KR900001389B1 - Water-dispersible coating compositions and process - Google Patents

Abstract

Water-dispersible block copolymer coating compsns. are prepd., from a reaction mixt. of (I) water-indispersible filmforming organic polymer contg. 3.0H or more per mol.; (II) on org. polymer, ethylene-maleic anhydride copolymer, contg. 2 or more carboxylic acid anhydride gps. per mol., which is dispersible in water after neutralisation of anhidride gps. with a base; and (III) an esterification catalyst. Process comprises (A) reacting OH gps. of (I) with anhydride gps. of (II) to form ester and carboxy gps. producing a film-forming compsn. dispersible in aq. medium of PH more than 5; and (B) controling reaction to prevent gelation by incorporating water or low Me org. cpd. contg. 1-2gps. reactive with an hydride gps.

Description

[Name of invention]

Water-dispersible paint composition and preparation method thereof

Detailed description of the invention

The present invention relates to a process for producing a water-dispersible block copolymer coating composition. In particular, the present invention relates to the condensation reaction of a water non-dispersible, film-forming organic polymer having a plurality of hydroxyl groups with a water-dispersible organic polymer having a plurality of carboxylic acid anhydride groups without causing gelation. The invention also relates to a block copolymer composition prepared in this way.

In preparing paints, it is well known in the art to use organic polymers dissolved or dispersed in organic solvents. Molding paints using such solvents or dispersions involves the removal of large amounts of organic solvents, particularly in recent years, which are considered to be undesirable due to ecological and environmental agents. Therefore, attention is focused on paint compositions in which the organic polymer is dissolved or dispersed in a medium consisting mainly of water. Many of these aqueous paint compositions, including those containing amine salts of carboxyl groups to increase water dispersibility, have been found to be unsuitable because the reagents introduced in their preparation have a detrimental effect on the final paint. For example, the vinyl chloride resin produced by the emulsion polymerization method needs to use a surfactant that remains in the final paint to lower the water resistance of the paint. Film-forming polymers prepared by condensation polymerization, such as epoxy resins, have carboxyl-containing stages on the polymers using peroxide catalysts.

It is therefore an object of the present invention to provide a coating composition which is simple and economical in production and which can be easily converted into a water-dispersible composition by neutralization.

It is also an object of the present invention to provide a method for producing a water-dispersible paint composition that does not have a gelling problem in the manufacturing, and to provide a method for producing a water-dispersible coating composition that is stable in itself.

The present invention is (1). (i) a water non-dispersible, film-forming organic polymer having an average of at least three hydroxyl groups per molecule (hereinafter referred to as “reactant A”) and (ii) having an average of at least two carboxylic acid anhydride groups per molecule, and at least A reaction mixture consisting of an organic polymer other than an ethylene-maleic anhydride copolymer (hereinafter referred to as “reactant B”) capable of being dispersed after hydrolysis and neutralization of some anhydride groups with a base, and (iii) an esterification catalyst. To prepare; (2). To the extent necessary to prepare a film-forming composition that is capable of neutralizing at least some carboxyl groups with a base and then dispersing it in a first aqueous medium having a pH of 5 or more, the hydroxyl group of reactant A and the anhydride group of reactant B are reacted to produce an ester group. And carboxyl groups are formed: (3). anhydride

The process of the invention described above is carried out from (A) a water non-dispersible, film-forming organic polymer component (component I ') and (B) an ethylene-maleic anhydride copolymer having an average number of hydroxyl groups per molecule of at least 3. Organic polymer components other than those derived from ethylene-maleic anhydride copolymers which are derived and are dispersed in water after the neutralization of at least some carboxyl groups with a base with at least two average carboxylic acid groups per molecule (VIII-II) (A) the number of ester groups linking at least some component I and at least some component II with an average of 0.1 to 3.1 preferably 0.5 to 2 per molecule of component I, and (b) at least some After neutralizing the two carboxy groups with a base, a new block copolymer coating composition is provided which is dispersed in a first aqueous medium having a pH of 5 or greater.

The relative amounts of component I and component II present in the composition of the present invention are not precisely determined. Component I is present in an amount sufficient to allow the composition to form a satisfactory coating on the substrate and component II is sufficient to disperse the composition in a first aqueous medium having a pH of 5 or greater after neutralizing at least some carboxyl groups with a base. Present in quantities. The weight ratio of component I and component II in the composition is preferably from 1: 0.01 to 1: 1, more preferably from 1: 0.15 to 1: 0.4. To prepare such compositions, the corresponding amounts of reactant A and reactant B are used in the process of the invention.

Reactant A used in the process of the invention is a film forming material. The term "film forming material" herein means a material that can be added to a solid substrate to form a continuous anhydrous film. this

Reactant A and resultant component I used in the process of the invention are not water-dispersible on their own. After conversion to salts, reactant B, resultant component II, and the block copolymer composition of the present invention used in the process of the present invention are water-dispersible. For the purposes of the present invention, the water non-dispersity and water-dispersity of a substance are determined by the following experiment (hereinafter referred to as dispersion experiment): 25% by weight of the substance to be tested and 0 to 100% by weight A solution consisting of methyl ethyl ketone and 0-100 wt% water-miscible organic solvent and ethylene glycol) 75 wt% is prepared. The base is at least sufficient to convert 35% by weight of water, 80% by weight of monobutylene ethylene glycol (additional organic solvent) and 100 mol% of any carmokyl group present in the material to be tested into salt groups with vigorous stirring. : Dilute gradually with mixture consisting of tertiary amyl). The relative amounts of material to be tested, the total organic solvent, and the water present in the resulting dispersed aqueous solution are 5:26:69. If the average dispersion particle size of the fraction is less than 5 microns and less than 10% by weight of the material present in the dispersion is filtered through a 325 mesh screen, the material according to the invention is considered water-dispersible. On the other hand, if the average particle size of the dispersion is at least 5 microns and at least 10% by weight of the material present in the dispersion is filtered through a 325 mesh screen, the material to be tested is considered water-dispersible. The water non-dispersible material preferably forms a dispersion in which the average dispersed particle size is less than 1 micron and / or less than 2% by weight of the material to be tested is filtered through a 325 mesh screen. In addition, the water non-dispersible material has an average molecular particle size of 10 microns or more and 95% by weight or more of the tested material is filtered through a 325 mesh screen.

The composition of the present invention is dispersed in a first aqueous medium having a pH of 5 or more after neutralizing at least some carboxyl groups with a base. When component I is PVC, it is preferred to use the salts of the compositions according to the invention in dispersions having a pH of 5 or below in order to reduce the rate of decomposition (primarily hydrogen halide removal) of component I. Carboxyl ions tend to have stabilizing effects in these dispersions. However, when the pH is about 5 or less, the stabilization action is insufficient. Therefore, dispersions at low pH tend to become unstable. This instability can be somewhat overcome by adding a nonionic surfactant, such as an ethoxylated noyl phenol, to the dispersion. The pH of the aqueous dispersion solution prepared according to the invention can be inhibited and controlled by using sufficient bases to neutralize the sculptures produced by the invention. The preferred pH range of the dispersion is from 6 to 9 and the most preferred range is from 7 to 8 (except when the hydrogen halide removal reaction is involved).

The following table shows the range of preferred and most preferred number average molecular weights for the preferred types of reactants A and reactants B used in the process of the present invention.

TABLE 1

Note: *; Relatively large amounts of hydrophilic groups such as hydroxyl, ester or acetal groups

**; Relatively few hydroxyl groups and only a few other hydrophilic groups.

The preferred and most preferred molecular weights of components I and II in the compositions according to the invention correspond respectively to the said molecular weights of reactants A and B used in the process of the invention.

When the molecular weight of reactant A is too high relative to the amount of hydrophilic groups present, it indicates that a water-dispersible composition cannot be formed, and the maximum molecular weight suitable for forming the water-dispersible composition will vary depending on the form of the polymer. Usually within the molecular weight range above, a water-dispersible composition is formed.

In the reaction mixture used in the method of the present invention, the molar ratio of the hydroxyl group of the reactant A and the anhydride group of the reactant B is preferably from 0.5: 1 to 5: 1 and most preferably from 1: 1 to 3: 1. The hydroxyl group may be phenolic but aliphatic is preferred.

Any water non-dispersible, film-forming organic polymer having at least three hydroxyl groups per molecule can be used as reactant A in the process of the invention. Suitable as such polymers are addition polymers of ethylenically unsaturated monomers, epoxy polymers, phenoxy polymers, urethane polymers, polyester polymers, phenolic polymers and polyamide polymers.

In the process of the present invention, examples of the addition polymer of the ethylenically unsaturated monomer which can be used as the reactant A include an ethylenically unsaturated monomer containing a group which can be converted into a hydroxyl group or a hydroxyl group (hereinafter referred to as “monomer I ′). ) And a community of at least one other ethylenically unsaturated monomer (hereinafter referred to as "monomer II"). Monomer I includes hydrolyzed vinyl acetate, hydroxyalkyl acrylate having 2 to 6 carbon atoms of the alkyl group.

Stability issues follow when reacting an epoxy polymer with an anhydride polymer in the presence of an esterification catalyst to form a water-dispersible composition. In order to overcome this stability problem in the practice of the present invention using epoxy polymers, epoxide groups can be removed ('terminal introduction') by reacting with monocarboxylic acids or mono hydroxyphenols before reacting with reactant B. On the one hand, the epoxy groups can be hydrolyzed to form less reactive hydroxy groups.

Examples of end-induced epoxy polymers that can be used as reactant A in the process of the invention include the following: by reaction of carboxy groups with epoxy groups under conditions such that the hydroxy groups of the epoxy polymer become substantially non-reactive. A reaction product of a monocarboxylic acid (including hydroxy-containing monocarboxylic acid) and an epoxy polymer formed. Above

The endduction reaction proceeds in the presence of a suitable catalyst. Catalysts which can be used here include amines such as benzyldimethylamine and lithium compounds such as organic lithium salts. When the terminal introduction catalyst (ie, the amine catalyst) also promotes the reaction of reactant A with reactant B, it may remain in the terminally introduced epoxide, which may be used for the following purposes. In the process of the invention, the endduction reaction introduces ester or ether groups and hydroxyl groups into the polymer. The use of hydroxy-containing carboxylic acids in the endduction reaction of the epoxy polymer further introduces hydroxyl groups into the polymer. Such hydroxyl groups should be considered as possible interactions with anhydride groups in reactant B.

Epoxy polymers that can be used, such as (if necessary) or after termination, as reactant A in the present invention, are described in US Pat. No. 4,212,781. The epoxy polymer used may be aliphatic or aromatic. Most preferred epoxy resins are polyglycidyl ethers of bisphenol A, in particular 1,2-epoxy equivalents of about 1.3 to about 2, preferably about 2. The molecular weight should be about 350 to about 20,000, preferably about 4,000 to about 10,000. Sometimes it may be convenient to use a processed epoxy resin with the desired molecular weight, but it is more practical to use commercially available bisphenols and bisglycidyl ethers of A. Bisglycidyl ethers of bisphenol A, commonly known as "liquid epoxy resins,"

The physical properties of the supercatalyzed liquid epoxy resin “Epon-829” are as follows:

TABLE 2

Note: *; Epoxide equivalent is g of resin containing 1 g equivalent of epoxide.

In order to increase the initial molecular weight of the liquid epoxy resin to a more satisfactory level for many coating applications, the initial liquid epoxy resin can be further reacted with bisphenol A and other materials. Other polyfunctional aromatic alcohols can be used to make glycidyl ethers and increase the molecular weight, such as: bis (4-hydroxyphenyl) methane, [bisphenol F]; 2,2-bis- (4'-hydroxy-2 ', 3', 5 ', 6'-tetrachlorophenyl) propane; Tetrachlorobisphenol A; 4,4-bis (hydroxyphenol) -pentanoic acid; Diphenol calculation; Novolac or low molecular weight phenol-formaldehyde polymers; 1,8-bis (hydroxyphenyl) pentadecane; Resorcinol; And 2,2,5,5-tetrakis (4'-hydroxyphenyl) hexane, such as to increase the weight of the initial liquid epoxy resin, and through the process

By way of example, the ratio of bisphenol A and “EPON-829” used to prepare the epoxy resin with the most preferred molecular weight is 65 to 68 weight percent of bisphenol A and 35 to bisphenol A to prepare the polymer having an epoxy end group. 32% by weight, for preparing polymers having hydroxyl end groups: ＂EPON-59.5-62% by weight and 40.5-38% by weight bisphenol A. The following table shows the properties of the final epoxy resins produced from the ratios of the different starting materials.

TABLE 3

The reaction conditions used to increase the molecular weight of liquid epoxy resins or other low molecular weight epoxy resins are reaction temperatures of about 175 ° C. and pressure at atmospheric pressure. While this reaction can be carried out without solvent, it is preferred to use about 15% by weight of ethylene glycol monobutyl ether based on the total reactants.

Epoxy resins that can be used can also be transformed into other condensates such as phenolic resins, phenols, and polyols. Examples of modified epoxy resins are as follows: glycidyl esters formed by the reaction of phenol novolak resins with epichlorohydrin; 4,4'-isopropylidenediphenol epichlorohydrin or one or more anhydrous oils or fatty acids (beech

[여기서 R 및 R¹은 동일하거나 다를 수 있다]그룹을 가지고 있으며, 반복단위로서

를 함유하고 있다.Examples of phenoxy polymers that can be used as reactant A in the process of the present invention are described in US Pat. Nos. 3,530,28 and 3306872. The phenoxy polymer of US Pat. No. 3,305,028 is a nearly linear, gel-free thermoplastic poly (hydroxyether). This is the condensation product of dihydric polynuclear phenol with epichlorohydrin, the general formula -OEO- [where E is the nucleus of dihydric polynuclear phenol having hydroxyl groups attached to other nuclei, and -OEO- is di Residue obtained by removing the hydroxyl hydrogen atom of a hydric polynuclear phenol.

Where R and R ¹ may be the same or different and have a repeating unit

It contains.

The phenoxy polymers described in US Pat. No. 3,306,872 are nearly linear polymers that produce condensation of dihydric phenols and diepoxides with high impact strength during molding and extrusion.

In the case of phenoxy polymers having epoxy groups which cause crosslinking in the process of the invention, the epoxy groups can be end-induced or hydrolyzed as in the case of epoxy polymers.

An example of a urethane polymer useful as reactant A in the process of the invention is the reaction product of a stoichiometric excess of polyol and polyisocyanate. Typical of such polyols are poly (oxyalkylene) polyols, which are polyhydric organic compounds or alkylene oxide addition products of water used as initiators or starting agents. Suitable polyhydric organic initiators include, for example: ethylene glycol, diethyl glycol, propylene glycol, 1,5-pentanediol, hexylene glycol, dipropylene glycol, 1,2-cyclohexanediol, 3-cyclohexane-1,1-dimethanol, glycerin, 1,2,6-hexane triol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, sucrose, alpha-methyl glucoside, or Combinations thereof. The polyisocyanates are represented by the following general formula:

Q- (NCO) i

In the above formula, i represents an aliphatic, cycloaliphatic or aromatic radical having an average value of at least 2 and usually less than or equal to 6 and Q may be an unsubstituted hydrocarbyl group or a hydrocarbyl group substituted with halogen or alkoxy. For example, Q is the corresponding halogen- and-

Organic polymers, in particular ethylene-maleic anhydride copolymers, which are dispersed in water when the number of average carboxylic acid anhydride groups per molecule are at least two and hydrolyzed and neutralized at least some anhydride groups can be used as reactant B in the process of the invention. . Suitable organic polymers are addition polymers derived from ethylenically unsaturated monomers containing anhydride groups such as maleic anhydride, phenyl maleic anhydride, chloro maleic anhydride, dichloromaleic anhydride, itaconic anhydride and aconic acid anhydride. Anhydride-containing monomers are usually copolymerized with other ethylenically unsaturated monomers, such as monomers II as defined above. Useful as reactant B is a butadiene polymer prepared by adding ＂ENE＂ of maleic anhydride to the quaternary carbon of liquid butadiene. Particularly preferred copolymers of this kind include the styrene-maleic anhydride copolymer and the number-average molecular weight of about 1600, the number of acids being 480 and the ratio of styrene to maleic anhydride being 1: 1 (molar). Styrene-maleic anhydride-maleic anhydride half ester terpolymers available under the name 이름 SMA ＂, including. Reactant B preferably contains 4-12 carboxylic acid anhydride groups per molecule of Reactant B, more preferably 6-9.

Any esterification catalyst can be used as an esterification catalyst in the method of this invention. Typical examples of such a catalyst include amines, alkali metal hydroxides and inorganic acids. Preferred of these are trialkylamine catalysts having 1 to 5 carbon atoms in the alkyl group, for example as triethylamine and tripropylamine. Such catalysts are preferably present in an amount of 2 to 40 (more preferably 4 to 15) mole percent per mole of carboxy group in the reaction mixture.

The organic solvent (reaction solvent) is preferably present in the reaction mixture used in the present invention. Suitable solvents include ketones, hydrocarbons, esters and chlorinated hydrocarbons. Preferred reaction solvents are saturated aliphatic ketones having 2 to about 4 carbon atoms in each aliphatic moiety.

Examples of such ketones include acetone, methyl ethyl ketone, ethyl propyl ketone, methyl butyl ketone and ethyl butyl ketone. Preferred solvents are acetone or other solvents having the following properties:

(1) Minimize thermal decomposition of reactant A and reactant B because of boiling at low temperatures.

(2) can be easily removed from the composition of the present invention.

(3) Nonreactive to the reaction mixture used in the process of the invention.

(4) Water soluble.

Suitable amounts of reaction solvent are 75 to 500 parts by weight per 100 parts by weight of reactants A and B. When a reaction solvent is used in the method of the present invention, the product is an organic solvent solution of the composition of the present invention. These solutions (new varnishes) are new and also form part of the present invention.

The reaction pressure in the process of the invention is not exactly defined, but economical

After the composition of the present invention is produced, it is preferable to substitute a high boiling point solvent (coating solvent) for at least a part of the reaction solvent. Suitable coating solvents include alkyl monoethers and glycol ethers of glycols. Such coating solvents improve the properties of the final coating composition. Examples of such glycols and ethers are mono butylethylene glycol, monopropylethylene glycol, monoethylethylene glycol, monomethylethylene glycol, monomethyl diethylene glycol, and monoethyldiethylene glycol, monopropyldiethylene glycol. In general, the substitution of the solvent ('solvent exchange') can be achieved by volatilizing at least a portion of the reaction solvent (removing the solvent) and adding a coating solvent to the residue. The initial composition can be separated just before the point at which the viscosity is exceeded. After removal and addition of the coating composition, the remaining reaction solvent may be further removed to make the solids content higher. The degree of removal will depend on the thermal stability of the solid material, the desired solids content and final viscosity, and the flash point. The coating solvent-composition solution of the present invention is new and also forms part of the present invention.

Reactant A used in the process of the invention is not dispersed in an aqueous medium having a pH of 5 or greater. In the process of the invention the resulting composition can be dispersed in an aqueous medium having a pH of 5 or more.

Since water-dispersity can be achieved by the formation of ester bonds between component I and component II, the point at which dispersion is achieved is additionally or alternately by titrating the reaction mixture sample with aqueous caustic soda (titrant) during the reaction. It can be measured according to the loss of the carboxyl group in B. The ester bond formation monitoring experiment is the “ester group monitoring experiment” described above. As such experimental data, the number of moles of ester groups formed per molecule of reactant B can be determined using the following equation:

In the above formula, X = ＂potential＂ COOH groups (ie, twice the number of anhydride groups initially present in reactant B plus the number of carboxy groups initially present), ml _C = when the esterification reaction starts Milliliters of titrant reacted with a sample of the reaction mixture.

ml _R = milliliters of titrant that reacts with a sample of the reaction mixture at a given time in the esterification reaction.

Wt _C = Weight of the reaction mixture sample at the start of the esterification reaction.

Wt _R = weight of the reaction mixture sample reacting with the titrant at a given time during the esterification reaction.

If the esterification reaction included in the process of the present invention is allowed for too long, a gel is formed which does not disperse in the aqueous medium. Therefore, the reaction should be adjusted so that the reaction proceeds only to an appropriate degree (ie, to produce a composition having an appropriate degree of dispersion and aqueous dispersion viscosity).

In the process of the invention, the reaction of the hydroxy group of reactant A with the anhydride group of reactant B (hereinafter referred to as “first reaction”) contains one or two groups reactive to the anhydride group of reactant B. A low molecular weight organic compound and / or water (hereinafter referred to as `` float amount '') is used to control to prevent gelation.

This control is in accordance with the fact that the reactive groups provided by the immersion consume anhydride groups, thus slowing the rate of ester formation between reactants A and B. If a solution is added before any reaction takes place (called initial addition), the first reaction starts at a moderate rate and the resulting water-dispersible properties, even if no additional steps are taken to control the first reaction. The composition is gradually reduced at a slow rate that can be stored without relatively long gelling. If the solution is added after the first reaction has started (hereinafter referred to as the "continuous addition method"), the first reaction rate will be relatively fast up to the point where the maximum solution is applied. The first reaction rate is then reduced in the same way as observed in the initial addition method. The amount of immersion used is not so high as to reduce the first reaction rate to such an extent that the water-dispersity of the composition is not achieved in a reasonable time. When using the initial addition method, dipped per equivalent of anhydride group in reactant B

The alcohols include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, and methyl, ethyl, propyl and butyl monoethers of ethylene glycol. The above amines include diethylamine and dimethylamine. The hydroxy group in the alcohol immersion is preferably a primary hydroxy group. In addition, the immersion liquid preferably has a molecular weight of 200 or less, more preferably 120 or less. Since the dihydric alcohol and the primary amines form the composition of the present invention having a higher viscosity than desired, the immersion solution is preferably a monohydric alcohol or a secondary amine. By the way, water is the most preferable solution.

As described above, the composition resulting from the reaction of component A and component B is a group in which a significant portion of the carboxy groups in the composition (ie, carboxy groups formed from anhydride groups simultaneously with the formation of ester groups) are more hydrophilic (ie, Water-dispersible only when converted to a carboxyl group and a salt group formed by the reaction of a base). This salt formation can be achieved by using an excess of base as esterification catalyst in the ester-forming reaction (first reaction). In this case, the catalyst acts as a catalyst and as a reactant. It is preferred that only a catalytic amount of base is initially added and further a base is added to the composition to react with the carboxy group after the first reaction has occurred to render the composition water-dispersible. The neutralized composition is a new salt of the present invention.

In the process of the present invention, formation of a non-gelling composition by reacting reactant A and reactant B is foreseen that many of the crosslinking potential sites in the reaction mixture cause the formation of largely gelled networks (three-dimensional). Not unexpected Prior to the present invention, one would have thought that a suitable anhydride-based cross reactant for reactant A was tailored by pretreatment of the anhydride-containing polymer with water to achieve hydrolysis of the majority of the anhydride groups.

An unexpected both side of the present invention is the fact that water or other diluents can be used with reactant A and reactant B and the first reaction can be carried out without obtaining a gel since the competition involved is self-regulating.

The compositions and salts of the present invention contain block copolymers. By "block-copolymer" is meant a substance composed of at least one block or fragment consisting of at least one type of monomeric unit and at least one other block or fragment consisting mainly of other types of monomeric unit. “Block copolymers” in their overall structure are linear [ABA, AB or (AB) _n ] and grafted copolymers.

The block copolymer composition (and salt thereof) prepared by the process of the invention is a complex mixture. The compositions or salts are usually of the unreacted reactant A, the unreacted reactant B, the anhydride group hydrolyzed to the carboxy group (converted to the salt group in the salt of the present invention) but not esterified (when the solution is water). Derivatives, esters or amides and carboxy derivatives formed by the reaction of anhydride groups of reactant B with an immersion solution (when the immersion is an alcohol or an amine) and have different molecular weights and / or different numbers of linking ester groups and / or different numbers of blocks It contains a random mixture of copolymer distributions of component I and component II.

As components I and II are present in the block copolymer compositions (or salts thereof) of the present invention as blocks in block copolymers linked by ester groups, their water-non-dispersity, film-formability, water-dispersity, Molecular weight and other properties can be measured by hydrolyzing ester groups to regenerate the polymer corresponding to the block. The polymer thus formed can be separated and the properties of the isolated polymer can also be measured. When components I and II are unbound (unreacted) polymers in the block copolymer composition (or salts thereof) of the present invention, the components I and II are measured by simply separating the components I and II and measuring the properties of the separated polymer. The properties of II can be measured.

The compositions of the present invention can be co-dispersed with other polymers (ie unreacted reactant A) and can be combined with alkyd, polyurethane, epoxide or latex polymers to produce blends useful as paints, inks and adhesives. .

The compositions of the present invention can also be used for coating applications in the form of salts in the first aqueous dispersion solution (ie, dispersions in which the continuous phase is mostly water). Such dispersions comprise 15 to 55% by weight (more preferably 20 to 35% by weight), 40 to 84% (more preferably 50 to 70% by weight) of the salt of the composition according to the invention and an organic solvent for the composition ( That is, it is preferable to contain 0 to 35% by weight (more preferably 5 to 25% by weight) of the reaction solvent, or more preferably the coating solvent, described above. Such aqueous dispersions can be prepared by conventional methods, (Reference Example 16) A part of the present invention is formed.In general, a dispersion aqueous solution can be prepared by solvent exchange of the reaction solvent solution described above and then diluting the resulting coating solvent solution by mixing with an aqueous base. Wherein the base neutralizes the carboxy groups in the composition to form salts that can be dispersed in the water-organic solvent mixture.

[Characteristics of Dispersed Aqueous Solution]

(A) viscosity

The initial viscosity of the aqueous dispersion prepared by the process of the invention is influenced by the number of ester bonds in the composition of the invention and the type and nature of the solvent (reaction solvent and coating solvent) and the method of addition of the solvent.

(B) Aging

Aqueous dispersions prepared by the process of the present invention are present as a homogeneous fluid which does not generate gels, coagulum, precipitates or bubbles upon storage for at least 3 months at room temperature and 50 ° C. under conditions of which the pH is not too low. However, upon aging of a dispersion containing a composition prepared from hydroxy-containing vinyl chloride polymer as reactant A, the viscosity and pH will change. Both of these unstable mechanisms are responsible for the latter phenomenon when reactant A is derived from vinyl chloride (ie, dehydrochlorination of vinyl sites and hydrolysis of ester bonds). Hydrolysis occurs relatively low under moderately acidic and basic conditions, as evidenced by removing the coagulum in the dispersion upon prolonging the shelf life at 50 ° C.

(C) cured coating properties

Paints prepared with the compositions of the present invention using hydroxy-containing vinyl chloride polymers as reactant A generally have a balance of chemical resistance, softness and hardness in common with paints made from vinyl chloride polymers. The cured paint properties of the various dispersion aqueous solutions of the new composition salts according to the invention are in the same range as those of the solvent-vinylchloride / vinylacetate / hydroxypropyl acrylate terpolymer corresponding to reactant A in the new composition. Haircuts on solid substrates, such as metal substrates including aluminum or steel

It is preferred that the curable mixture contains about 10 to 20 parts by weight per 100 parts by weight of the salt-containing composition of the present invention. The curable mixture is preferably prepared by mixing the crosslinking agent with the aqueous dispersion of the invention described above, in which case the curable mixture is prepared with a large amount of water, a small amount of the salt-containing composition according to the invention, a small amount of the crosslinking agent, and optionally a small amount. It is a curable dispersion aqueous solution containing the organic solvent of. Cured coatings on solid substrates can be formed by well known crosslinking, coating methods using the curable compositions of the invention. If necessary, the substrate may be primed by a known method before adding the curable composition to the substrate. As a crosslinking agent, melamine-formaldehyde resin (for example, hexamethoxymethylmelamine), urea-formaldehyde resin, or polyaziridine resin is preferable. The mixture of the block copolymer composition (or salt thereof) of the invention with the crosslinking agent is new and forms part of the invention.

The present invention will be described in more detail with reference to the following Examples, and the meanings of the various names, abbreviations and symbols used in the Examples and Comparative Examples are summarized below:

TABLE 4

[Ester Group Monitoring Experiment]

In the process of the invention the formation of ester groups linking component I and component II is observed as follows.

I. Reagents

A. 0.1N NaOH

B. thymol blue (0.1 g / 100 g pyridine) dissolved in pyridine

II. Ester Link Verification Procedure

1. Before starting the reaction, weigh 10 ml of NaOH titrant and weigh the sample rich in the acid and anhydride groups in reactant B as required.

2. Add 125 ml of anhydrous acetone.

3. Add 6 drops of indicator.

4. Titrate with NaOH until blue lasts 30 seconds. This amount of titrant is used as a control.

5. Titrate a sample of the reaction mixture or reaction product and record the weight and amount of the titrant.

6. Determine the amount of ester linkage by calculating it according to formula A.

Example 1

One liter, equipped with a mechanical stirrer, heating mantle, reflux cooler and funnel, was placed in the reaction vessel in order to form the initial reaction mixture. Then dissolve each component before adding the next ingredients.

Note: * Vinyl claw with a number average molecular weight of 4,000 and a hydroxyl content of 2.62% by weight.

** Styrene / maleic anhydride copolymer having a number average molecular weight of 1600, a number of acids of 480, and a molar basis of styrene: maleic anhydride of 1: 1 (trade name: SMA 1000 ').

The initial mixture of ingredients is heated to reflux temperature of 59 ° C. with continued stirring. When the temperature reached 59 ° C., 3.0 g of acetone and 3.0 g of a premixed triethylamine catalyst were added (0.173 moles of amine per equivalent of anhydride in the initial mixture). The reaction mixture is stirred at reflux for 35 minutes.

The degree of esterification and the dispersion of the product are checked periodically for 35 minutes under reflux by dropping a drop of the reaction mixture into a beaker containing a test solution consisting of 10 g of water, 2 g of solvent B and 0.6 g of dimethylethanolamine. Prior to the esterification reaction, reactant A-I precipitates in the solid phase in the test solution. After esterification, the product is completely dispersed in an experimental solution that produces a cloudy solution free of visible particles or condensation as measured by visual observation (this is referred to as “dispersion monitoring experiment”. Specific dispersion is shown in Examples 1-24). In this example, this dispersion was reached after about 35 minutes under reflux. At this time, solvent A129g was added and 196g of acetone was distilled off. The product at this time is pale yellow ＂varnish＂. Such varnishes are stable and can optionally be packaged for future use or immediately dispersed in water.

The aqueous dispersion is prepared by stirring the warm varnish obtained above in 200 g of water containing 6 g of dimethylethanolamine and 40 g of solvent B, wherein the resulting aqueous component

The initial reaction mixture described above contains the following molar equivalents:

TABLE 5

Comparative Example A

Instead of reactant AI, vinyl chloride / vinyl acetate / hydroxypropyl containing a number average molecular weight of about 8000, containing 15% by weight of polymerized hydroxypropyl acrylate, 5% by weight of polymerized vinyl acetate and 80% by weight of polymerized vinyl chloride. The procedure of Example 1 is repeated using acrylate. And reaction (reflux) time is made longer than Example 1. Reaction A-II contains 1.96 weight% of hydroxyl groups whose 25 weight% is a 1st hydroxyl group. The experiment of this example is not satisfactory in that the product does not become water-dispersible in the dispersion furnace monitoring experiment. After heating for 100 minutes under reflux, reactant B-I precipitated because it reacted with water and catalyst to form acetone-soluble salts.

This result is obtained because reactant A-II forms a water-dispersible composition by using an insufficient initial addition method of the hydrophilic group. An aqueous dispersion was then prepared from reactants A-II using the continuous addition method described in Examples 26, 27 and 28.

[Comparative Example B]

The procedure of Example 1 is repeated except slightly increasing the water content and significantly increasing the amine content. The following starting materials were used:

TABLE 6

Reaction mixture

Note: * Defined in Example 1.

step :

Components other than the catalyst solution are placed in a flask and refluxed at 60 ° C. The catalyst solution is then added over 35 minutes. As a result, the product was dispersed in a 5% DMEA solution 5 minutes after the addition of the catalyst solution, and again after 3 minutes a gel formed.

The product contains a relatively high concentration of catalyst, while water (soak solution) to control the reaction.

[Comparative Examples C and D]

All components except the catalyst mixture are placed in a flask and refluxed. Next, a catalyst mixture is added. The dispersion of the sample is periodically measured using a 5% DMEA solution.

TABLE 7

Reaction mixture

* Defined in Comparative Example A.

In Comparative Examples C and D, the product does not become water-dispersible because the number of hydrophilic groups that form the water-dispersible composition using the initial addition method is insufficient for reactants A-II with respect to its molecular weight. The aqueous dispersion from reactant A-II was

[Comparative Examples E and F]

General procedures and starting materials of Comparative Examples E and F are as follows:

TABLE 8

Reaction mixture

Reactant A-III is a tripolymer containing 91% polymerized vinyl chloride, 3% polymerized vinyl acetate and 6% polymerized vinyl alcohol by weight and having a molecular weight of about 15,000.

In Comparative Examples E and F, the product does not become water dispersible because the number of hydrophilic groups forming the water-dispersible composition using the initial addition method is insufficient for the reactants A-III relative to its molecular weight.

Comparative Examples G and H

Add the following ingredients to the flask:

TABLE 9

* Defined in Example 1

Reactant B-V is commercially available under the trade name “EMA 1103” and has a number average molecular weight of 8000 as a copolymer of ethylene / maleic anhydride (1: 1 molar ratio).

Combining the solutions of A-I and B-V solidifies the polymer blend.

This example illustrates the inability to ethylene-maleic anhydride copolymers in the process of the present invention.

EXAMPLES 2, 3, and 4

The general procedure of Example 1 is repeated with different catalyst concentrations. Starting materials used are as follows:

TABLE 10

Reaction mixture

In Examples 2, 3 and 4, all the resulting compositions are water-dispersible in contrast to the gels produced in Comparative Example B above. These results illustrate the importance of the proper relationship between catalyst concentration and soak concentration. In Examples 2, 3 and 4, the catalyst concentration decreases while keeping the level of the immersion constant. Therefore, the first reaction (esterification reaction) rate (measured as the time required to reach the water-dispersible state) becomes slow. Conversely, at high catalyst levels it is necessary to make the concentration of the immersion higher in order to moderate the esterification (grafting) reaction in order to avoid gelation.

Example 5

A stirrer, a thermometer and a heating mantle to a 500ml reaction A-IV solution to the reactor equipped with ^* 310g, and the reaction is BI 30g and 2.8g of water. After 30 minutes of stirring under heating,

200 g of warm varnish was added to 200 g of a water / solvent B / dimethylethanolamine (5/1 / 0.28 weight ratio) solution to stir to prepare an aqueous dispersion. The resulting product is characterized as follows:

pH = 8.4

Viscosity = 510cp (Brookfield RVT, T-A Spindle, 100rpm)

Solid content = 35.1%

The reactant A-IV solution ^* used in this example contains 48.4% reactant A-IV, 47.1% acetone and 4.5% MIBK, and reactant A-IV contains 53.9 mol% of polymerized methyl methacrylate and polymerized butylacrylic. It contained 28.6 mol% of rate and 17.5 mol% of polymerized hydroxypropyl acrylate (Mn = 4880).

Example 6

시간후, 반응물 B-I 10g 및 THF 30g을 추가로 가하고 다시

시간동안 가열을 계속한 결과 이렇게 하여 생성된 생성물(바니쉬)의 소량의 샘플이 물/용매B/디메틸에탄올아민(5/1/0.28중량비)내에서 2시간 교반후 분산성으로 되었다.1 liter equipped with a stirrer, thermometer, cooler and heating mantle is a polymer consisting of reactant AV (80% by weight polymerized vinyl butyral, 18.5% polymerized vinyl alcohol and 1.5% polymerized vinyl acetate) by Mn 38,000), 40 g of reactant BI, 400 g of tetrahydrofuran (THF) and 6.1 g of water are added. After heating and stirring for 20 minutes, the resin is dissolved and 8.0 g of triethylamine are added. The dispersity test for water / solvent B / dimethylethanolamine (5/1 / 0.28 weight ratio) is periodically performed while heating is continued at 67 ° C. under reflux. 1 hour later,

After time, add 10 g of reactant BI and 30 g of THF and again

Heating was continued for a time. As a result, a small sample of the resulting product (varnish) became dispersible after stirring for 2 hours in water / solvent B / dimethylethanolamine (5/1 / 0.28 weight ratio).

A crude aqueous dispersion is prepared by mixing 250 g of warm varnish with water / solvent B / dimethylethanolamine (5/1 / 0.28 weight ratio) (using Cowles Dissolver). Most THF is distilled off in a distillation flask. Distillation is stopped after the temperature of the material in the flask reaches 93 ° C. The properties of the final product (dispersed aqueous solution) are as follows:

pH = 8.5

Viscosity = 150 cps (Brookfield RVT, # 2, 100 rpm)

Solid content = 27.9%

The use of more suitable paint solvents can give an aqueous dispersion better than the product from the varnish.

Example 7

349 g of a 43% reactant AI / acetone solution in a 500 ml reactor equipped with a stirrer, thermometer, cooler and heating mantle, reactant B-II [vinyl methyl ether and maleic anhydride (1/1 molar ratio) copolymer, 1 g / MEK 100 ml) is 0.11, and the number average molecular weight is 20,000 ± 7,000] and 30 g and 3.0 g of water are added. After heating and mixing, a homogeneous solution is obtained, and then 4.5 g triethylamine dissolved in 4.5 g of acetone is added. At this time, it turns from amber to purple. Continue heating and mixing to a temperature of 62 ° C. under reflux. 20 minutes later

500 g of warm varnish was added to a water / solvent B / dimethylethanolamine (5/1 / 0.28 weight ratio) solution, stirred, and 350 g of water was added to prepare an aqueous dispersion. The properties of the resulting stable product are as follows.

pH = 8.6

Viscosity (Brookfield RVT, # 5 spindle, 100 rpm)

Initial = 600cp

6 days later = 72CP

Solid content = 6.5%

The initial reaction mixture of Examples 5-7 contained the following equivalents and levels.

TABLE 11

Example 8

End group introduction reaction

1 liter reactor with stirrer, thermometer, cooler and heating mantle

First reaction

60 g of diacetone alcohol is slowly added to the epoxy polymer into which the hot end groups are introduced at a temperature of the polymer to a temperature of 129 ° C. Next, 35 g of acetone are added at a temperature of the polymer to a temperature of 78 ° C. Add 5.5 g of water and 120 g of 50% reactant B-I / acetone solution. The components are stirred under reflux (75 ° C.). The esterification reaction is periodically monitored by adding large drops of the reaction mixture to a beaker containing 10 g of water, 20 g of solvent B, and 0.6 g of dimethylethanolamine. Epoxy resin is precipitated before the esterification reaction and after the esterification reaction the product (varnish) drops are completely dispersed to form a cloudy solution free of visible particles or coagulum. The dispersion reached about 90 minutes, at which time an additional 18 g of water produced varnish. 200 g of warm varnish was added to 300 g of a solution of water / solvent B / dimethylethanolamine (5: 1: 1 by weight) and stirred to prepare an aqueous acid solution.

Example 9

The procedure of Example 8 was followed except the terminal introduction reaction was allowed to proceed for 30 minutes at 160 ° C. (where 92.7% of the original oxirane action was consumed), 60 g of acetone were added, and only 3.2 g of water before the reaction BI was added. Repeat. After refluxing at 70 ° C. for 55 minutes, the first reaction was stopped. At this point the water-dispersibility stage is reached to produce the varnish. 204 g of warm varnish was added to 300 g of a water / solvent B / dimethylethanolamine (5/1 / 0.28 weight ratio) solution and stirred to prepare an aqueous acid solution.

Example 10

In the end group introduction reaction, xylene is used instead of diacetone alcohol, and 50 g of MIBK is used instead of 60 g of diacetone alcohol to dilute the epoxide to which the end group is introduced, except that 23 g of water is added before reactant BI is added. Repeat the procedure in Example 8. The water-dispersible state was reached after refluxing at 73 ° C. for about 70 minutes. Heating was continued before adding 83 g of solvent B to remove 54 g of acetone, resulting in varnish. 204 g of varnish was added to 200 g of a water / solvent B / dimethylethanolamine (5/1 / 0.28) solution, followed by stirring to prepare an aqueous acid solution. While this experiment shows that solvents other than diacetic alcohol (aqueous solvent) can be used as the end group introducing solvent, water soluble solvents are preferred because of the excellent film-forming properties of the resulting dispersion.

Example 11

Example 1 except that only 16.4 g of DMPA was used for the end group introduction reaction, after 75 minutes at 173 ° C., 91.5% of the initial oxirane group was consumed and then only 4.6 g of water was added before the reaction BI was added. Repeat the procedure. The water-dispersible state reached about 100 minutes after refluxing at 72 DEG C. At this time, 62 g of the distillate was collected and solvent B was added to the varnish.

Example 12

End group introduction reaction

To the same reactor as in Example 8-11 was added 300 g of reactant A-VI (defined in Example 8) and 45.5 g of dehydrated Castor oil acid (＂9-11 acid). The resin is heated without stirring until it is in a fluid state that can sufficiently stir. 1.6 g of BDMA is added dropwise at 156 ° C. and the reaction is heated to 175 ° C. After 35 minutes, the number of acids was 1.3 and 94.9% of the original oxirane content was consumed.

First reaction

60 g of diacetone alcohol is added followed by 60 g of acetone. At 70 ° C., 3.2 g of water are added and 120 g of 50% acetone solution of reactant B-I and 100 g of diacetone alcohol are added. Heat and remove 87 g of distillate. The reaction temperature at this time is 110 degreeC. After refluxing is continued for 90 minutes at this temperature, the dispersion state becomes dispersed. 20 g of water is added to convert the remaining anhydride groups to an acid to form a varnish. 200 g of the varnish was added to 450 g of water / solvent B / dimethylethanolamine (5/1 / 0.28 weight ratio) to stir to prepare an aqueous dispersion.

Example 13

The procedure of Example 12 is repeated except that 4.6 g of water is added before the reaction B-I is added and 100 g of solvent B is added instead of diacetone alcohol before removing 89 g of distillate. The dispersible state was reached in 40 minutes at 110 ° C. After an additional 30 minutes of heating, varnishes were produced. 200 g of the resulting varnish was added to 250 g of water / solvent / dimethylethanolamine (5/1 / 0.28 weight ratio).

Example 14

The procedure of Example 8 was followed except for the following changes: 1.76 g of an aqueous solution containing 2% lithium in the form of organolithium salt (Pentecat W-2 ') instead of BMDA was used as the end group introduction catalyst. After 30 minutes at 175 ° C, the analysis consumed 92.6% of the initial oxirane content. The heating is continued for another 33 minutes, diluted and cooled. Add 60 g instead of 30 g of acetone. 3.0 g of triethylamine (TEA) is added to promote the first reaction. After 2 hours at reflux (69 ° F.), another 3.0 g of TEA is added. The product (varnish) became water-dispersible after 37 minutes. No additional water is added. 200 g of the warm varnish is added to 400 g of a solution of water / solvent B / diethylethanolamine (5/1 / 0.28 weight ratio) and 100 g of water to prepare an aqueous dispersion.

Comparative Example I

Into a 1 liter reactor equipped with a stirrer, thermometer, cooler, and heating mantle, 200 g of reactant A-VI, 200 g of acetone, 40 g of reactant B-I, and 3.1 g of water. The contents were stirred at reflux (58 ° C.) for 1 hour, and then a mixed solution of 3.5 g of TEA and 3.5 g of acetone was added. Stirring was continued for 58 minutes under reflux, in which the aqueous fat dispersion was found to be dispersed in a test solution consisting of 10 g of water, 2 g of solvent B, and 0.6 g of diethylethanolamine. 1.5 g of water is added, heating is continued, and 120 ml of acetone is restrained, followed by 89 g of solvent B. Again 40 g of acetone are removed and the resulting varnish is drained. 200 g of warm varnish was added to 285 g of water / solvent / dimethylethanolamine (5/1 / 0.28) solution and stirred to prepare an aqueous dispersion. The aqueous dispersion gelled in 3 days at room temperature.

Summary of Results

The results of Examples 8-14 and Comparative Example I are summarized in Table 12 below.

TABLE 12

* Solvent B added to the esterification zone (hydroxyl: anhydride equivalent ratio = 3.3)

** Liquid still after 3 months at 50 ° C

# Comparative Example

REFERENCE TO TABLE 12: A stable aqueous dispersion was first reacted with oxirane monocarboxylic acid (terminal introduction reaction) to reduce the oxirane content by at least about 90% and then 1: 1 styrene / maleic anhydride in the presence of controlled amount of water. It can be made from an epoxy polymer by grafting reaction (esterification reaction in the first reaction) with a copolymer (Examples 8, 10, 11, 12, 13 and 14).

The rate of esterification (first reaction) is greater than when the first hydroxyl group (provided by DMPA) is present on the epoxy resin (Examples 8, 10, 11, 14 VS 12, 13). However, by raising the esterification (first reaction) temperature (Examples 12 and 13), it is possible to esterify an epoxy polymer containing only secondary hydroxyls (which are initially present in the epoxy polymer).

The amount of water required for complete hydrolysis of the anhydride group can be at least fivefold while achieving dispersion in water (Example 10).

The product of Comparative Example 1 is not stable to water because of the high level of unreacted diepoxide.

The properties of commercial epoxy polymers (“Epoxy-l”) for the aqueous dispersions of Examples 8-14 and aluminum and beverage can paints are shown below:

TABLE 13

Film properties

The properties of films (on aluminum panels) made from the various compositions of the invention cured with 10 and 20 phr Cymel 370 kPa (melamine formaldehyde resin) are summarized in Table 14. The film is formed as follows: The film is wound onto a wire bobbin on an aluminum panel and then heated to 300 ° F. to form a dry film of about 5 mg per in ² . The overall properties obtained with the aqueous dispersion containing the composition of the present invention are superior to conventional commercial aqueous (WB) epoxy paint resins (Epoxy-1).

TABLE 14

(1) Described in Table 20

(2) changed to 6 upon aging overnight at room temperature.

(3) Curable mixtures tested in each experiment containing the compositions of the present invention made with the indicated examples and the indicated amounts of Cixelmel 370 crosslinking agent.

(4) ASTM D3359-78

(5) ASTM D2794-69 (approved again in 1974)

(6) Described in Table 21

(7) 0.5 cc of concentrated hydrochloric acid or concentrated ammonium hydroxide was coated on the aluminum panel, covered with watch glass, and then the standing panel was washed and evaluated for 1 hour. "Excellent" means that no corrosion occurs on the film, and "Poor" means that some corrosion occurs.

Example 15

The phenoxy resin (Reactant A-VII) used in this Example is a general formula

And a copolymer of bisphenol A and epichlorohydrin represented by (where n is a number from 80 to 90, E is a residue of bisphenol A). The number average molecular weight of the resin was about 25,000 and the viscosity of the solution (measured as a 40% solution in methyl ethyl ketone at 23 ° C.) was 4000 cps. In a 0.5 liter reactor equipped with a reflux cooler, thermometer, stirrer, and heating mantle, 100 g (0.35 hydroxyl equivalent) of phenoxy resin, reactant BI 40 g (0.17 anhydride equivalent), water 6 g (0.33 equivalent), and cyclohexa 300 g Put it. The contents were stirred and heated to give a clear solution, then 0.21 g of benzyl dimethylamine was added. The temperature is adjusted to 119-122 ° C. After 75 minutes, a small amount of samples was found to be dispersed in a water / solvent B / dimethylethanolamine (DMEA) (5/1 / 0.28 weight ratio) solution. After 100 minutes, 25 g of water is added to increase the hydrolysis of the anhydride and slow the esterification of the phenoxy resin to prepare a varnish. 200 g of the varnish was added to 200 g of a water / solvent B / DMEA (5/1 / 0.28 weight ratio) solution, further 50 g of water was added, followed by stirring to prepare an aqueous dispersion. The pH of the resulting dispersion was 8.5 and the viscosity (Brookfield RVT, # 5 spindle, 100 rpm) was 1600 cps. Analysis by aqueous and alcoholic base titration revealed that a large 0.3 anhydride group was esterified per reactant B-I molecule.

This corresponds to the esterification of approximately 1.7 hydroxyl groups per phenoxy polymer molecule.

Example 16

Feed selection

Reactant A may be in any suitable form, such as pellet form or with a suitable solvent such as acetone.

Solvent selection

The aqueous dispersions of the present invention can be prepared in several ways. One method is the "solvent exchange" method described in Example 1. In addition, the block copolymer composition with acetone or THE can be added directly to basic water and stirred, wherein the aqueous dispersion formed can optionally be: 1. used as such, or 2. removed after removal of some or all organic solvents. have. The solvent-free product may optionally be modified with a high boiling point solvent to increase film adhesion.

The wide choice of organic solvents and the wide choice of methods for incorporating the block copolymer compositions of the invention into water to prepare aqueous dispersions. Some examples of general choices are given in the following Tables 15, 16 and 17 for the case where reactant A used to prepare the composition is PVC, such as reactant A-I. In the comparison between the solvent exchange method and the non-solvent exchange method, the latter selection has the advantage that the solvent removal temperature is low when the solvent removal is performed under atmospheric pressure.

Choices 2 and 3 (Tables 16 and 17) result in about 28% volatile organics (solvents and amines) in the final aqueous dispersion with a solids content of 30%.

Choice 3 (Table 17) has several advantages: The block copolymer composition can optionally be recovered in the form of a solid from an acetone solvent by casting or melt stripping the film on a release paper. In addition, drying the varnish results in a very fast formation of a non-stick film

The volatile organics (solvent and amine) content of choice 3 (Table 17) can be further reduced if necessary by vacuum post-striping acetone from the aqueous dispersion. The stripped acetone is replaced with water. The weight ratio of water / volatile organics of the post-striped dispersion is 84/16 calculated. Volatile organics consist of solvent B 76% and amines 24%. Such systems with very low solvent content provide a great deal of freedom for later addition of the desired solvent mixture for a particular end use.

Once special solvent choices are specified, solvent exchange steps can be tailored to produce the optimum dispersion for the desired end use.

TABLE 15

Choice 1: Partial Step by Step Without Solvent Let-Down

TABLE 16

Alternative 2: Partial Solvent Exchange

TABLE 17

Option 3: no solvent exchange

Example 17

Reactant B-I / Reactant A-I Ratio

About 20 parts Phr of reactant B-I (based on 100 parts of reactant A-I) is the preferred amount for the aqueous coating. This composition is sufficient for reactants A-I to preserve the intrinsic properties of PVC. There is also a sufficient amount of reactant B-I to confer good freeze-thaw resistance. Furthermore, systems containing 20 Phr Reactant B-I can be prepared in a wide range of immersion to anhydride ratios.

Prepare a dispersion in which the ratio of reactants A-I and reactants B-I is from 1:10 to about 1: 1. Below a ratio of about 1: 10, the freeze-thaw stability of the aqueous product is not good and the shelf life is reduced. On the other hand, the product is hardly dispersed in the aqueous base below the ratio of 1:20.

In order to properly control the water in the reaction system, the composition of the present invention can be prepared from reactant B-I and reactant A-I mixtures containing up to 100% of reactant B-I. The effect of reactant B-I concentration is summarized below:

TABLE 18

(1) Test method: same as in Example 1.

(2) Test method: Visually measure signs of bubble garden particles, signs of gelation or separation after 7 days at 50 ° F.

(3) Test Method: If no clear condensation appears after 24 hours at 6 ° F, heat to room temperature.

(4) Test method: On glass, visually measure the blurriness in the cast of dry film of wheat thickness.

Example 18

Experimental scale

Several compositions of the invention made of reactant B-I and reactant A-I are scale-up into a 5-gallon reactor. The apparatus used is a 5 gallon stainless steel equipped with a u-type stirrer and a copper cooler. The reactor has a bottom outlet.

Details of typical scale-ups are shown in Table 19 below. The reactant A-I solution is metered into a 5-gallon can. Anhydrous reactants B-I and TEA catalyst are mixed into the solution using a Cowles mixer. The reactant A-I / reactant B-I / catalyst solution formed is transferred to the reactor and refluxed for 30 minutes. The reactor is sometimes "bumped" with nitrogen gas through the bottom port to purify stagnant material in the outlet port. In addition, acetone is removed for 25 minutes to make the solids content in the varnish 63.5%. The lower port of the reactor is opened and the five gallons containing the water / solution B / DMEA mixture are discharged directly to the bin. In this way only 75% of the reactor contents can be discharged.

The water let-down mixtures shown in Table 19 are scaled down in proportion. Optionally, an appropriate amount of let-down mixture can be added to the varnish remaining in the reactor. The result still recovered nearly 100% of the clear product solids).

TABLE 19

Scale-up Procedure to 5-gallon Reactor

The two-phase mixture (with viscous varnish as bottom layer) produced in the let-down step is mixed into a homogeneous aqueous dispersion using a Cowles mixer. (Initially there is a risk of the varnish bouncing off the stirrer shaft and splashing. A low rpm is required until the system is partially homogeneous.) Experiments yielded about 4 gallons of good dispersion. The total treatment time for this example is about 4 hours.

Example 19

Characteristics of Cured Paint

Compositions of the present invention made from hydroxy-containing PVC polymers, which are generally common to PVC polymers, are well balanced in chemical resistance, flexibility, and hardness. The cured paint properties of the aqueous dispersion prepared in Example 18 were in the same range as those of reactant A-I dissolved in an organic solvent and also in the range similarly formulated using a crosslinking additive.

The film properties of the Example 18 product cured with 10-20 phr Cymel 370 are summarized in Tables 20, 21, 22. The paints formed from the dispersions prepared in Example 18 were compared with commercially available waterborne epoxy can paints (Epoxy-2 and Epoxy-3). The solvent-containing formulation of the varnish prepared in Example 18 is also compared to the physical mixing of reactants A-I and reactants B-I and to reactants A-I.

TABLE 20

# Immerse in boiling water for 10 minutes. Grade: 10 = no change Weak bleaching, slow speed indicates severe bleaching.

## Carried out at the indicated Cecsimel 370 ＂concentration.

* 10phr Cucamel 370 ＂.

** 20phr Cessamel 370 ＂.

*** Refers to the reaction product of Example 18 prior to dilution with water. This reaction product is diluted with MIBK.

TABLE 21

All beanie chloride polymer systems (except epoxy-2 and epoxy-3 systems) are cured with 10phr Simel 370.

# Solvent resistance test (＂MEK double-friction test): The one-sided chewing cloth is grouped into a fire of about 1/2＂ diameter. Immerse in saturated MEK solvent. Squeeze the cheese at moderate pressure. The panel is rubbed back and forth (1 cycle) and continued until:

1) The coating is completely consumed on the surface and the number of friction cycles is recorded.

2) If there is no effect at 100 cycles, record the result as 100+. Other test conditions and ratios are described in Tables 20 and 21.

*** denotes the reaction product of Example 18 prior to dilution with water. This reaction product is further diluted with MIBK.

Table 22

* Increased impact at test 4 inch-pound consumption increase on 28 mil aluminum panel, highest pass, value in inch-pound, using the procedure of ASTMD 2794.

* 10phr Cucamel 370 ＂

** 20phr Chamamel 370 ＂

*** is the reaction product of Example 18 prior to dilution with water, the reaction product being further converted into MIBK

The brush resistance in boiling water is very sensitive to the presence of chloride salts in the film and the state of curing. In this characteristic, the coating made with the composition of Example 18 is superior to the coating made with solvent-containing reactant A-I and is in the same range as commercial waterborne epoxy can paints (Epoxy-1 and Epoxy-2). Depending on the impact resistance or the state of hardening, both properties above need to be considered along with the definition of crosslinker concentration and hardening cycle. Solvent resistance of the aqueous and solvent-containing vinyl chloride polymers is superior to commercial aqueous aqueous epoxy can paints.

The color and glossiness of the paint prepared from the composition of Example 18 is very good. Decolorization by sunlight is superior to solvent containing reactant AI. Heating at 385 ° F. for 3 minutes or at 300 ° F. for 30 minutes is allowed without adding a heat stabilizer. The boundary at this time is 3 minutes at 385 ° F .: When this limit is exceeded, discoloration begins in the thicker areas of the film. Color stability is excellent when heated at can paint weight (4-6 mg of anhydrous paint per coated surface in ² ).

Example 20

Film Properties of Aging Compositions of the Invention

The film properties are not significantly affected by the aging of the composition of the present invention prepared in Example 1 (in the form of an organic solution (varnish) or in the form of an aqueous dispersion of a composition salt). One experimental result supporting this is shown below:

TABLE 23

Film Characteristics: Initial / After Aging *

Initial: Aged the varnish of Example 1 for 15 weeks. Aqueous base and Cymel were added immediately before testing.

After aging: The aqueous dispersion of Example 1 was aged for 15 weeks at room temperature. Cymel was added immediately before testing.

Other experimental conditions and data are shown in Tables 20-22.

Example 21

* Styrene-maleic acid having a number average molecular weight (Mn) of 1700 as the brand name SMA-2000;

Procedure: Add acetone and reactant A-I to the reactor, then add reactant B-III and dissolve. Raise to reflux (about 60 ° C). Water is added and mixed, then a catalyst solution is added and mixed. The reflux temperature is maintained until the reaction mixture droplets are dispersed in DMEA / Solvent B / Water (5/9/86 wt.%) Test solution. The reaction mixture was dispersed in the test solution after 55 minutes at reflux temperature from the addition of the catalyst solution.

Next, 129 g of solvent B is added and 220 g of solvent (mostly acetone) are removed by distillation. The resulting product was a viscous varnish with a solids content of 66.0%. The viscous varnish is diluted with the test solution to form a translucent, uniform aqueous dispersion with a solids content of 21.4% and a viscosity of about 200 cps.

Example 22

Partial ester of reactant B-I (35-50% is esterified) and marketed under the trade name SMA-17352.

step :

Acetone and reactants A-I are placed in a reactor and mixed. Reactant B-IV is added thereto and then dissolved. Raise to reflux (about 60 ° C.). Add catalyst solution and mix. Continue reflux until the reaction mixture droplets are dispersed in the DMEA / Solvent B / Water (5/9/86 wt.%) Test solution. After adding the catalyst solution, 64 minutes at reflux temperature, the reaction mixture is dispersed in the test solution.

Next, 129 g of solvent A is added and 216 g of solvent (mostly acetone) are distilled off. The resulting product is a viscous varnish with a solids content of 64.8%. Viscous varnish is added to a DMEA / Solvent B / water (5/16/79 wt.%) Solution and stirred to form a clear, uniform aqueous dispersion with a viscosity of 348 CP and a solids content of 35.2%.

[Comparative Examples J and K]

In a 500 cc reactor, 400 g of 50% acetone solution of reactant A-VI, 100 g of 40% acetone solution of reactant B-V and 11.4 g of water are added. The reactor is heated to reflux (57 ° C.). At this time, 6 g of TEA / 6 g of acetone are added. In 10 minutes the contents gelled.

The experiment is repeated using reactant B-V (ie, 25 g of 40% solution). The hydrolysis of reactant B-V removes water because it causes reactant B-V to become insoluble. After 140 minutes at 57 ° C., if water dispersibility is not achieved, add 25 g of reactant B-V solution again. After 40 minutes, the contents gelled.

This example illustrates that the ethylene-maleic anhydride copolymer is not suitable for the process of the present invention.

Example 23

In this example, bisphenol-A-terminated epoxy resin is used as solvent B as a single solution.

To a 500 cc three-necked glass reactor equipped with a stirrer, cooling and thermocouple are added 179.8 g of EPON-829 (as defined in the present description) and 120.2 g of bisphenol-A. The resulting mixture is heated and stirred to a temperature of 175 to 180 ° C.

After 25 minutes, 45 g of solvent B is added. After 4 hours, analysis of the content of epoxy groups revealed only 0.08% of the epoxy groups, which was then cooled to 63 ° C. 120 g of reactant B-I / acetone 50% solution are added together with 6 g TEA / 6 g acetone. Heat to 91 ° C. and distillate to collect. 35 g of solvent B is added to lower the viscosity. When the temperature of the batch reaches 111 ° C., the distillation is exchanged for reflux. The total amount of distillate collected was 26 g. Heating is continued under reflux and the dispersion to water / solvent B / DMEA (5/1 / 0.28% by weight) is measured every half hour. The temperature was raised to 123 ° C. in 3 hours 17 minutes, and the sample became water-dispersible.

The varnish formed is cooled to 93 ° C. 200 g of the varnish is added to a mixture of 159.2 g of water, 31.9 g of solvent B, and 8.9 g of DMEA, and stirred. As a result, a creamy, uniform aqueous dispersion with the following properties was formed.

＂Cymel 370＂ (15phr) is added to the above dispersion and formulated. Using the curable mixture formed, the film is predominantly on an aluminum θ panel and cured at 350 ° F. for 15 minutes. Cured film properties are as follows:

Experimental methods are described in the previous examples.

[Comparative Example L]

In a 500 cc reaction vessel, 400 g of 50% acetone solution of reactant A-VII, 36 g of 28% acetone solution of reactant B-VI, 6 g of TEA, and 14 g of solvent B were added. Heat to reflux temperature of 59 ° C and periodically test the dispersion for water / solvent B / DMEA (5/1 / 0.28). After 167 minutes, 37 g of 28% PA-18 / acetone are added. After 68 minutes additional 6 g TEA is added. After 11 hours at 59 ° C., gelation occurred without reaching the water-dispersed state.

Reactant B-VI used in this example is a solid linear polyanhydride polymer derived from octadeken-1 and maleic anhydride. The comonomer used to make reactant B-VI is a molar ratio of 1: 1. The number average molecular weight of reactant B-VI is about 50,000. Moreover, it is marketed under the brand name of "PA-18".

This example shows that reactant B is too high in molecular weight and cannot be used in the present invention.

Example 24

200 g of reactant A-VI, 160 g of solvent B, and 40 g of acetone were placed in a 500 cc three-necked glass reactor equipped with a stirrer, reflux, cooler, and thermocouple. The resulting mixture is heated to 80 ° C. for 1 hour with stirring. At this time, reactant A-VI is dissolved and 40 g of reactant B-I is added. Stirring is continued at 80 ° C. for 30 minutes to dissolve Reactant B-I. At this time, a solution of 6.0 g of TEA / 6 g of acetone was added. After 40 minutes, the test sample was dispersed in basic water. 25 g of water are added and heated at reflux for an additional 156 minutes.

200 g of the varnish are added to 200 g of water / solvent B / DMEA (5/1 / 0.28% by weight) and 250 g of water are added again. After 2 weeks at 50 ° C., the sample was still fluid, and after 2 weeks at room temperature, some precipitate was observed.

Example 25

This example relates to experiments by spraying the various compositions and various reactants of the present invention.

25 parts by weight of reactant R-I are dissolved in 50 parts of acetone. The resulting solution is diluted with a mixture of 345 parts by weight of water and 80 parts by weight of solvent B. The resulting solution contains approximately 5% by weight of reactant A-I.

The following reactions were tested in the manner described above with the base used to neutralize the carboxy group;

Each of the three reactants formed a clear solution without any solids. The solution was passed through a 325 mesh screen to give no solids. The reactants are therefore all water-dispersible.

The composition of the present invention prepared in the Examples was tested according to the above procedure with the indicated amount of base (DMEA) used to neutralize 100% of the carboxy group to prepare an aqueous dispersion:

TABLE 24

Dispersion Characteristics

* Based on reactant A-I.

As a result of particle size measurement (Coulter sub-Micron particle size analyzer, Model N-4, used), all compositions were water-dispersible and no solid remained.

[Examples 26, 27 and 28]

Three kinds of aqueous dispersions of the present invention are prepared as follows:

TABLE 25

Reaction mixture

Both reactants are placed in the reactor as a solution with acetone, the solution is raised to reflux (about 60 ° C.) and then TEA is added. The resulting reaction mixture was heated for 30 minutes, resulting in a varnish containing a composition having a reactant B-I molecular weight ester group of 1.2. To prepare the varnish, the following equivalent groups of water and anhydride were used.

TABLE 26

Next, 9 g of water was added to each reaction mixture and reacted at 30 to 40 ° C. for 1 hour to prepare a varnish.

A solution consisting of solvent B 57.4, DMEA 8.1, and 221 g was added to each varnish

The film was cast (5 mils thick into a glass plate) from an aqueous dispersion free of acetone and water, resulting in a clean film free of grit-like material.

Preferred Procedure for Use of Hydrophobic Vinyl Polymer as Reactant A

As shown in Examples A, C, D, E and F above, the compositions having a number average molecular weight of about 6000 (as in Reactant II and Reactant III) prepared from hydrophobic hydroxyl-containing vinyl resins were initially It did not dissolve in water when the addition method was used.

Compositions with high molecular weight and low hydroxy content (2% OH in React II and 2.9% OH in React I) partially fulfill this behavior. Other important factors include high vinyl chloride levels (80% for reactants A-II and A-III and 69% for reactants A-I). In addition, in order to understand the effect of the composition factor, polyvinylpolyol is combined with a small amount of toluene diisocyanate. As a result, the hydrophilicity of the polyol was maintained but its molecular weight increased. The results of this method should be interpreted with caution as branched polymers can be formed. However, at low levels of binding (about 10% of hydroxyl groups reacted) this effect is almost negligible. The results obtained are reported in Table 27 below. The data show that the compositions made from certain polyvinylpolyols and reactants B-I disperse very well despite the molecular weights of 9000 to 12000. Alcoholic reactant IX (defined in Example 33), on the other hand, comparable in hydroxyl content and molecular weight, is not dispersed even after reacting with reactant B-I. Amount of ester group, type of reactant used and ratio amine

TABLE 27

1. Dispersibility Test

2. Reaction product of reactant A-XII with toylene diisocyanate, reactant A-XII is about 62% by weight of pre-polymerized vinyl chloride, about 4% by weight of polymerized vinyl acetate and about 34% by weight of polymerized hydroxy propyl acrylic Contains the rate. About 10% of OH of reactant A XII reacts with diisocyanate.

3. Copolymer containing 35 wt% polymerized vinylchloride and 65 wt% polymerized hydroxy propyl acrylate.

4. The reaction product of reactant A-XIII with about 10% of tolylene diisocyanate of OH of reactant A-XIII reacts with the diisocyanate.

Although molecular weight composition is important in determining the degree of dispersion of a composition made of vinyl polymer, physical factors are equally important as well. Dispersion monitoring tests may be insufficient for other compositions, even if the water-dispersible composition (such as those made with reactant AI and reactant BI) is accurate at the level of esterification to pass the dispersion test. ₂

TABLE 28

During the above procedure, the viscosity of the reaction mixture rises to its maximum and then falls. The changes that occur during emulsion formation appear in three steps. Initially, when the aqueous medium is slowly added to the hot polymer solution, it dilutes the acetone solvent and eventually dissolves any insoluble amine / carboxylate salt present. In the second step, the solution becomes opaque and rises in viscosity as the polymer phase separates. In the last step, a sudden drop in viscosity occurs when the water-swelled polymer particle-acetone mixture becomes an O / W type dispersion. In this preferred procedure the variables are used to prepare the compositions described below.

[Effect of Composition Variable]

The specific physical requirements for preparing a stable dispersion from a specific combination of reactants A and reactant B will depend on the chemistry of the bond. Factors that need to be considered include: (a) molecular weight of reactant A, (b) hydrophilic / hydrophobic balance (eg% OH, and halogen levels), (c) level of esterification, (d) COO ^- the level and position (amount and type of the reactants B and immersion conditions), (e) the type of the used amine.

Four different vinyl polymers as shown in Table 29 having a hydroxyl content of 1.1 to 5.3% by weight and a number average molecular weight of 8500 to 23000 are tested. Aqueous dispersions can be prepared in the preferred procedure using reactant combinations, although they differ in stability from one another. Excellent dispersions can be prepared with a combination of reactants B-I and reactants A-V, X or XI. Although compositions prepared from reactants B-I and reactants III or X can be injected in the form of a dispersion from acetone, they are less stable and soon precipitate.

TABLE 29

1. Vinyl chloride weight before polymerization

2. Polymerized vinyl acetate weight%

3. Polymerized hydroxypropyl acrylate weight%

4. Vinyl alcohol weight%

a. Reactant A-II / Reactant B-I Combination

A composition having an ester group of 0.5 to 1.5 per molecule of reactant B-I is prepared at a reactant B-I level of 2.5,5,10, and 20 phr reactant A-II in anhydrous acetone with a sieving content of 30%. This intermediate level of esterification is chosen because very low levels of product can be dispersed and access to the three ester bonds / reactants B-I presents a risk of gelation. Although the TEA catalyst concentration is constant, the reaction time required to achieve increased desired ester levels as reactant B-I is reduced. Excellent dispersions can be prepared from the 5,10 and 20 phr reactant B-I addition products, but the results are not satisfactory with 2.5 phr reactant B-I. The 5 phr product did not pass the freeze-thaw experiment.

TABLE 30a

Binding method of reactant A-II / reactant B-I

TABLE 30b

Binding method of reactant A-II / reactant B

In preparing scale-up compositions, several studies are performed. This experiment shows that at the highest concentration (50% solids) for acetone, the esterification reaction proceeds rapidly and the polymer gels before cooling. The reaction can be easily controlled by adding 3% water at the starting point, but since the heat transfer is not easy, a gel layer forms at the bottom of the reactor. Subsequent experiments were carried out with a solids content of 45%, resulting in 0.7 ester groups per molecule of reactant B within 1 hour without difficulty, which is used for scale-up.

As a result of the above, about 4 gallons of each 5 to 10 phr scale-up composition were prepared.

For reactant B, the ratio of styrene-maleic anhydride was changed from 1: 1 (reactant BI) to 2: 1 (reactant B-III) and finally 3: 1 (reactant B-VII). The stability was significantly reduced when used as. Dispersions can be prepared using 20 phr of reactant B-III (ester group 1.3 per molecule of reactant B), but will precipitate out when the acetone is removed. 20 phr of reactant B-VII in acetone cannot remove the dispersion. When the solvent is replaced with MEK, a water-dispersion liquid is formed, but when the solvent is removed, it becomes granular. However, doubling the amount of intersolvent results in a good final dispersion.

When the reaction proceeds in order to BI, reactant B-III and the reactant B-VII of the observed stability ^-

b. Reactant A-XI / Reactant B-I Combination

Satisfactory dispersions are prepared with compositions prepared with reactants A-XI and 5,10, and 20 phr of reactant B-I. The large batch of acetone removed 20 phr product had a pH of 8.3 and a viscosity of 60 cp 27.4% reactant B-I (Table 31). The particle size (weight average obtained using the spectrophotometry) was 1029 mm 3.

Table 31

Preparation of Compositions from Reactants B-I and Various Reactants A

c. Reactant A-X / Reactant B-I Combination

Despite the fact that the hydroxyls in reactants A-X are derived vinyl alcohols,

A 20 phr product was formed and vacuum removed to give a solids content of 19.4% and a pH of 9.4. The viscosity was 80 cps and the particle size was 1145 kPa.

d. Reactant A-III / Reactant B-I and Reactant IX / Reactant B-I.

In contrast to the excellent dispersions with reactants A-X, reactants III and IX, containing hydroxyl in the form of vinyl alcohol, satisfactory results were not obtained when prepared in acetone. In all of the above cases, the stability of the emulsion was at a minimum and precipitation occurred within one week when left at room temperature. An excellent product was formed when the dispersion was prepared using methyl ethyl ketone.

Examples 26-33 describe in more detail the above preferred method for preparing a water-dispersible composition using a hydrophobic polymer as reactant A.

Example 29

Procedures similar to those described in Examples 26, 27, and 28 are repeated using the following starting materials:

(1) Reactant B-VII is a styrene / maleic anhydride copolymer sold under the trade name “SMA-3000” having a number average molecular weight of 1900, an acid number of 275 and a styrene / maleic anhydride ratio of 3: 1 on a molar basis.

The reaction is placed in the reactor as a solution with the indicated amount of MEK. TEA is added and heated to the reaction mixture reflux temperature (about 80 ° C.) formed at this time. Reflux is continued until about 0.8 ester groups are formed per reactant B-VII molecule.

Example 30

The reaction mixture of 60 g of reactant A-III, 12 g of reactant B-I, 212 g of acetone and 1.6 g of TEA is heated to 60 ° C. (reflux temperature) for about 45 minutes to form 0.9 ester groups per molecule of reactant B-I. The mixture is then cooled with 9.0 g of water to form a varnish. The following materials are used:

The varnish is then diluted with a mixture of 58.9 g solvent, 8.2 g DMEA and 235.7 g H ₂ O. Detailed procedure: The following material is added to a three necked round bottom flask equipped with a stirrer, funnel and reflux condenser:

1) 60 g of reactant A-III / 300 g of acetone

2) 12 g solution of reactant B-I / 12 g of acetone

3) At reflux, 1.6 g of TEA is added.

The resulting mixture is refluxed until about 0.9 ester groups are formed per reactant B-I molecule. Water is added and the mixture is kept at a temperature varying from 40-80 ° C. for 1 hour to prepare a varnish.

Next, 287.1 g of varnishes are added with stirring:

A sample of diluted material (aqueous dispersion containing organic solvent) is cast on a glass plate to a thickness of 5 mils. The dispersion was air dried to form a clear, glossy film.

The dispersion is then vacuum distilled under about 26 inHg pressure until the solids content reaches 35.7 weight percent (removing the organic solvent).

The dispersion with a total solids content of 35.7% is cast on a glass sheet with a thickness of 5 mils. Air drying resulted in a clear, glossy film.

e. Its neutrality for cooling-dispersity

In most cases, the composition produced by esterifying the hydroxyl groups of the vinyl polymer with styrene-maleic anhydride is not stable, but the molecular weight continues to increase, ultimately forming a gel. In order to prevent this phenomenon, a small amount of water can be added to inhibit the esterification reaction by hydrolysis of the remaining anhydride groups. The cooling method also uses the ratio

The dispersity can be compared with reactant A-I with 20 phr of reactant B-I, whereas the initial dispersity is not good with 10 and 5 phr while increasing after 8-12 hours. Here, high molecular weight and reduced hydroxyl content (Mn12000, [OH] = 1.1%) require additional COO-groups in the esterification reaction.

To 25 g of warm (50 ° C.) varnish formed above, a solution of 5 g of solvent B, 0.7 g of DMEA and 20 g of water is added with stirring to disperse. At this time, the formed water-dispersion liquid was cast on the glass plate to a thickness of 5 mils, and then air-dried to form many films.

Example 31

Follow a similar procedure to Examples 26, 27, and 28 using the following combinations:

Table 32

(1) Reactant A-IX is a tripolymer having 91 weight percent vinyl chloride, 3 weight percent vinyl acetate and 6 weight percent vinyl alcohol, having a number average molecular weight of about 23,000.

The reaction is dissolved in MEK, then placed in a reactor and heated to reflux temperature of about 77 ° C. The reaction mixture formed with the addition of TEA was approximately 1.2 S per molecule of reactant B-VII.

At this time, the formed varnish is processed again as follows:

To 25 g of varnish, 5 g of solvent B, 1 g of DMEA, and 5 g of water are added. At this time, water is slowly added while stirring. When 5 g of water is completely added, the varnish becomes cloudy. The partially diluted varnish was then transferred to an ultrasonic stirrer and the stirrer was run completely, and 20 g of water was added to form an aqueous dispersion. The dispersion was cast on a glass plate to a thickness of 5 mils and air dried to form a clear, glossy film.

Example 32

Three aqueous dispersions (dispersions A, B and C) according to the invention are prepared as follows:

Dispersion A

Table 33

Reaction mixture

(1) Reactant A-X is a tripolymer with 80% by weight vinyl chloride, 6% by weight vinyl acetate and 14% by weight vinyl alcohol, having a number average molecular weight of about 23,000.

The reaction mixture was heated for 45 minutes at a reflux temperature of about 60 ° C. for 45 minutes to form a dispersion with 1.2 ester groups per molecule of reactant B-I. Next, 9.0 g of water is added and the reaction is stopped by heating to 60 DEG C for 1 hour. The amount of material used for the reaction is as follows:

Next, 54.3 g of solvent B was added, a solution of 5.4 g of DMEA and 217.0 g of water was added, and most of the acetone was evaporated to form an aqueous dispersion (dispersion A).

Dispersion B

Dispersion B is prepared in the same manner as in dispersion A, except that 54.3 g of solvent C is used instead of solvent B.

Dispersion C

Dispersion C is prepared in the same manner as in dispersion A, except that both half of DMEA is used.

Example 33

Follow a similar procedure to that shown in Examples 25, 26, and 27 using the following combinations:

Table 34

(1) Reactant A-IX is a tripolymer consisting of 60% by weight vinyl chloride, 32% by weight vinyl acetate and 8% by weight hydroxyl propyl acrylate, having a number average molecular weight of about 12,000.

Add reactant A-XI / acetone solution and reactant B-I / acetone solution to the reactor

Next, 9.0 g of water was added, and the reaction mixture was maintained at about 60 ° C. for 1 hour to form a varnish. Then, while stirring, a solution of solvent B 45.3, DMEA 5.1, and 181.4 g of water was added to 307.0 g of varnish to form an aqueous dispersion. An aqueous dispersion sample was cast to a thickness of 5 mils on a glass plate and air dried to form a clear, glossy film.

The dispersion is vacuum distilled to a pressure of 26 inHg to remove the organic solvent until the solids content reaches 27.4% by weight. A final dispersion sample of 27.4% solids content was cast on the glass substrate to a thickness of 5 mils and air dried to form a clear, glossy film.

Example 34

Follow the procedure of Examples 25, 26 and 27 using the following combinations:

Table 35

The reactant B-VIII (1) above is a maleated polybutadiene commercially available under the trade name “BN-1015”, having a number average molecular weight of about 1150 and anhydride equivalents per mole.

The reaction is dissolved in acetone and placed in a reactor, then heated to reflux temperature of about 60 ° C.

TEA is added and refluxing is continued for about 58 minutes until about 0.3 ester groups are formed per mole of reactant B-VIII. Next, 10 g of water is added and a temperature of 60 ° C. is maintained for about 1 hour.

Using the ultrasonic device described in Example 31, 30 g of the formed varnish was mixed with 24.8 g of water, 5.0 g of solvent B and 0.2 g of DMEA to form an aqueous dispersion. The dispersion was cast on a glass sheet to a thickness of 5 mils and air dried to form a clear, glossy film.

Example 35

The composition of the varnish of Example 1 is as follows:

To 128.3 g of varnish is added 65.7 g of a 35% solid solution of a MEK solvent with a tripolymer having a molecular weight of about 15,000 consisting of 86% vinyl chloride, 13% vinyl acetate and 1% maleic anhydride.

Next, 26.0 g of solvent B, 8.0 g of DMEA, and 226.0 g of water (260.0 total) were slowly added while stirring. The formed aqueous dispersion is cast on the glass plate as a film. The film was air-dried to some extent, but it was found to be a tough film when measured by nail marks.

Example 36

The composition of the aqueous dispersion of Example 1 is as follows:

Using the above dispersion, the following paint combinations are prepared:

TABLE 36

* ＂NV＂: Non-volatile component.

** ＂NeoRez resin is an aqueous dispersion of urethane elastomer.

Combinations A, B, C, D and F are cast on a steel “Q panel” into a film about 0.9 mils thick. All treated panels are heated to 300 ° F for 10 minutes. Next, the impact value is measured according to ASTM D-2744. The result is as follows:

Table 37

* Highest value that passed the test

Combinations A, C and E are applied to a poly (ethylene terephthalate) film to form an anhydrous film about 0.2 mils thick. The combination is then dried at 250 ° F. for 2 minutes. The adhesion of the treated film is graded by the Scotch Tape # 610 Test (ASTM D-3359). The result is as follows:

TABLE 38

Combinations A, C, and E are prepared as inks by adding [Tint-Ayd® WE-2228, phthalo blue pigment dispersions of 4.2 to Combinations A, C and E, respectively. The ink is cast into aluminum foil and the vinyl film is plasticized to a thickness of about 0.2 mils. The ink is dried at 90 ° C. for 1 minute. The adhesion is tested by the above method. The result is as follows:

TABLE 39

Example 37

The aqueous dispersion of Example 1 is combined with various other acrylic and vinyl acrylic latexes and phenolic resins as follows.

TABLE 40

* Total solids in acrylic resin (%)

＂Sl＂ means some degree and ＂mod＂ means moderate.

The blend is predominantly in the glass plate to produce a 0.9 mil thick dry film. After air drying for 20 minutes, the film is then dried at 60 ° C. for 30 minutes. As a result of the above, the transparency of all films is measured. All films were formed into films that were tough on nail marks.

Next, mainly on a glass plate and air-dried, a clear coating formed on the nail marks was formed.

Example 38

Put a solution of the following substances into the reactor:

Reactant B-I (43.3 g) is dissolved in the solution and the resulting mixture is refluxed to about 60 ° C. 3.1 g of TEA is added and the resulting mixture is refluxed for 75 minutes. A mixture of 399 g of water, 40 g of solvent B and 11 g of DMEA are added slowly with stirring. Solvent removal of the mixture under reduced pressure resulted in an aqueous dispersion having a final non-volatile content of 43% by weight.

Example 39

Water-reducible alkyd resin sold under the trade name “kelsol 3909” in solvent B and butanol mixtures with a solids content of 75% by weight, an acid value of 37, a weight of 8.56 pounds per gallon, a Gardner-Holt viscosity of Z5 + 37.5 g of the mixture was thoroughly mixed with 30 g of 2.5% aqueous ammonium hydroxide solution, and a uniform emulsion was formed. Next, 21 g of the varnish of Example 1 was mixed with 28.5 g of an aqueous 2.5% ammonium hydroxide solution to form a uniform emulsion (Vannish emulsion). The alkyd emulsion and varnish emulsion are thoroughly mixed. The emulsion mixture was applied on a glass plate to a thickness of 5 mils and then dried to form anhydrous films faster than with the alkyd emulsions themselves.

Example 40

Water-reducible alkyd resin 37.5 with a solids content of 75% by weight in solvent B and butanol mixtures, an acid value of 37, a weight of 8.56 pounds per gallon, a Gardner-Holt degree of Z5 + and a kelsol 3909 ＂trademark g was thoroughly mixed with 21 g of varnish of Example 1 to form a mixture of 70 parts by weight of alkyd resin and 30 parts by weight of varnish. The mixture was mixed uniformly and then 58.5 g of 2.5% aqueous ammonium hydroxide solution was added with stirring to form a uniform emulsion. Applying the emulsion on a glass plate to a thickness of 5 mils; Control alkyd resin prepared in a similar manner except that it does not contain varnish as a result of drying

Example 41

333 g of 15% reactant A-IXcyclohexanone solution is added to a 500 cc reaction flask equipped with a heating anetle, stirrer, reflux cooler and thermocouple followed by 10 g of reactant B-VII. Heat and stir to dissolve reactant B-VII, then add 3.0 g of TEA and continue stirring at 82-83 ° C. for 2 hours and 37 minutes. The product is cooled to 4.3 g of water (10 times the anhydride equivalent) and then heated to 60 ° C. for 4 hours. Vacuum distillation then separates 14 g of distillate (to remove residual water). As a result, the anhydride level was 37% (measured as acid) and 9% acid group esterified (ester group 0.8 per mole of reactant B-VII). The resulting varnish remained stable upon storage at room temperature for 5 months.

The varnish is tested as an improved iron oxide pigment dispersant for magnetic recording tapes. The varnish is mixed with an equivalent amount (solid basis) of reactant A-IX and then reactant A using 2,1,0.5 and 0.0% ＂GAFAC RE-610 (alkylphenol ethoxylate phosphate surfactant) as a combination. Test glossiness for -IX.

The results show that the varnish improved markedly. Varnishes are also tested in combinations containing Reactant IX and “Estane 5701” (used as polyurethane component of the self-tape binder composition). The combination used (mixed to cyclohexanone) contains:

Gamma-ferric oxide (＂P Ferrox 2228-Hc＂)-100 g

-20 g of polymer, and "GAFAC RE-160" -0.0 to 2%

The result is as follows.

Table 41

Weight ratio

Example 42

The following materials and procedures were followed to produce a stable aqueous dispersion. :

Table 42

The reaction mixture containing the material is heated to reflux temperature of 80 ° C. for 1 hour. At this time a varnish containing a composition having an ester group of 1.0 per mole of reactant was formed. To the varnish add the following solution:

Table 43

Vacuum distillation removed the MEK and some water, resulting in an aqueous dispersion with the following properties.

As a result of drying the dispersion, a clear and glossy film was formed.

Example 43

A stable aqueous dispersion was prepared as follows:

Table 44

Reactant A-XV, reactant B-I and acetone solution are placed in a flask and refluxed at about 59 ° C. TEA catalyst was added and the reaction mixture was refluxed for 45 minutes.

The reactant A-XV is a tetrapolymer of about 80 wt% vinyl chloride, 6 wt% vinyl acetate, 13 wt% vinyl alcohol, and 1 wt% maleic acid, and has a number average molecular weight of about 23,000.

Claims (51)

(One). (i) a water non-dispersible, film-forming organic polymer (reactant A ') having an average number of hydroxyl groups per molecule of at least three, and (ii) an average number of average carboxylic acid anhydride groups per molecule having at least two, After polymerizing the anhydride group with a base to form a reaction mixture consisting of an ethylene-maleic anhydride copolymer which is an organic polymer which becomes water-dispersible and (iii) an esterification catalyst; (2). To the extent necessary to prepare a film-forming composition capable of polymerizing at least some carboxyl groups with a base and then dispersing it in a first aqueous medium having a pH of 5 or more, the hydroxyl groups of reactant A and the anhydride groups of reactant B are reacted to produce esters. Forming a group with a carboxy group; (3). A water-dispersible, block copolymer coating composition characterized by binding a low molecular weight organic compound or water containing one or two groups reactive with anhydride groups to the reaction mixture to prevent gelation, thereby controlling the reaction of the composition. Manufacturing method. The method of claim 1, wherein the reaction mixture also contains an organic solvent and the product in the composition is dissolved in the solvent to form a varnish. The method of claim 2 wherein the organic solvent is a water soluble dialkyl ketone. The process of claim 1 wherein reactant A is a vinyl chloride / vinyl acetate / hydroxy alkyl acrylate terpolymer having 2 to about 6 carbon atoms in the hydroxy alkyl moiety. The process of claim 1 wherein reactant B is a styrene / maleic anhydride copolymer. The process of claim 2 wherein the organic solvent is removed from the varnish and exchanged with a monoalkyl glycol ether having from 1 to about 6 carbon atoms in the alkyl site. The process of claim 6 wherein the organic solvent removed is acetone and the monoalkyl glycol ether is a monobutyl ether of ethylene glycol. The method of claim 1 wherein the catalyst is a trialkylamine having from 1 to about 4 carbon atoms in the alkyl moiety. The method according to claim 2, wherein the block copolymer varnish is contacted with an aqueous solution containing a base and an organic solvent to obtain a stable aqueous dispersion. The method of claim 9, wherein the base is dimethylethanolamine and the organic solvent is alkyl glycol having 2 to about 4 carbon atoms in the alkyl moiety. The method of claim 9, wherein the aqueous dispersion is mixed with a water soluble crosslinker. The method of claim 11, wherein the crosslinking agent is hexamethoxymethylmelamine. The method of claim 1, wherein the reaction is controlled to prevent gelation by introducing water into the reaction mixture. The method of claim 1, wherein the reaction is controlled by introducing a low molecular weight organic compound having a molecular weight of 200 or less into the reaction mixture to prevent gelation. The method of claim 1, wherein the reaction is controlled by introducing a low molecular weight organic compound having a molecular weight of 120 or less into the reaction mixture to prevent gelation. The method of claim 1, wherein the reaction is controlled by introducing monohydric alcohol into the reaction mixture to prevent gelation. (A) a water non-dispersible, film-forming organic polymer component (component I ') having an average number of hydroxyl groups per molecule of at least 3, and (B) an average number of average carboxylic acid groups per molecule having at least two, and at least some Esters linking at least some component I with at least component II, consisting of an organic polymer component derived from ethylene-maleic anhydride copolymer (VIII-component II), which is dispersed in water after the carboxyl group of Wherein the number of groups averages 0.1 to 3.1 per mole of component I, and after neutralizing at least some carboxyl groups with a base, the block copolymer coating composition is dispersed in a first aqueous medium having a pH of 5 or more. 18. A parent according to claim 17 wherein the number average molecular weight of component I is from 500 to 35,000 or 50,000 18. The composition of claim 17, wherein the component I is a hydrophilic addition polymer having a number average molecular weight of 3,000 to 35,000 or 50,000. 18. The composition of claim 17, wherein component I is a hydrophobic addition polymer having a number average molecular weight of 500 to 6,000 or 20,000. 18. The composition of claim 17, wherein the component I is a hydrophobic addition polymer having a number average molecular weight of 3,000 to 5,000 or 15,000. 18. The composition of claim 17, wherein the component I is an epoxy polymer or phenoxy polymer having a number average molecular weight of 500 to 50,000. 18. The composition of claim 17 wherein the number average molecular weight of component I is between 3,000 and 40,000 epoxy polymers or phenoxy polymers. 18. The composition of claim 17, wherein component II has a molecular weight of 300 to 30,000. 18. The composition of claim 17, wherein component II has a molecular weight of 800 to 2,500. A solution comprising the composition according to claim 17 and a solvent selected from ketones, hydrocarbons, esters and chlorinated hydrocarbons. A solution comprising the composition according to claim 17 and a solvent selected from acetone, methyl ethyl ketone, ethyl propyl ketone, methyl butyl ketone and ethyl butyl ketone. A solution comprising the composition of claim 17 and a solvent selected from glycols and ethers. The composition according to claim 17 and selected from monobutyl ethylene glycol, monopropylethylene glycol, monoethylethylene glycol, monopropylethylene glycol, monoethylethylene glycol, monomethylethylene glycol, monomethyldiethylene glycol and monoethyldiethylene glycol Solution consisting of a solvent. 18. The composition of claim 17, wherein the composition contains on average 0.5 to 2 ester groups per component I molecule. (A) a water-dispersible, film-forming organic polymer component (component I ') with an average number of hydroxyl groups per molecule of at least 3, and (B) an average number of salt groups derived from carboxylic acid groups and bases per molecule At least 2, consisting of a water-dispersible organic polymer component derived from an ethylene-maleic anhydride copolymer, having an average number of ester groups linking at least some component I to at least some component II on an average of 0.1 to 1 mole of component I 3.1, water-dispersible, salt-containing block copolymer coating composition An aqueous dispersion consisting of a large amount of water and a small amount of the salt-containing coating composition according to claim 31. An aqueous dispersion consisting of a large amount of water, a small amount of the composition according to claim 31 and a small amount of the solvent for said composition. An aqueous dispersion containing 15 to 55% by weight of the composition according to claim 31, 40 to 84% by weight of water and 0 to 35% by weight of the organic solvent for the composition. An aqueous dispersion containing 20 to 35% by weight of the composition according to claim 31, 50 to 70% by weight of water and 5 to 25% by weight of the organic solvent for the composition. A curable mixture consisting of the composition according to claim 31 and a crosslinking agent. 37. The curable mixture of claim 36 wherein the crosslinker is melamine-formaldehyde resin, urea-formaldehyde resin or polyaziridine resin. An aqueous dispersion consisting of a large amount of water and a small amount of the composition according to claim 31 and a crosslinking agent A curable mixture which is an aqueous dispersion consisting of a large amount of water and a small amount of the composition according to claim 31, a crosslinking agent for the composition and an organic solvent for the composition. A solid substrate coated with a coating resulting from curing the mixture according to claim 36 on a substrate. 41. The solid substrate of claim 40, wherein the substrate is a metal. A method of coating a solid substrate, wherein the film of the curable mixture according to claim 36 is added to the substrate and the mixture is cured on the substrate. 33. The dispersion of claim 32, wherein the average particle size of the dispersed particles is no more than 5 microns and no more than 10% by weight of the salt-containing paint composition is filtered through a 325 mesh screen. 33. The aqueous dispersion of claim 32, wherein the dispersed particle has an average particle size of less than 1 micron and less than 2% by weight of the salt-containing composition is filtered through a 325 mesh screen. 33. The aqueous dispersion of claim 32, wherein the average particle size of the dispersed particles is no greater than 5 microns and up to 10% by weight of the salt-containing paint composition is filtered through a 325 mesh screen. 33. The dispersion of claim 32, wherein the average particle size of the dispersed particles is no greater than 1 micron and up to 2% by weight of the salt-containing composition is filtered through a 325 mesh screen. 33. The dispersion of claim 32, wherein the pH is 6-9. 33. The dispersion of claim 32, wherein the pH is 7-8. The method of claim 1, wherein the average particle size of the reactant I and the particles dispersed therein is at least 5 microns or at least 10% by weight of the reactant I and component I form a basic aqueous dispersion filtered through a 325 mesh screen, and reactant II, And wherein the average particle size of the particles in which component II and the block copolymer paint composition are dispersed is 5 microns or less and no more than 10% by weight of the salt formed from reactant B, component II or the composition forms a basic solution filtered through a 325 mesh screen. The process of claim 1 wherein reactant A is a vinyl chloride / vinyl acetate / vinyl alcohol terpolymer. The process of claim 1 wherein reactant A is vinyl chloride / vinyl acetate / vinyl alcohol / maleic acid tetrapolymer.