JPS6059925B2 - Method for producing improved vinyl resin metal coating compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of stable aqueous colloidal dispersions of vinyl resins containing carboxylic or sulfonic acids, and more particularly to the preparation of stable aqueous colloidal dispersions of vinyl resins containing carboxylic or sulfonic acids, and more particularly to the preparation of stable aqueous colloidal dispersions of vinyl resins containing said resins, water, bases, organic solvents, organic co-solvents, and a polymer compound.

Solution polymerized vinyl halide resins have been widely used as internal coating resins for beer cans and beverage cans.

They are US FDA approved vehicles;
To protect a metal substrate well from the corrosive action of its contents, and to provide excellent fogging resistance without any adverse effect on flavor properties during pasteurization. For these reasons, these resins are preferred over most other coating resins for this demanding application. Since these halogenated vinyl resins are usually applied as lacquers, large amounts of organic solvents are released during application.

Because this technology is ecologically undesirable and expensive, it was quickly replaced by other technologies that could reduce the need for solvents to very low levels. The most outstanding technology is water retention, i.e. water retention.
rbOrne) paint technology. Water-retaining coatings can be produced from water-soluble resins, latexes or emulsions.

Water-soluble resin formulations are often too sensitive to water in order to pass the required fog resistance tests. On the other hand, latexes and emulsions obtained by conventional methods may contain one or a combination of surfactants to effect dispersion;
as well as a minor portion from the polymerization initiator system employed. These additives often cause poor fog resistance and/or perhaps bad flavor. It is therefore an object of the present invention to produce water-holding colloidal dispersions of vinyl resins suitable for various coating applications.

The present invention has discovered a method for producing hydrocolloidal dispersions of vinyl resins suitable for a variety of coatings.

- The method comprises: (4) a vinyl resin selected from the group consisting of vinyl chloride, vinylidene chloride, or vinyl chloride/vinylidene chloride copolymer having a carboxylic acid group or a sulfonic acid group in the resin; , (b) a water-miscible base, (c) an organic water-miscible polymer compound, (d) having an affinity for the resin and having a temperature of 160'C or higher.
(e) an organic and water-miscible solvent which is a weak solvent for the resin but is miscible with the organic solvent d; (B) mixing with a solvent and (f) optionally a water-immiscible organic diluent until a stable colloidal dispersion is formed;
The colloidal dispersion thus produced is divided into the total organic solvent and diluent in the final colloidal dispersion, D, e and f.
by stripping until the content is 0.2 to 2% by weight.

These colloidal dispersion systems contain (4) a carboxylic acid group or a sulfonic acid group, and the following moiety copolymerized in the resin: [In each of the above formulas, m and n each have a value of O to 99%. f is a percentage of 100 with a value of 0 to 59%; p is a percentage of 1 to 30 with a value of 0 to 59%;
10 with a value of %; q is m+n+t>
70% and 99%, m+n+t+p+
1 to 1 for p=0, provided that q=100%, n is at least 1 if m=0, and m is at least 1 if n=0. 10 with a value of 30%; X is a monovalent radical selected from the group consisting of -H and lower alkyl having 1 to 4 carbons; W is -H1 lower alkyl, 6 carbons; an aryl having from about 9 . 1100 (where a is 1
-0H1-C-H(R1)2, where R1 is selected from the group consisting of -H1 methyl or ethyl; is a monovalent radical),
is a monovalent radical selected from the group consisting of and -CN; or is a monovalent radical selected from the group consisting of: -SO3H and - provided that and Z are never -COOH and -SO3H at the same time.
is a monovalent radical selected from the group consisting of C6H4-SO3H]; (B
) sufficient water-miscible groups to neutralize 10% to 100% of the carboxylic or sulfonic acid groups; (C) a water-miscible and normal liquid to the vinyl resin;
Solvents having a boiling point of 160° C. or below, selected from the group consisting of lower aliphatic ketones, esters or ethers having 3 to about 6 carbon atoms and cycloaliphatic ketones or ethers having 4 to 6 carbon atoms. 1 to 5 parts by weight of the selected solvent per 100 parts by weight of vinyl resin
(D) Formula (1): (where R″″, R″″″ are each H or CH3, r is an integer having a valence of 1 to 3, and R' is an alkyl group having 1 to 6 carbon atoms or phenyl),
1(2): an aliphatic acidic ether represented by the formula: (wherein R″″″″ is an alkyl group having 1 to 4 carbon atoms);
1 (3) An amino ester represented by the formula:
2 (4): an aminoketone of the formula: (5): an aliphatic alcohol of the formula (6): (wherein R2 is alkyl having 1 to 5 carbons); aliphatic carboxylic acids represented by: H or alkyl having 1 to 4 carbons;
Formula (7): (where R4 and R5 are H or 1 to 6
is an alkyl having 4 carbons, and R6 is R4+R5+
an alkyl having 1 to 6 carbons on the condition that the total number of carbons in the sum of RG is 6),
An aliphatic amine of the formula (8): (wherein R7 is methyl or ethyl and g has a valency of 1 to 4), an aliphatic aminoether of the formula (9): (wherein aliphatic dialkylamides of the formula: where R8 is H or alkyl having 1 to 5 carbons, N of the formula: where R9 is H or -CH3 -(hydroxymethyl)acrylamide and N-(
hydroxymethyl) methacrylamide, formula (11): (where RlO is alkylene having 1 to 3 carbons, and v is an integer having a valence of 1 to 5)
Cycloaliphatic ether alcohol represented by (12)
A compound selected from the group consisting of a hydroxyester represented by the formula: and a hydroxyketone represented by the formula (13), which is a weak solvent for the vinyl resin but is a liquid in a normal state and is a miscible agent with water and solvent C. (E) an alkane having from about 5 to about 2 carbon atoms and a halogenated alkane having from 2 to (8) carbon atoms; , cycloalkanes and halogenated cycloalkanes having 5 to 12 carbon atoms, aromatic hydrocarbons having 6 to 12 carbon atoms, aliphatic or cycloaliphatic ketones having 7 to 12 carbon atoms, cycloaliphatic ketones having 7 to 12 carbon atoms, a water-immiscible organic diluent selected from the group consisting of alkaryl ketones having 12 carbon atoms, aliphatic or aromatic esters having 7 to 12 carbon atoms and olefins having 6 to 2 carbon atoms;
O to 4 parts by weight per 100 parts by weight of organic solvent D;
F) Cellulose ether; poly(alkylene oxide)
; Vinyl alcohol, acrylic acid, methacrylic acid, N-
Homopolymers of vinylpyrrolidone or acrylamide;
and vinyl alcohol, acrylic acid, methacrylic acid, N
- a water-miscible normally solid polymeric organic compound selected from the group consisting of copolymers of vinylpyrrolidone, maleic acid or acrylamide, having the following lipophilic moieties copolymerized therein: (G) sufficient water to obtain an aqueous colloidal dispersion having a total solids content of up to 6% by weight; and then the total content of organic solvents C and D and diluent E is 0.2 to 20% by volume.
Preferably, it is produced by stripping the colloidal dispersion until .

Vinyl resins useful in the present invention in the broadest sense are copolymers of vinyl chloride and vinylidene chloride, or vinyl comonomers having at least one carboxylic acid group -COOH, or a sulfonic acid group, -SO3H. Both are copolymerized with the top gloss.

Typical examples of these resins include copolymers of vinyl chloride and acrylic acid or methacrylic acid, vinyl chloride and maleic acid, vinyl chloride and styrene sulfonic acid; vinylidene chloride and acrylic acid or methacrylic acid, vinylidene chloride and maleic acid. Acids, including copolymers of vinylidene chloride and styrene sulfonic acid. These vinyl resins also include, for example, ternary copolymers containing the following monomers copolymerized therein.

Vinyl chloride / Vinyl acetate / Vinyl acrylate chloride / Vinyl acetate / Vinyl maleate chloride / Vinyl acetate / Vinyl chloride crotonate / Vinyl acetate / 5-norbornene-2,3-dicarboxylic acid monobutyl ester vinyl chloride / Vinyl acetate / Fumaric acid Vinyl chloride / Methyl methacrylate / Vinyl maleate chloride / Acrylonitrile / Vinyl maleate chloride / Styrene / Vinyl maleate chloride / Vinyl stearate / Vinyl maleate chloride / 2-propenyl acetate / Vinyl maleate chloride / Hydroxypropyl acrylate / Maleic acid Vinyl chloride/glycidyl methacrylate/vinyl maleate chloride/acrylamide/vinyl maleate chloride/vinyl alcohol/vinyl maleate chloride/vinyl butyl ether/vinyl maleate chloride/ethyl acrylate/vinyl maleate chloride/ethylene/vinyl maleate chloride/ethylene / vinyl acrylate chloride / propylene / vinyl maleate chloride / styrene / vinyl acrylate chloride / vinyl acetate / vinyl styrene sulfonate chloride / vinyl acetate / vinyl sulfonic acid, etc. and vinylidene chloride was substituted for vinyl chloride in the above table. Other terpolymers.

Additionally, it is also possible to use four-component quadripolymers in which both vinyl chloride and vinylidene chloride are copolymerized with other copolymers as indicated in the terpolymers in the previous section.

The amount of each monomer copolymerized into the vinyl resin is not strictly critical.

The ethylenically unsaturated carboxylic acids listed above as well as other comonomers are commercially available.

The more common sulfonic acid-containing monomers are also commercially available, or the known sulfonation of ethylenically unsaturated monomers ranging from aliphatic monomers such as ethylene to aromatic monomers such as styrene. For example, UnitP Process In Organic Synthesis by P.H. CrOggins.
rOcessesinOr? NicSynthesis
) [McGraw-Hill CO.I.
nc. ), p. 262, NYC (1947), can be synthesized by sulfonation. The invention is not limited to a single copolymer, and a wide variety of combinations of two or more of these vinyl resins can be emulsified as well. Preferred vinyl chloride resins include vinyl chloride terpolymers containing 60 to 91% by weight of vinyl chloride copolymerized therein, 10 to 25% by weight of vinyl acetate, and 1 to 15% by weight of maleic, fumaric, or crotonic acids. Included.

Such terpolymers are commercially available or can be synthesized by free radical initiated polymerization reactions of vinyl chloride, vinyl acetate, and maleic acid or anhydride, fumaric acid or crotonic acid. The vinyl chloride resins described above can also be mixed with vinyl chloride/vinyl acetate terpolymers containing glycidyl or hydroxyalkyl acrylates (or methacrylates) with 2 or 3 carbons in the alkyl group to form cross-linked coatings. You can also get a drug.

Further, thermosetting resins such as epoxy resins, urea resins and melamine resins can be added to the resins to obtain higher degrees of cross-linking. Preferred epoxy resins include liquid or solid diglycidyl ethers of bisphenol A. This bisphenol A is commercially available and is available from H.P., which is incorporated herein by reference. Thor (H.
Lee) and K. Epoxy, resins (EpOxyResines) by K. Neville;
Published by McGraw-Hill, NYC (1957). A preferred melamine resin is hexamethoxymethyl melamine resin.

A preferred urea resin is a methylated urea-formaldehyde resin. These are commercially available. Fog or whitening of a coating is determined subjectively by tests well known to those skilled in the art.

Wet adhesion was measured using the crosshatch adhesive failure measurement method (CrOs
s-Hatchadhesive failure
erminatiOn).

These measurement methods involve immersing a coated specimen in 75°C water for four times, then scratching the coated substrate in a criss-cross pattern with a device with a pointed tip, and applying Scotch tape over the scratched area. This is done by pressing the pieces together and then peeling the Scotch tape from the coated surface. Failure is indicated by the amount of coating pulled away from the substrate. Representative examples of cosolvents are shown below.
Typical glycol monoalkyl (phenyl) ethers are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, monomethyl, ethyl,
These are propyl and butyl ethers and phenyl glycol ether.

1 Representative aliphatic acid ethers include ethoxyacetic acid, α-methoxypropionic acid, dimethoxyacetic acid, and ethoxypropionic acid.

Representative amino esters include methyl-β-aminopropionate, ethylaminoacetate and ethylaminopropionate. Representative aminoketones include aminoacetone and 2-aminoptanone. Typical aliphatic alcohols include methanol,
Includes ethanol, propanol, butanol and pentanol.

Representative aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, and butyric acid.

Representative aliphatic amines include methylamine, dimethylamine, methylethylamine, diethylamine, triethylamine, n-butylamine, and hexamine.

Representative aliphatic amino ethers include gamma-methoxy n-propylamine, gamma-ethoxy n-propylamine, beta-methoxyisobutylamine, and beta-methoxy n-butylamine.

Representative aliphatic dialkylamides include N,N-dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.

Representative cycloaliphatic ether alcohols include glycidol and tetrahydrofurfuryl alcohol.

Representative hydroxy esters include methyl lactate, methyl-β-hydroxypropionate and ethyl-β-hydroxypropionate.

A typical hydroxyketone is 1-hydroxy-2
-propanone, 1-hydroxy-3-ptanone, 3-methyl-4-hydroxy-2-ptanone, 1-hydroxy-2-pentanone and 4-hydroxy-2-pentanone.

The order of addition of the components used to make these colloidal dispersions is not critical.

Thus, for example, it is possible to first prepare a vinyl resin varnish using a solvent and co-solvent and optionally a diluent, then convert it to the ionomer with a base and then carry out the emulsification with water. In this case, water can be added to the varnish and vice versa! Wear. Alternatively, these colloidal dispersions are not made from a varnish of the vinyl resin, but from a dry vinyl resin by adding pellets of powdered resin to a mixture of solvent, cosolvent, base, water, and optionally a diluent. It can also be manufactured by 4 Alternatively, the resin may be fed in the molten state from a vented extruder or thin film evaporator into a mixture of solvent, co-solvent, water-miscible organic polymer, base and water with vigorous stirring. can. The degree of neutralization of the acid moieties in the vinyl resin component ranges over a very wide range, as pointed out above, i.e. 10
% to 100%.

The optimum degree of neutralization is related to the amount of acid moieties in the vinyl resin.
Thus, for example, vinyl resins containing small amounts of acid moieties, such as 2 or 3% by weight, must be neutralized by bases to a much greater extent than vinyl resins containing large amounts of acid moieties. This is believed to be due to the higher degree of polarity of vinyl resins containing a higher degree of acid moieties. To carry out the emulsification, no special equipment is required other than stirring or mixing equipment known to those skilled in the art.

Without wishing to be bound by any theoretical explanation, the colloidal dispersion formulations of the present invention are: (A) (1) water miscible, i.e., at least 1% by weight;
Preferably it is capable of dissolving 10% or more of water; (Ii) it has an affinity for the vinyl resin used, ie the solvent/resin interaction is greater than the resin/resin interaction; (iii) an organic solvent having a boiling point of 16 or less, and (B) (1) water-miscible like the solvent in the above-mentioned solution; and (Ii) a weak solvent for the vinyl resin used. (C) an optional water-miscible organic diluent; (2) within the resin; (E) a water-miscible organic polymeric compound that provides greater stability and better viscosity control of the dispersion; It is believed that this can be accomplished without the need for the use of surfactants.

The combination of solvents and cosolvents described above surprisingly reduces the interfacial tension between the vinyl resin and the aqueous phase while avoiding coagulation.

This produces a colloidal dispersion in which the droplets are stabilized by the ionic repulsion of the ionomer moiety and the surfactant-like properties of the co-solvent. When this state is reached, it is no longer necessary to maintain the initial levels of solvent, co-solvent and/or diluent, and the concentration of the colloidal dispersion should be such that it has a high solids content. I can do it. When these colloidal dispersions are applied to a substrate to form a coating, the co-solvent can also be removed from the system along with the water, leaving only the vinyl resin to form the coating. In the case of a vinyl resin that has been neutralized with a volatile base, the ionomer in the vinyl resin reverts to its original free acid moiety. The presence of water-miscible polymeric compounds ensures greater storage stability as well as the correct viscosity-total solids relationship during the spraying operation.

It is a unique feature of the dispersion described herein that all the necessary ingredients for a sufficient internal can coating can be introduced during emulsification.

The finished colloidal dispersion can be used as is, stripped to a high total solids content by vacuum distillation, or purified with reconstituted water (B
It can be diluted to a low total solids content by adding ackwater. Coating formulations prepared by such methods are absolutely necessary for airless spray painting. It will exhibit sufficient flow, atomization and wetting properties. Furthermore, because of the extremely fine particle size in these dispersions, both metal and non-metal substrates can be coated with very thin continuous protective films.

The resulting protective film has no pinholes, is fog resistant, and firmly adheres to the substrate. If desired, the water-soluble polymer compound can be partially or completely limited in use during emulsification and can be introduced after stripping the solvent.

In addition to those mentioned above, thickeners can also be used to adjust the viscosity, preferably after emulsification. Suitable thickeners include hydrolyzed polyvinyl acetate or polyvinyl alcohol, water-soluble cellulose derivatives (eg hydroxyethylcellulose), polyethylene glycol, polymers of acrylic or methacrylic acid, poly(
ε-caprolactone), polyvinylpyrrolidone and poly(methyl vinyl ether). If desired, other additives known to those skilled in the art can also be incorporated into the colloidal dispersion.

These include dyes, pigments, fillers, antioxidants, UV stabilizers and heat stabilizers. For purposes of this invention, the term water-miscible base broadly refers to the acid functionality in the vinyl resin, i.e. the -COOH group or the -S
A proton acceptor that will neutralize the O3H group,
Moreover, it is used to mean any proton acceptor whose solubility is at least 1y per 1000 cc of water.

Typical bases can be organic or inorganic and include alkali metal or alkaline earth bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Hydroxides; ammonium hydroxide; organic amines including monoalkylamines, alkenediamines, alkanolamines, aromatic amines, cyclic amines and alkaryl amines. Alkali metal, alkaline earth and ammonium hydroxides are the preferred inorganic bases for economical reasons and for reasons of easy availability. When coating, fugitive
), and therefore it is preferred to use volatile bases that produce reversible ionomers. For example, ammonium hydroxide or low molecular weight alkyl amines produce the ionomer that provides the coating, where the ionomer portion reverts to acid from which the fugitive base is removed. This enhances fog resistance and minimizes color development when the finished coating is exposed to the elements.
Particularly preferred alkylamines include monomethylamine, dimethylamine, trimethylamine and triethylamine. Generally, preferred alkylamines have the formula: (wherein each Ra, Rb and Rc are H or C1-C,
It is an alkyl.

However, it has 6 carbon atoms (Ra+Rb+Rc). Preferred alkylene diamines have the formula: where x=1-8 and D is an alkylene radical.

Preferred alkanolamines include mono-, di- and tri-ethanolamine, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-aminoethylethanolamine and N-methyldiethanolamine. .

Preferred cyclic amines include morpholine, N-methylmorpholine, piperidine, pyrrolidine, piperazine, N-
Includes methylpiperazine, N-(2-hydroxyethyl)piperazine, N-aminoethylpiperazine, 2,5-dimethylpiperazine and hexamethylenetetramine.

Preferred lower aliphatic ketone solvents include acetone, methyl ethyl ketone (MEK), diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, acetylacetone and 1-methoxy 2-propanone.

Preferred lower aliphatic ester solvents include methyl formate, ethyl formate, methyl acetate, ethyl acetate and isopropylacetate.

Preferred lower aliphatic ether solvents include diethyl ether, ethyl propyl ether and di-n-propyl ether.

Preferred cycloaliphatic ketone solvents include cycloptanone, cyclopentanone and cyclohexanone.

Preferred cycloaliphatic ether solvents include dioxane and tetrahydrofuran. Depending on the particular vinyl halide resin used, it may be preferable to use a mixture of these solvents rather than a single solvent. For example, acetone with vinyl chloride/vinyl acetate/maleic acid terpolymer, methyl ether. The combination with another ketone, such as tylketone, results in a better dispersion than that formulated with acetone alone. Mixtures of cosolvents can also be used instead of a single cosolvent. Sometimes it is preferable to modify the solvent system with a small amount of a water-immiscible organic diluent in order to balance the solubility parameters between the solvent system and the resin(s) to be dispersed.

This modification can be done without adversely affecting the quality of the finished dispersion, as long as the solvent system maintains adequate overall water miscibility. However, it is preferred that the water-immiscible organic diluent, or its azeotrope with water, boils at a lower temperature than water to facilitate removal of the diluent during vacuum distillation. Representative water-immiscible organic diluents that are miscible with both the solvent and the co-solvent include: pentane, hexane, heptane, 1-chloropentane, 1,2
- alkanes having 5 to 2 carbon atoms and about 2 carbon atoms, such as dichloroethane, trichlorethylene, tetrachloroethylene and 1,2-dibromohexane;
halogenated alkanes having from 5 to about 2 carbon atoms: cycloalkanes and halogenated cycloalkanes having 5 to 12 carbon atoms, such as cyclopentane, cyclohexane, cycloheptan, chlorocyclohexane; benzene, toluene, xylene, chlorobenzene and o-
including both unsubstituted and alkyl- or halogen-substituted hydrocarbons, such as chlorotoluene;
Aromatic hydrocarbons having 6 to 12 carbon atoms; aliphatic ketones having 7 to 12 carbon atoms, such as propyl butyl ketone, dibutyl ketone and butylhexyl ketone; cyclohexyl ketone and cycloheptyl ketone , cycloaliphatic ketones having 7 to 12 carbon atoms; alkaryl ketones having 7 to 12 carbon atoms, such as acetophenone and probiophenone; ethyl benzoate, hexyl benzoate, methylhexanoate, propyl octanoate; 7 to 1 carbon atoms, such as ate and hexyl acetate
Aliphatic esters and aromatic esters having two;
Contains olefins having 6 to 20 carbon atoms, such as hexene-1, octene-2, octene-1 and eicosene-1.

These water-immiscible diluents contain 4 parts per 10 weight parts of organic solvent.
Although it can be used at a level up to 1 part by weight, it is preferably used at a level of 1 to 25 parts by weight per 10 parts by weight of the organic solvent.

A particularly preferred method for producing the colloidal dispersion system of the above vinyl resin is A: the resin, (a) water, (b) a water-miscible base, (c) an organic water-miscible polymer compound, (d) the resin. and has an affinity for 160°C
1 to 500 parts by weight of at least one water-miscible organic solvent per 10 parts by weight of resin (e
) An organic water-miscible co-solvent that is a weak solvent for the resin but is miscible with the organic solvent d is added to the resin 10.
and (f) a water-immiscible organic diluent in an amount of 0 to 4 parts by weight per part by weight of organic solvent DlOO.
B and B are mixed until a stable colloidal dispersion is formed, and then the colloidal dispersion is mixed until the total content of organic solvents d and e and diluent f in the final colloidal dispersion is 0.
．． It consists of stripping to 2 to 2% mass.

If the total organic solvent content falls below 0.1% by volume,
Coatings obtained from such formulations may have pinholes and other voids.

General ecological standards are disturbed when the combined content of organic solvent and diluent exceeds about 8% by weight of 2Cf. Although not absolutely necessary, an organic coalescing agent can optionally be added to the stripped colloidal dispersion.

Typical fusing aids include (1) glycols having 2 to 6 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, diethylene glycol and triethylene glycol, and (2) glycerin. do.

If used, the fusing aid should be present in the colloidal dispersion in an amount up to 25 parts by weight per 100 parts by weight of water.

The colloidal dispersions of the present invention are particularly suitable for coating cans, but as will be apparent to those skilled in the art from the description herein, they may also be used on other substrates, both metallic and non-metallic.
These dispersions can be coated to improve the usefulness of the substrate in packaging and myriad other applications.

The cupric sulfate test is a commonly used test to check for the presence of pinholes in internal can coatings.

A sufficiently good coating should not show any visual defects in this test. Internal can coatings are usually applied by airless spraying. This method is well known to those skilled in the art. Although most embodiments described in this invention are based on two-piece aluminum cans, the invention is equally useful in two-piece as well as three-piece cans constructed from other metals. These metal cans are widely used for beer, beverage, and food packaging. The invention will be further illustrated by the following examples.

All parts and percentages are by weight unless otherwise specified. A laboratory airless can spray apparatus consisting of an emulsion reservoir, a positive device, a pressure gauge, a timer, a heating device, a nozzle assembly, and a rotating can stand was used. Example 1 Preparation of ammonium hydroxide ionomer dispersion Bakelite MCC vinyl resin (terpolymer containing 81% copolymerized vinyl chloride, 17% vinyl acetate and 1% maleic acid) 211.9' and Bakelite VERR vinyl resin (ter'polymer containing 80% copolymerized vinyl chloride, 11% vinyl acetate and 9% glycidyl methacrylate) 105f and 40% methyl ethyl ketone.
8.8y and 68.1g of butyl cellosolve (trademark of the Union Carbide Company for the monobutyl ether of ethylene glycol) were added with 10.5y1 of a % ammonium hydroxide solution of GeIvatol.
Ol)-2600 poly(vinyl alcohol) resin (partially hydrolyzed poly(vinyl acetate) resin manufactured by Monsanto) 21y1 and Beetle-
1,423 y of an aqueous solution containing 10.5 fI of 60 (methylated urea-honohimaldehyde resin manufactured by American Cyanamid Co.) was added with vigorous stirring.

An aqueous dispersion characterized by a strong Tyndall scattering effect was obtained. This Tyndall scattering effect is due to L. M. Edited by Prince, Academic Press (Acad)
1 Microemulsion Theory and Practice (MicrOemuls) published by emicPress
It is commonly thought of in connection with the production of microemulsions or colloidal dispersions as defined in J. On-The Oryar Kl Practjce, p. 7 (1977). The finished dispersion after vacuum stripping had the following composition and physical properties. Example 2 Bakelite VMCC vinyl resin
A vinyl resin (terpolymer containing 78% copolymerized vinyl chloride, 20% vinyl acetate, and 2% maleic acid) and Gelbatol-2030 poly(vinyl alcohol) resin to Gelbatol-2060 poly(vinyl alcohol) resin.
Example 1 above was repeated except that a partially hydrolyzed low molecular weight poly(vinyl acetate) resin was substituted.

The finished dispersion after vacuum stripping exhibited the following composition and physical properties. Example 3 Bakelite VMCH vinyl resin (vinyl chloride 86
．． 5%, vinyl acetate 12.5% and maleic acid 1
% of terpolymer) 45y, methyl ethyl ketone 113.3y and butyl cellosolve 22.7y, 58% ammonium hydroxide solution 3y1 Gelbatol-2090 poly(vinyl alcohol) resin [
Partially hydrolyzed poly(vinyl acetate) resin 6f and Cymel from Monsanto
301 Melamine-Formaldehyde Resin (American
(Hexamethoxymethylmelamine sold by Cyanamid)
Aqueous solution 3649 containing 3y was added with vigorous stirring.

A homogeneous dispersion was obtained which was stripped under reduced pressure to yield the product below. Example 4 Bakelite VMCH vinyl resin 90y1MEK102
A varnish consisting of y and t-butyl alcohol 34y,
An aqueous solution containing ammonium hydroxide 3y1 Gelbatoru 2090 poly(vinyl alcohol) resin 6q1 Cymeru 301 melamine formaldehyde resin 3y and water 357y was added with vigorous stirring.

The resulting emulsion was concentrated under reduced pressure at 50°C to obtain a product with the following composition and properties. Example 5 Example 4 above was repeated except that the Bakelite VMCH vinyl resin was replaced with an equal amount of Bakelite VMCC vinyl resin.

The completed dispersion had the following composition and properties. Example 6 Example 4 above was repeated except that the Bakelite ■MCH vinyl resin was replaced with an equal amount of Bakelite VMCA vinyl resin.

The completed dispersion had the following composition and properties. Example 7 Example 1 above was repeated except that the Beetle 60 urea-formaldehyde resin was replaced with an equal amount of Cymeru 301 melamine-formaldehyde resin.

The completed dispersion had the following composition and properties. Example 8 Beetle 60 urea-formaldehyde resin was replaced with 14.3 g of Beetle 55 urea-formaldehyde resin (partially methylated formaldehyde resin manufactured by American Cyanamid), and Gelvatolu 2060 was replaced with Elvanol-51-05. -G [Partially hydrolyzed poly(vinyl acetate) manufactured by DuPont
[Resin] Example 1 was repeated except that the resin was changed to 28.59y.

The completed dispersion had the following composition and properties. Example 9 Example 1 is repeated except that the Gelbatol® 206 poly(vinyl alcohol) resin is replaced with vinyl (VinO So 540, a partially hydrolyzed poly(vinyl acetate) manufactured by Air Products and Chemicals). Ta.

The completed dispersion had the following composition and properties. Example 10 Beetroot 60 urea-
Formaldehyde resin 6y1 and ammonium hydroxide 3
404y of an aqueous solution containing y was added.

A homogeneously dispersed emulsion was obtained. Example 11 Example 10 above was repeated except that the isopropyl acetate was replaced with an equal amount of hexane.

A homogeneously dispersed emulsion was obtained. Example 12 Example 10 above was repeated except that the isopropyl acetate was replaced with an equal amount of tetrahydrofuran.

A homogeneously dispersed emulsion was obtained. Example 13 Half of the amount of isopropyl acetate used in Example 10 was replaced with toluene.

A homogeneously dispersed emulsion was obtained. Example 14 Bakelite VMCC vinyl resin 90y1MEK108
．． 8y1 Butyl cellosolve 27.2y varnish, Gelbatol 2060 poly(vinyl alcohol) resin 5q1 Beetroot 55 urea-formaldehyde resin 3
An aqueous solution 393y containing g, 3y ammonium hydroxide and 381y water was added with vigorous stirring.

The diluted dispersion was vacuum stripped at 55°C to yield the product below. Example 15 Example 14 was repeated except that Beetroot 55 was replaced with an equal amount of Cymeru 301.

The finished dispersion after vacuum stripping had the following composition and properties. Example 16 (vinyl chloride/vinyl acetate/maleic acid) terpolymer 909, methyl acetate 108. with the following composition and properties: (measured in cyclohexane at 25° C.)
A varnish consisting of 8y1 butyl cellosolve 27.2y,
The same water used in Example 14 above. solution 393
y was added with vigorous stirring.

The diluted dispersion was concentrated under reduced pressure to obtain the product below. Example 17 Example 16 was repeated except that ammonium hydroxide 3f was replaced with N,N-dimethylethanolamine 6y.

After stripping of the solvent, the finished emulsion had the following composition and properties: Example 18 The water-retentive coating formulations prepared in each of the above examples can be modified with various additives commonly used in the coatings industry.

For example, the dispersion prepared in Example 1 above has better wetting, rheological, and filming properties.
ng) can be modified with additional organic solvent(s) to achieve properties. Some examples are shown in Table 1. All formulations in Table 1 contain 2% total solids by volume. Dilution was accomplished by mixing the initial dispersion with an aqueous solution containing the appropriate solvent or solvents. Example 19-
- The emulsions prepared in each of the above examples were evaluated as internal can coatings for several typical two-piece aluminum cans.

Paint storage tank, pump device, preheater, spray time adjustment device,
The paint was applied by an airless spray device consisting of a nozzle assembly and a rotating can stand. Sprayed cans are ventilated (
The paint was cured by baking in an Air-Drift oven. The dispersion prepared according to Example 1 above was diluted with water and butyl cellosolve to produce the following formulation. The above dispersion was heated to 90 pS at room temperature.
The coating was dried by spraying for 150 microseconds under a pressure of 150 m to give a coating weight of 187 m9/can.

Baking was performed at 175°C for 2 minutes.

The finished internal coating exhibited the following properties. Can Type Aluminum Cans Only Cleaned Example 20 The dispersion prepared according to Example 3 above was diluted with water and Probasol Solventol B to give the following formulation.

The above dispersion was heated at room temperature under a pressure of 85 pSi.
A dry coating weight of 170 m9/can was obtained by spraying for 0 microseconds. The finished internal coating exhibited the following properties. Can type Ray nozzle
Olds) A bottom Alodine with can structure
(AlOdin) 404 (non-chromium).

Example 21 The dispersion prepared according to Example 14 above was mixed with isopropyl alcohol and propazole solvent P.
The following formulation was obtained by diluting with an aqueous solution containing:

Burtskfield viscosity 275 centiboas NO. 4
Foed cup flow time 31 seconds The above dispersion was sprayed at 40°C under a pressure of 95 pSi for 100 microseconds to give a dry coating weight of 183
m9/can was obtained.

Baking was carried out for 2 minutes at a temperature of 175°C.

The finished internal coating exhibited the following properties. Example 22 A dispersion was prepared according to Example 1 above.

However, the Beetle-60 urea formaldehyde resin was not used in the production of the heat sealable laminate described below. The laminate was applied in a dry 112 mil thick coating onto 1 mil unannealed aluminum foil using a wire wrapped rod and then baked at 175° C. for 8 minutes. The coated aluminum foil was smooth and shiny. Sentinel with a HOtbarset of 235°C, a clamping pressure of 50PSi and a duration of 2 seconds.
A heat seal was created using a heat sealer.

This seal has sufficient peel strength of 2 bonds/inch (AST
MD-1876-61T).
A control sample coated from a MEK/toluene solution had a peel strength of 21 bonds/inch. Example 23 Bakelite ■MCC vinyl resin 90y, . A varnish consisting of MEK108q and t-butyl alcohol 27.2y,
Ammonium hydroxide 3y1 beetroot 55 3y. ,G
AT(7)PVP/■A1-3A Aqueous solution containing 12y of resin (copolymer of 30% N-vinyl pyrrolidone and 70% vinyl acetate) and 386.5y of water 416.
5y was added with vigorous stirring.

An aqueous dispersion characterized by a strong Tyndall scattering effect was obtained. The finished dispersion after vacuum stripping had the following composition and properties. Example 24 - GAF (7) PVP/VAI-335 resin
Example 23 was repeated except that VA/■AI/535 (a copolymer of 50% N-vinylpyrrolidone and 50% vinyl acetate) was used.

The finished dispersion after vacuum stripping had the following composition and physical properties. Example 25 - GW's PVP/VAI-335 resin was mixed with GAF's PVP/VAI-335 resin.
Example 23 was repeated except that VAI-735 (a copolymer of 70% N-vinylpyrrolidone and 30% vinyl acetate) was substituted.

The finished dispersion after vacuum stripping had the following composition and physical properties.
Weight percent Example 26 Bakelite VMCC vinyl resin 92.81y1 acetone 207.5dah, toluene 46.6y and n-butyl alcohol 69.3dah varnish was coated with Gelbatol 4010 (partially hydrolyzed PVOH from Monsanto). resin) 4.64y1
An aqueous solution containing 4.2 y of ammonium hydroxide and 404 d of water was added with vigorous stirring.

A fine dispersion was obtained. The finished dispersion after vacuum stripping had the following composition and physical properties. Example 27 Bakelite VMCC vinyl resin 60y. ．． VERR vinyl resin 30y. ．． Gelbatol 40 was added to the varnish consisting of MEK102y1 and t-butyl alcohol 34y.
316 g of an aqueous solution containing 10 4y1 Beetroot 60 3y and ammonium hydroxide 3y were added with vigorous stirring.

A fine dispersion was obtained. The finished dispersion after stripping under reduced pressure had the following composition and physical properties. Example 28 Example 27 above was repeated except that only VMCC vinyl resin 90V was used and the Beetle 60 in the aqueous phase was replaced with an equal amount of Cymeru 301.

A translucent dispersion was obtained. The finished dispersion after vacuum stripping had a total solids content of 38.4% by weight. Example 29 The stripped dispersion 200f prepared in Example 28 above was mixed with 5.1f of Gelbatol 2090P 0H resin in a Waring blender.
．． 12.3y of sn-butyl alcohol was mixed with 2.3f of propazole solvent Bl and 100 Da of water.

This diluted dispersion had the following composition and physical properties. Example 30 ■MCA vinyl resin 87.1y,. A varnish consisting of MEK98y and Ethyl Cellsolve 32.7y was added with CellOsize-QP-40-
Hydroxyethyl cellulose resin manufactured by Carbide) 1
q1 Kumeru 301 to 2y1 and trimethylamine (2
8.7y of 5% aqueous solution) was added with vigorous stirring.

A homogeneous dispersion was obtained. A dispersion containing 36.7% total solids was obtained after vacuum stripping at 50°C.

The dispersion had a PI of 6.75 and a Bruckfield viscosity of 656 centiboise. Example 31 VMCA vinyl resin was combined with VMCC6Oy and ERR vinyl resin 30
g, replace Cerosize QP-40 with Cerosize QP
-Example 3 except that 1f of 15,000 was changed.
Repeated 0.

A homogeneous dispersion was obtained. After vacuum stripping at 50°C, a dispersion containing 32.4% total solids was obtained.

The dispersion has a pH of 7.8 and a Bruckfield viscosity of 7.
It had 56 centiboise. Example 32 The aqueous solution was mixed with CarbOwax 200
[Poly(ethylene glycol) resin manufactured by Union Carbide Co., Ltd.] 24y) Example 30 except that another aqueous solution containing 59% of Beetle 60, 2.7y of ammonium hydroxide, and 258% of water was used. repeated.

A homogeneous dispersion was obtained. After stripping the solvent, the finished product had a total solids content of 1%, a pH of 6.95, and a Bruckfield viscosity of 10 centiboise. Example 33 Example 32 above was repeated except that Carbo Wax 6000 was substituted for Carbo Wax 200.

A fine dispersion was obtained. The finished product after vacuum stripping had a total solids content of 33.6%, a pH of 7.2, and a Bruckfield viscosity of 176 centiboise. Example 34 Example 26 above was repeated except that Gelbatol 4010 was not used in the aqueous solution during emulsification.

A fine dispersion is obtained, which is distilled under reduced pressure to reduce the total solids to 3
Obtained 5%.

In a Waring blender, add 100 y of the above concentrated dispersion to 2.45 Da of Gelbatol 4010 and 3 ml of water.
7.6y and 2 drops of ammonium hydroxide to obtain a homogeneous formulation.

The formulation had a total solids of 25%, a pH of 7.8, and a Bruckfield viscosity of 75 centiboise. Example 35 A dispersion prepared as described in Example 14 above was modified with an aqueous solution containing Gelbatol-209 to Beet-R5 anti-butyl cellosolve and propylene glycol to give the following formulation.

Weight % Total solids 20 Gelbatol 2060 and 2060 1.8 Beetroot 550.9 Butyl cellosolve 4.8 Propylene glycol 1.6 Ammonium hydroxide (approximately) 0.8 Water 70.1 Burckfield viscosity 285 centiboise NO. 4 feed cup flow time 3 side' The above dispersion was sprayed at a temperature of 40°C and a pressure of 95as1 for 120 microseconds to give a dry coating weight of 165
m9/can was obtained.

Baking was performed at 175°C for 2 minutes. The completed internal coating exhibited the following properties. can type
Same appearance as used in Example 20 Clear and glossy No mottling CuSO, passed enamel reviewer test 20 MA or less Fog resistance Good enough Wet adhesion Good enough Flavor test Good enough

Claims (1)

[Claims] 1. Having a carboxylic acid group or a sulfonic acid group in the resin,
A method for producing a water-retentive colloidal dispersion of a vinyl resin selected from the group consisting of vinyl chloride, vinylidene chloride or vinyl chloride/vinylidene chloride copolymers, comprising: A the resin; (a) a water-miscible base; (b) Water; (c) Organic water-miscible polymer compound; (d) Having affinity for the resin and at 160°C
at least one water-miscible organic solvent boiling in: (e) an organic water-miscible co-solvent that is a weak solvent for the resin but miscible with the organic solvent d;
and (f) 0 to 49 parts by weight of a water-miscible organic diluent per 100 parts by weight of the organic solvent d, until a colloidal dispersion is formed; and then B. the organic solvent d in the final colloidal dispersion. A method for producing a water-retaining colloidal dispersion of a vinyl resin as described above, characterized in that the colloidal dispersion is stripped until the total content of . 2 Vinyl resin is 60 to 91% by weight of vinyl chloride
, 10 to 25% by weight of vinyl acetate and 1 to 15% by weight of carboxyl-containing ethylenically unsaturated hydrocarbons.
The method according to claim 1, comprising: 3. The method according to claim 2, wherein the carboxyl-containing ethylenically unsaturated hydrocarbon is maleic acid or fumaric acid. 4. The method of claim 2, wherein the vinyl resin contains 75 to 99% by weight of vinyl chloride copolymerized in the resin and 1 to 25% by weight of acrylic acid or methacrylic acid. 5 Vinyl chloride/vinyl acetate/maleic acid terpolymer and vinyl chloride/vinyl acetate/
2. A method as claimed in claim 1, in which a mixture of glycidyl acrylate (or methacrylate) with a terpolymer is used. 6. Claim 1, which uses a mixture of vinyl chloride/vinyl acetate/maleic acid terpolymer and vinyl chloride/vinyl acetate/hydroxyalkyl acrylate (or methacrylate) having 2 to 3 carbon atoms in the alkyl moiety. the method of. 7 Vinyl chloride/vinyl acetate/maleic acid terpolymer and vinyl chloride/vinyl acetate/
2. A method as claimed in claim 1, in which a mixture of vinyl alcohol with a terpolymer is used. 8. The method according to claim 1, wherein the vinyl resin is a terpolymer of vinyl chloride, vinylidene chloride, and ethylenically unsaturated carboxylic acid. 9. The method according to claim 8, wherein the ethylenically unsaturated carboxylic acid is maleic acid or fumaric acid. 10. The method according to claim 8, wherein the ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid. 11. The method according to claim 1, wherein the vinyl resin is a copolymer of vinyl chloride and ethylenically unsaturated carboxylic acid. 12. The method according to claim 1, wherein the ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid. 13 Claim 1 in which the vinyl resin is a copolymer of vinylidene chloride and ethylenically unsaturated carboxylic acid
The method described in section. 14. The method of claim 1, wherein a cross-linked amount of thermosetting resin is mixed into the colloidal dispersion. 15. The method according to claim 14, wherein the thermosetting resin is an epoxy resin. 16. The method according to claim 14, wherein the thermosetting resin is hexamethoxymethylmelamine. 17. Three methods according to claim 14, wherein the thermosetting resin is a methylated urea-formaldehyde resin. 18. A method for producing a water-retaining colloidal dispersion of a vinyl resin having a carboxylic acid group or a sulfonic acid group in the resin and selected from the group consisting of vinyl chloride, vinylidene chloride, or vinyl chloride/vinylidene chloride copolymer, comprising: A. (a) a water-miscible base; (b) water; (c) a part of the organic water-miscible polymer; (d) has an affinity for the resin and has a boiling temperature of 160°C or less. (e) at least one water-miscible organic solvent, although it is a weak solvent for the resin;
and (f) 0 to 49 parts by weight of a water-miscible organic diluent per 100 parts by weight of the organic solvent d, to form a colloidal dispersion. B. The total content of organic solvents d and e and diluent f in the final colloidal dispersion is between 0.2 and 2.
Strip the colloidal dispersion until 0% by volume:
C. A method for producing a water-retaining colloidal dispersion of a vinyl resin, characterized in that the remainder of the organic water-miscible polymer compound c is then added to the colloidal dispersion. 19. A method for producing a water-retaining colloidal dispersion of a vinyl resin having a carboxylic acid group or a sulfonic acid group in the resin and selected from the group consisting of vinyl chloride, vinylidene chloride, or vinyl chloride/vinylidene chloride copolymer, comprising: A. (a) a water-miscible base; (b) water; (c) having an affinity for the resin and at 160°C.
(d) an organic water-miscible co-solvent that is a weak solvent for the resin but miscible with the organic solvent c;
and (e) 0 to 49 parts by weight of a water-miscible organic diluent per 100 parts by weight of said organic solvent c, mixed until a colloidal dispersion is formed; d and the total content of diluent e is 0
．． A method for producing a water-retaining colloidal dispersion of vinyl resin, characterized in that the colloidal dispersion is stripped to a concentration of 2 to 20% by volume; and then an organic water-miscible polymer compound is added to the colloidal dispersion. 20. The method of claim 1, wherein the organic solvent d is acetone or methyl ethyl ketone, the organic co-solvent e is butyl cellosolve or butanol, and the water-miscible organic diluent f is toluene or hexane. 21. The method according to claim 1, wherein the organic water-miscible polymer compound is a vinyl alcohol homopolymer or copolymer. 22. The method according to claim 21, wherein the copolymer has a moiety: ▲a mathematical formula, a chemical formula, a table, etc.▼ where R is as defined above. 23. The method according to claim 1, wherein the organic water-miscible polymer compound is a homopolymer or copolymer of N-vinylpyrrolidone. 24. The method according to claim 23, wherein the copolymer has a moiety: ▲a mathematical formula, a chemical formula, a table, etc.▼ where R is as defined above. 25. The method of claim 1, wherein the resin is mixed with 1 to 25 parts by weight of a water-miscible organic diluent per 100 parts by weight of the organic solvent d. 26. The method of claim 25, wherein the water-miscible organic diluent is n-hexane. 27. The method of claim 25, wherein the water-immiscible organic diluent is toluene. 28. The method of claim 25, wherein the water-immiscible organic diluent is dibutyl ketone. 29 Water 10 of a welding aid selected from the group consisting of glycols having 2 to 6 carbon atoms and glycerin
2. The method of claim 1, wherein up to 25 parts by weight per 0 parts by weight are added to the stripped colloidal dispersion.