reflux for 8 hours, then cooled to 75-80 ° C and cooled to 1
50 g of water was added dropwise over 20 minutes. The temperature was raised to the reflux temperature (about 88 ° C.) and held for 2-3 hours. The resulting solution can be used as is for feeding to the polymerizations described below, or it can replace the solvent with EGME if desired. Solvent exchanges were carried out using the products described above, and by equipping the flask with a vacuum distillation unit and providing a dropping funnel to allow MIBK to be distilled off while simultaneously adding EGME.

Example 2 Preparation of TMA / HEA Giant Monomer A 1 liter round bottom flask was equipped with a heating mantle, stirrer, condenser, air blow tube and thermocouple. The flask was charged with 384 g TMA, 232 g HEA, 100 g acetone, 0.15 g methoxyphenol and 0.01 g phenothiazine. The mixture is heated to 60 ° C., a slow introduction of air is started and 2.0 g
TEA was added. After reacting for 4 hours, the mixture was cooled, 200 g of EGME was added, and the mixture was placed in a rotary evaporator where acetone and triethylamine were driven off under vacuum at 50 ° C.

Example 3 TMA / H in MIBK solvent
Preparation of a mixture of EA and SMA / HEA macromonomers 500 g MIBK, 0.6 in a 3 liter round bottom flask equipped with heating mantle, stirrer, condenser and air inlet tube.
g methoxyphenol and 82 g TMA were added.
The mixture is briefly heated to 80-100 ° C. to dissolve the TMA, then cooled to about 50 ° C. and 100 g MI.
124 g of HEA mixed with BK was added. The reaction mixture is then mixed with 1 while continuing the slow introduction of air.
Heated to 11-112 ° C. The reaction mixture was kept at this temperature for 7 hours. Then the mixture is cooled to 40 ° C.,
Add 500 g of MIBK, then 636 with stirring
g of SMA was added. The temperature is then raised to 80 ° C. until all the SMA has dissolved, then 111-11
The temperature was raised to 2 ° C. and kept for 3 hours. At the end of this period,
The mixture was cooled to 80-84 ° C, 200 g water was added and the mixture was heated for an additional 1.5 hours. The final mixture was cooled to room temperature, diluted with about 700 g of acetone and used as the feed for the polymerizations described below.

Example 4 TMA / HEA in acetone
And the production of a mixture of SMA / HEA macromonomers A stainless steel 2 liter high pressure reactor equipped with an external heating device, an internal cooling coil, a magnetic stirrer and several sampling ports was used for this synthesis. 220 g acetone, 0.
44 g methoxyphenol, 55 g TMA and 81.
4 g HEA was charged to the open reactor and then the device was assembled. The mixture was heated to 120 ° C. for 8 hours then cooled to room temperature. Then 420 g of SMA dissolved in 440 g of acetone was added. The reaction mixture was heated again to 120 ° C. for 4 hours, then cooled and 132 g of water was added. This reactor for another 12 hours
Reheated to 0 ° C., after which the final reaction mixture was removed from the reactor cooled to room temperature.

Polymerizations were carried out in a jacketed 3 liter continuous loop reactor filled with Examples 5-7 and Controls AE . There were two or three feed streams to this reactor. The first feed stream, Monomer Feed Stream 1, contained vinyl chloride, vinyl acetate, acetone and optionally some additional reagents. The second feed stream, Feed Stream 2, contained the IPP initiator in acetone. The third feed stream, Feed Stream 3, contained a second monomer solution in acetone, if present.

The reactor was operated under continuous feed until the appropriate resin solids were reached by densitometer readings and spot samples. The IPP input was adjusted to maintain the desired solid content. A representative resin varnish was collected only when the solids were within the desired range to make the original aqueous product. The collected varnish was batch driven out using a vacuum pump to remove unreacted vinyl chloride and some acetone and vinyl acetate.

Example 5 Monomer Feed 3: Made as in Example 3. 95 g / 10
00 g monomer feed Feed 2: 5 wt% IPP in acetone, about 50 g / h
r to about 2000 g / hr monomer feed Resin solids: 15 to 17 wt% Temperature: 60 ° C

Example 6 Monomer Feed 3: Made as in Example 4. 96 g / 10
00 g monomer feed Feed 2: 2.5 wt% IPP in acetone, about 45 g /
hr to about 1300 g / hr monomer feed Resin solids: 16 wt% Temperature: 59 ° C

Example 7 Monomer Feed 3: Made as in Example 1. 140 g / 1
000 g monomer feed Feed 2: 10 wt% IPP in acetone, about 55 g /
hr to about 1300 g / hr monomer feed Resin solids: 16-17 wt% Temperature: 59 ° C

Control Example A *): Made as in Example 2 Monomer Feed 3: None Feed 2: 10 wt% IPP in acetone, about 25 g /
hr to about 1900 g / hr monomer feed Resin solids content: 10 wt% Temperature: 60 ° C

Control Example B Monomer Feed 3: None Feed 2: 10 wt% IPP in acetone, about 45 g /
hr to about 2000 g / hr monomer feed Resin solids: 11-13 wt% Temperature: 60 ° C

Control Example C Monomer Feed 3: None Feed 2: 20 wt% IPP in acetone, about 20 g /
hr to about 1400 g / hr monomer feed Resin solids: 11-12 wt% Temperature: 60 ° C

Control Example D Monomer Feed 3: None Feed 2: 10 wt% IPP in acetone, about 80 g /
hr to about 2100 g / hr monomer feed Resin solids: 14-15 wt% Temperature: 60 ° C

Control Example E Monomer Feed 3: 17.6 wt% acrylic acid in acetone, fed at 250 g / 1500 g monomer feed,
Alternating no feed for the next 1500 g of monomer feed Feed 2: 10 wt% IPP in acetone, about 150 g
/ Hr to about 2600 g / hr monomer feed Resin solids: 15-17 wt% Temperature: 59 ° C

Example 8 Preparation of Water-Retaining Vinyl Dispersion This example shows that a mixture of SMA / HEA and TMA / HEA macromonomers is excellent at simultaneously achieving small particle size and good shelf life.

An essentially solvent-free aqueous dispersion by stirring a polymer solution (varnish) in acetone as described in Example 5 in an amine to neutralize some of the acid groups in the polymer. Changed to. Then water was added with stirring to form an aqueous dispersion. The residual solvent was then driven off. Finally, additional amine was added to adjust the pH.

In this example, the polymer had the following analytical composition expressed in% by weight: VCl 66 VAc 6.6 HPA 10 SMA.HEA.H ₂ O adduct 14.7 TMA.HEA adduct 2. 7

A mixture of SMA / HEA and TMA / HEA macromonomers was prepared in MIBK as in Example 3 in a single vessel reaction. The acid value of the polymer solids was 70 (about 60 was derived from SMA and about 10 was T
Led by MA). The intrinsic viscosity of this polymer was 0.25. The polymer solution had a nonvolatile content of 28% by weight.

595.9 g of the above varnish was placed in a mixing tank equipped with a high speed disperser having a serrated mixing blade. The blade was shaped to maintain a good vortex at low and high viscosities, and was tuned to give a "viscous impact" when water was added. 9.61 g TEA was added with stirring, followed by 313.9 g distilled water. This water is about 30 to 9
Added over a 0 second time interval. P after adding water
H was 6.7. About 50% of the theoretical acid groups were neutralized.

The resulting dispersion was transferred to a 2 liter thin neck flask and placed on a Rotovap evaporator equipped with a hot water bath, condenser and vacuum pump. The dispersion was evacuated under a vacuum of 100 mm at a water bath temperature of 95-99 ° C. so as to be essentially free of solvent and residual monomers. The temperature of the expelled dispersion liquid was about 63 ° C. at a vacuum degree of 100 mm. The pH of the expelled dispersion was 5.6. The chased dispersion was cooled to room temperature and adjusted to pH 9.6 with 28% strength ammonium hydroxide. The final dispersion was a uniform, grain-free liquid with a look and viscosity similar to skim milk.
The total solid content was 40% by weight. Average grain size is 0.0
8 microns and 90% of the particles were 0.17 microns or less. This dispersion was stable at room temperature and 50 ° C. for 3 months or longer. The various properties of the water-retaining vinyl dispersion are listed in Table 1 below.

This aqueous dispersion was modified with 50 phr of EGME, a coagulating solvent. The wet coating was dropped onto a glass plate to a thickness of 1 mil. This dry coating film
There were no clear, colorless particles. The tendency of foaming during the volatilization of this dispersion was generally low. Foaming was controlled by adding an antifoaming agent, Colloids 770 available from Rhne-Poulenc, if necessary, in an amount of 0.1% by weight, based on polymer solids.

Example 9 Preparation of Water-Retaining Vinyl Dispersion This example shows that a mixture of SMA / HEA and TMA / HEA macromonomers is excellent for simultaneously achieving small particle size and good shelf life.

An essentially solvent-free aqueous dispersion was prepared by stirring a polymer solution (varnish) in acetone as described in Example 6 in an amine to neutralize some of the acid groups in the polymer. changed. Then water was added with stirring to form an aqueous dispersion. The residual solvent was then driven off. Finally, additional amine was added to adjust the pH.

In this example, the polymer had the following analytical composition, expressed in% by weight: VCl 66 VAc 6.6 HPA 10 SMA.HEA.H ₂ O adduct 14.7 TMA.HEA adduct 2. 7

A mixture of SMA / HEA and TMA / HEA macromonomers was prepared in a single vessel reaction carried out in acetone as in Example 4. The acid value of the polymer solids was 70 (about 60 derived from SMA and about 1
0 was derived from TMA). The intrinsic viscosity of this polymer was 0.21. The polymer solution had a nonvolatile content of 28% by weight.

555.6 g of the above-mentioned varnish was placed in a mixing tank provided with a high speed disperser having a saw-toothed mixing blade. The blade was shaped to maintain a good vortex at low and high viscosities, which resulted in a "viscous impact" when water was applied. Add 10.78 g TEA with stirring,
Then 32.0 g of distilled water was added. This water was added over a time interval of about 30 to 90 seconds. 0.156g
Antifoaming agent (Colloids 770) was mixed in with stirring. The pH was 8.2 after adding water. About 55% of the theoretical acid groups were neutralized.

The resulting dispersion was transferred to a 2 liter thin neck flask and placed on a Rotovap evaporator equipped with a hot water bath, condenser and vacuum pump. The dispersion was evacuated under a vacuum of 100 mm at a water bath temperature of 95-99 ° C. so as to be essentially free of solvent and residual monomers. The temperature of the expelled dispersion was 63 ° C. at a vacuum degree of 100 mm. The pH of the expelled dispersion was 6.3. The drive-off dispersion is cooled to room temperature and treated with 28% strength ammonium hydroxide 4.0%.
The pH was adjusted to 9.9 with g. The final dispersion was a uniform, grain-free liquid with a look and viscosity similar to skim milk. Total solid content is 39% by weight and viscosity is 148
It was cPs. The average particle size was 0.08 micron.
This dispersion had a storage stability similar to that of the dispersion of Example 8. The various properties of this aqueous vinyl dispersion are listed in Table 1 below.

The aqueous dispersion was modified with 50 phr of EGME, the coalescing solvent. The wet coating was dropped onto a glass plate to a thickness of 1 mil. The dried coating film was colorless and transparent and had no particles.

Example 10 Preparation of Water-Retaining Vinyl Dispersion This example shows that an aqueous vinyl dispersion with small particle size and good storage stability can be prepared by direct polymerization with HEA / SMA monomer in a monomer mixture. Indicates. However, in this varnish, HEA / S
Gel particles due to multifunctional moieties in the MA macromonomer need to be filtered or centrifuged before the varnish can be converted to an aqueous dispersion.

An essentially solvent-free aqueous dispersion was prepared by stirring a polymer solution (varnish) in acetone as described in Example 7 in an amine to neutralize some acid groups in the polymer. changed. Then water was added with stirring to form an aqueous dispersion. The residual solvent was then driven off. Finally, additional amine was added to adjust the pH.

In this example, the polymer had the following analytical composition expressed in% by weight: VCl 65 VAc 5 HPA 10 SMA.HEA (H ₂ O) 20

The macromonomer was prepared as in Example 1. The acid value of the polymer solid component was 87, which was all derived from SMA. The intrinsic viscosity of this polymer was 0.15. The polymer solution was hazy with 33 wt% non-volatiles. The coating that was cast onto the glass showed very fine insoluble particles. The varnish was diluted with acetone to a solid content of 10% and filtered. The obtained transparent varnish was concentrated to a solid content concentration of 23% and dispersed in water as follows.

6.9 g of the above varnish was placed in a mixing tank equipped with a high speed disperser having a serrated mixing blade. The blade was shaped to maintain good vortex flow at low and high viscosities, thereby giving a "viscous impact" when water was added. 4.21g TE
A was added with stirring, followed by 76.5 g of distilled water. This water was added over a time interval of about 30 to 90 seconds. The pH was 10.5 after adding water. 100% of the theoretical acid groups were neutralized.

The resulting dispersion was transferred to a 1 liter narrow neck flask and placed on a Rotovap evaporator equipped with a hot water bath, condenser and vacuum pump. Volatiles of this dispersion were expelled at a water bath temperature of 60 ° C. with a vacuum of 20 mm. The pH of the expelled dispersion was 8.9. The final dispersion was a uniform, grain-free liquid with a look and viscosity similar to skim milk. The total solid content was 28% by weight.

This aqueous dispersion was modified with 50 phr of EGME, a coagulating solvent. The wet coating was dropped onto a glass plate to a thickness of 1 mil. The dried coating film was colorless and transparent and had no particles.

The dispersion was stable at 50 ° C. for about 90 days and at room temperature for over 400 days. Table 1 shows various properties of this water-retaining vinyl dispersion.

Control Example F Preparation of Water-Retaining Vinyl Dispersion This example shows that vinyl copolymers containing trimellitic anhydride ester produce small particle size dispersions with short shelf life.

An essentially solvent-free aqueous dispersion by stirring a polymer solution (varnish) in acetone as described in Control A in an amine to neutralize the acid groups in the polymer. I changed to liquid. Then water was agitated to form an aqueous dispersion. The residual solvent was then driven off. Finally, additional amine was added to adjust the pH.

In this example, the polymer had the following analytical composition expressed in% by weight: VCl 77 VAc 3 HPA 10 HPA.TMA adduct 10

The HPA / TMA macromonomer was prepared in DMF as in Example 2. The acid value of the polymer solids was 37, which was all derived from TMA.
The intrinsic viscosity of this polymer was 0.28. The polymer solution in acetone was separated from the residual monomer by precipitation in cold water / isopropanol, then washed with cold water and dried in a vacuum oven overnight. The dry resin was redissolved in acetone to a non-volatile content of 23% by weight.

116.9 g of the above-mentioned varnish was placed in a mixing tank equipped with a high speed disperser with a serrated mixing blade. The blade was shaped to maintain good vortex flow at low and high viscosities, thereby giving a "viscous impact" when water was added. 2.15g TEA
Was added with stirring, followed by 76.5 g of distilled water. This water was added over a time interval of about 30 to 90 seconds. The pH was 10.0 after adding water. 100% of the theoretical acid groups were neutralized.

The resulting dispersion was transferred to a 1 liter narrow neck flask and placed on a Rotovap evaporator equipped with a hot water bath, condenser and vacuum pump. The dispersion was expelled with a 20 mm vacuum at a water bath temperature of 60 ° C. The pH of the expelled dispersion was 8.1. The drive-off dispersion was a low viscosity, grain-free liquid with a hazy, translucent appearance with an approximate particle size of about 0.1 micron. The total solids content was about 30-35% by weight.

This water-retaining dispersion was modified with 50 phr of EGME, the coagulating solvent. The wet coating was dropped onto a glass plate to a thickness of 1 mil. The dried coating film was colorless and transparent and had no particles.

The dispersion was stable at 50 ° C. for about 5 days and at room temperature for about 40 days. Table 1 shows various properties of this water-retaining vinyl dispersion.

COMPARATIVE EXAMPLE G Preparation of Water-Retaining Vinyl Dispersion This example illustrates the conversion of a vinyl copolymer of conventional carboxylic acid functional vinyl monomers VCl, VAc and HPA from an acetone solution to water / amine. It results in a water-retentive dispersion that is unstable and of poor quality.

In this example, the polymer had the following analytical composition, expressed in% by weight: VCl 81 VAc 3 HPA 13 maleic acid 3

The calculated acid value of the polymer solid component was 29. The intrinsic viscosity of this polymer was 0.27. A polymer solution in acetone was dispersed in water as follows:

370.2 g of the varnish described in Control B containing 79.5 g of polymer solids was placed in a mixing vessel equipped with a high speed mixing blade. 7.92 g TE with stirring
A was added, followed by 230.0 g of distilled water. This water was added over a time interval of about 30 to 90 seconds.
No dispersion was formed and the polymer solidified. Its pH was 9.8. 100% of the theoretical acid groups were neutralized.
Table 1 shows various properties of this water-retaining vinyl dispersion.

COMPARATIVE EXAMPLE H Preparation of Water-Retaining Vinyl Dispersion This example was prepared by dispersing a vinyl copolymer of conventional carboxylic acid functional vinyl monomers VCl, VAc and HPA from an acetone solution in water / amine. It results in an unstable and poor quality water-retentive dispersion.

The polymer solution (varnish) in acetone described in Control Example C was converted into an aqueous dispersion by stirring in the amine for neutralization of the acid groups in the polymer.
Then water was agitated to form an aqueous dispersion. The residual solvent was then driven off.

In this example, the polymer had the following analytical composition, expressed in% by weight: VCl 74 VAc 3 HPA 11 CEA 12

The acid value of this polymer solid component was 47.
The intrinsic viscosity of this polymer was 0.26. The polymer solution in acetone was purified by precipitating the residual monomer in cold water / isopropanol, then cold water, and drying in a vacuum oven overnight.
The dry resin was redissolved in acetone to a non-volatile content of 23% by weight. The obtained polymer solution was dispersed in water as follows.

155.8 g of the above-mentioned varnish was placed in a mixing tank provided with a high speed disperser with a serrated mixing blade. The blade was shaped to maintain good vortex flow at low and high viscosities, thereby giving a "viscous impact" when water was added. 3.0 with stirring
3 g TEA was added, followed by 102.0 g distilled water. This water was added over a time interval of about 30 to 90 seconds. The pH was 9.9 after adding water. 100% of the theoretical acid groups were neutralized. The resulting fine particle size dispersion was transferred to a 1 liter fine neck flask and placed on a Rotovap evaporator equipped with a hot water bath, condenser and vacuum pump. Volatiles of this dispersion were expelled at a water bath temperature of 60 ° C. with a vacuum of 20 mm.

The expelled dispersion became unstable and aggregated after less than half of the acetone had been expelled. Table 1 shows various properties of this water-retaining vinyl dispersion.

The partially volatile stripped dispersion had a pH of 9.3.

Control Example I Preparation of Water-Retaining Vinyl Dispersion This example is a dispersion of a vinyl copolymer of conventional carboxylic acid functional vinyl monomers VCl, VAc and HPA from an acetone solution in water / amine. It results in an unstable and poor quality water-retentive dispersion.

In this example, the polymer had the following analytical composition, expressed in% by weight: VCl 80 VAc 3 HPA 10 Itaconic acid 7

The calculated acid value of this polymer solid component was 61. The intrinsic viscosity of this polymer was 0.23. A polymer solution in acetone was dispersed in water as follows:

90.9 g of the varnish described in Control D containing 20.9 g of polymer solids was placed in a mixing vessel equipped with a high speed mixing blade. 2.53 g TEA with stirring
Was added, followed by 59.5 g of distilled water. This water was added over a time interval of about 30 to 90 seconds. 100% of the theoretical acid groups were neutralized. A homogeneous, hazy, translucent dispersion was formed when water was added, but the dispersion solidified after 1 hour.

The pH of the dispersion in which the volatile components had not been expelled was 9.2. This dispersion was too unstable to drive off the volatiles. Table 1 shows various properties of this water-retaining vinyl dispersion.

COMPARATIVE EXAMPLE J Preparation of Water-Retaining Vinyl Dispersion This example is a dispersion of a vinyl copolymer of conventional carboxylic acid functional vinyl monomers VCl, VAc and HPA from an acetone solution in water / amine. It results in an unstable and poor quality water-retentive dispersion.

In this example, the polymer had the following analytical composition, expressed in% by weight: VCl 72.8 VAc 4.5 HPA 13.6 acrylic acid 9.1

The acrylic acid monomer was intermittently and centrally fed into the reactor so as to create a block-shaped structure in which acrylic acid groups were concentrated. The calculated acid value for the solid content of this polymer was 61. The intrinsic viscosity of this polymer was 0.2. The polymer solution in acetone was dispersed in water as follows.

129.9 g of the varnish described in Control Example E containing 29.9 g of polymer solids was placed in a mixing vessel equipped with a high speed mixing blade. 3.82 g TE with stirring
A was added, followed by 60.0 g of distilled water. This water was added over a time interval of about 30 to 90 seconds. 100% of the theoretical acid groups were neutralized. A coarse and unstable dispersion was formed when water was added. The pH of the non-displaced dispersion of the volatiles was 9.9. Table 1 shows various properties of this water-retaining vinyl dispersion.

[0103]

[Table 2]

Note: 1) A small particle size stable dispersion can be prepared, but this cannot be done unless the varnish is filtered. 2) Typically contains small gels and requires filtration. 3) Solidify at 50 ° C. within about 5 days. NA = unpaintable

Although the present invention has been described by the various examples described above, it should not be considered that the present invention is limited thereto, and the technical scope of the present invention covers the comprehensive range disclosed above. . Various modifications and embodiments can be made without departing from the spirit and technical scope of the present invention.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventors James, Preston, Stanley 08805, Bound Brook, Middlebrook Road, USA, New Jersey 08805 (72) Inventor Walter, Paul, Mayer United States, New Jersey, 08833, Lebanon, Potterstown Roadbox 266, Earl Dean Number 2 (72) Inventor Eric, Jay, Nagel United States, New Jersey, 08876, Somerville, Country Square Way 30

Claims (10)

[Claims] 1. A) about 1 to 99.9% by weight of one or more vinyl group-containing monomers, b) about 0 to 98.9% by weight of one or more monoethylenically unsaturated monomers different from component a) above. %, And c) a monoethylenically unsaturated macromonomer comprising a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate or a hydrolyzed derivative of this reaction product, or i) trimellitic anhydride Giant monomer consisting of reaction product with hydroxyethyl acrylate and ii) Monoethylene containing huge monomer consisting of reaction product of styrene / maleic anhydride copolymer with hydroxyethyl acrylate or hydrolyzed derivative of this reaction product A vinyl copolymer comprising about 0.1 to 99% by weight of a reaction product of a mixture of macrounsaturated unsaturated monomers. 2. A reaction product of a) vinyl chloride, b) vinyl acetate, c) hydroxyalkyl (meth) acrylate, and d) styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or a reaction product thereof. Monoethylenically unsaturated macromonomer composed of hydrolyzed derivative, or i) macromonomer composed of reaction product of trimellitic anhydride and hydroxyethyl acrylate, and ii) styrene / maleic anhydride copolymer and hydroxyethyl acrylate The vinyl copolymer of claim 1 which comprises the reaction product of a mixture of monoethylenically unsaturated macromonomers, including macromonomers consisting of the reaction product of 1. or a hydrolyzed derivative of this reaction product. 3. a) about 50 to 95% by weight of one or more vinyl group-containing monomers, b) about 0 to 20% by weight of one or more monoethylenically unsaturated monomers different from component a) above, and c ) Monoethylenically unsaturated macromonomer comprising a hydrolyzed derivative of a reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or
Includes i) giant monomers consisting of the reaction product of trimellitic anhydride and hydroxyethyl acrylate and ii) giant monomers consisting of the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate. Included is a vinyl copolymer comprising the reaction product of about 5 to 40% by weight of a mixture of monoethylenically unsaturated macromonomers, wherein the vinyl copolymer comprises at least some carboxylic acid groups. A water dispersible coating composition which is capable of being dispersed in an essentially aqueous medium after being neutralized with a base. 4. A hydrolyzed derivative of a reaction product of a) vinyl chloride, b) vinyl acetate, c) hydroxyalkyl (meth) acrylate, and d) styrene / maleic anhydride copolymer and hydroxyethyl acrylate. Monoethylenically unsaturated giant monomer, or
Includes i) giant monomers consisting of the reaction product of trimellitic anhydride and hydroxyethyl acrylate and ii) giant monomers consisting of the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate. 4. The water dispersible coating composition of claim 3 including the reaction product of a mixture of monoethylenically unsaturated macromonomers. 5. A) about 50 to 95% by weight of one or more vinyl group-containing monomers, b) about 0 to 20% by weight of one or more monoethylenically unsaturated monomers different from component a) above, and c ) Monoethylenically unsaturated macromonomer comprising a hydrolyzed derivative of a reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or
Includes i) giant monomers consisting of the reaction product of trimellitic anhydride and hydroxyethyl acrylate and ii) giant monomers consisting of the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate. Included are vinyl copolymers consisting of a mixture of about 5 to 40% by weight of the reaction product of a mixture of monoethylenically unsaturated macromonomers, where the vinyl copolymer comprises the carboxylic acid groups and bases. It has at least some salt groups derived from the reaction,
A water-dispersible salt-containing coating composition. 6. An aqueous dispersion comprising a major amount of water and a minor amount of the water dispersible salt-containing coating composition of claim 6. 7. A curable mixture comprising the water dispersible salt-containing coating composition of claim 6 and a crosslinking agent. 8. A curable mixture which is an aqueous dispersion comprising a major amount of water, a minor amount of the water dispersible salt-containing coating composition of claim 6 and a crosslinking agent. 9. A giant monomer comprising a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or a hydrolyzed derivative of this reaction product. 10. A macromonomer comprising i) a reaction product of trimellitic anhydride and hydroxyethyl acrylate, and ii) a reaction product of a styrene / maleic anhydride copolymer and hydroxyethyl acrylate, or a reaction product thereof. A mixture of macromonomers, including macromonomers consisting of hydrolyzed derivatives.