FR2473537A1 - COATING COMPOSITIONS BASED ON VINYL ADDITION RESINS AND AMINO-MODIFIED RESINS - Google Patents

Abstract

Coating compositions. They contain a film forming resin consisting essentially of about 15% to about 90% of a vinyl addition resin and about 10% to about 85% of an amine modified resin. The amine modified resin results from the ring opening reaction of a 1,2-epoxy group on a polyepoxide resin with ammonia, a primary amine, a secondary amine, or mixtures thereof. Application to the interior lining of metal containers for food and drink.

Description

The present invention relates to coating compositions.

  The invention relates more particularly to

  coating compositions containing additive resins

  vinyl and resins modified with amines.

  Many works have been devoted to these

  years in the formulation of aqueous coating compositions.

  his. The reasons for these efforts have been concerns over pollution due to the presence of organic solvents in many conventional coating compositions, as well as the cost of the organic solvents themselves. However, the use of water in place of organic solvents for the dilution of the coating compositions has not been without problems. In principle, the resins forming the binder of

  coating compositions had to be reformulated.

  There has been a need for aqueous coating compositions in many areas of the technology using coated media. One area of technology where it has been particularly difficult to substitute aqueous coating compositions for solvent-based coating compositions has been for metal containers for food and beverages. The

  inner surface of these containers typically comprises

  as a resinous coating. The coating is essential, because the bare metal can affect the taste of the contents or even destroy the contents of the container. To be effective, the coating must be continuous and free of voids and must not itself have an effect on the taste of the contents of the container. Examples of attempts made in this area

  are described in U.S. Patents 3,943,187 and 3,997,694.

  The described compositions are based on acrylic polymers

  solubilized by amines, combined with resins

  epoxides. However, the aqueous coating compositions

  currently available do not fully

  Satisfaction for one reason or another.

  There is therefore a demand for compositions of

  aqueous coatings that are likely to be

  by conventional coating techniques and form

  a film having a set of features

  geous. In particular, there is a demand for

  coating positions capable of forming a durable film within the food and beverage containers. Such a coating must not communicate a goit to the contents of the container. In full agreement with these needs; water-based coating compositions have now been found which are particularly useful for coating

  containers for food and drinks.

  In this text, every percent, reports

  and parts are by weight unless otherwise indicated.

  According to the present invention, composi-

  coating compositions in which the film-forming resin which

  contained therein consists essentially of a) from about 15% to about 90% of a vinyl addition resin having an acid number of about 100 to about 700 and b) from about 10% to about 85% of a amine-modified resin resulting from the ring opening reaction of a 1,2 epoxy group on a polyepoxide resin with ammonia, an amine

  primary amine, secondary amine or mixtures thereof.

  The coating compositions according to the invention

  mainly consist of vinyl addition resins

  and amine-modified resins. The resins.indi-

  viduals and coating compositions enclosing them

  are described in the following paragraphs.

  The vinyl addition resins which have an acid number of from about 100 to about 700, preferably

  from about 110 to about 350, can be formed by

  from about 15% to about 95% of a carboxylic acid.

  boxylic alpha, beta-ethylenically unsaturated with approximately

  % to about 85% of at least one vinyl monomer copoly-

  mérisable. The preferred vinyl addition resins are

  formed from about 20% to about 70% of the car-

  alpha, beta-ethylenically unsaturated, and from about 30% to about 80% of the copolymerizable vinyl monomer. Examples of suitable alpha, beta-ethylenically unsaturated carboxylic acids are those containing 3 to 8 carbon atoms, such as acrylic acid and methacrylic acid, both of which are preferred. It is also possible to use acids such as itaconic acid, maleic acid, fumaric acid, monoesters of unsaturated dicarboxylic acids, for example methyl maleate acid and ethyl fumarate acid, as well as anhydrides. when they exist. The copolymerizable vinyl monomer is selected from a wide variety of substances depending on the properties

  desired. For example, at least one part of the other mono

  copolymerizable mother may be a vinyl aromatic compound

  such as styrene, alpha-methyl styrene, tert-

  butyl styrene, vinyltoluene and vinylxylene. These mono-

  Mothers are preferred because of their good resistance to water and pasteurization. Other monomers

  used are the alkyl esters of methacrylic acid

  crylic having 1 to 3 carbon atoms in the group

  alkyl. Specific examples of such esters are the

  methyl methacrylate and ethyl methacrylate. The mono-

  Mothers that can be used and conferring flexibility

  the coating are the alkyl esters of the acrylic acid

  with 2 to 12 carbon atoms in the alkyl group and alkyl esters of methacrylic acid with 4 to 12

  carbon atoms in the alkyl group. Examples of

  Such compounds are ethyl acrylate,

  propyl, butyl acrylate, hexyl acrylate, acrylic acid,

  2-ethylhexylate, butyl methacrylate and methyl

  2-ethylhexyl methacrylate. We can also use

  N- (alkoxymethyl) acrylamides and N- (alkoxy-methyl) metha-

  crylamides with 1 to 4 carbon atoms in the

  as well as N-methylolacrylamide and N- (methylol) methacrylamide. Other monomers that may be mentioned include vinyl halides, vinylidene halides, vinyl versatate, vinyl acetate, maleates of vinyl

  dialkyl, allyl chloride, allyl alcohol, 1,3-

  butadiene, 2-chlorobutene, methyl vinyl ether, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile. Mixtures of any of the

  Vinyl monomers described above can be used.

  Blends of vinyl addition resins formed

  separately from different monomers may also

  be used. A preferred mixture is based on a mixture of a) a vinyl addition resin formed from an alpha, beta-ethylenically unsaturated carboxylic acid and a copolymerizable vinyl monomer o at least one of the vinyl monomers is an N- (alkoxy-methyl) acrylamide and b) a vinyl addition resin formed from an alpha, beta-ethylenically unsaturated carboxylic acid and a copolymerizable vinyl monomer o at least one of the vinyl monomers is N-methylolacrylamide. The

  ratio of the resin a) to the resin b) lies between

  ron 1:19 and about 19: 1, preferably between about 1:10

  and about 10: 1. A particular N- (alkoxymethyl) acrylamide

  preferred and useful for the formation of the resin a) is

N- (ethoxymethyl) acrylamide.

  The vinyl addition resins described above can be prepared by radical polymerization of a mixture of the copolymerizable acrylic monomers by solution polymerization techniques. Usually, the monomers are dissolved in a solvent or a mixture of

  solvents and polymerized until the mono-

  free falls below about 0.5%, preferably below

  below about 0.1%. Examples of free radical initiators are azobis (alpha-gamma) -dimethylvaleronitrile, tertbutyl perbenzoate, tert-butyl peracetate, and the like.

benzoyl peroxide.

  As solvents that can be used in the polymerization phase, mention may be made of alcohols, such as ethanol,

  tertiary butanol, tertiary amyl alcohol, ketone

  such as acetone, methyl ethyl ketone, and ethers such as ethylene glycol dimethyl ether. The aforementioned solvents are either soluble in water or miscible with water. Moderate doses of insoluble solvents in water,

  such as toluene, can also be used.

  Usually, the solvent is first heated to reflux and

  a mixture of the monomers and the radical initiator

  bres is added simultaneously and slowly to the solvent at reflux. Additional catalyst is optionally added and the reaction mixture is maintained at room temperature.

  polymerization temperature to reduce the content of

  free names of the reaction mixture.

  The vinyl addition resins useful according to

  the invention may also be prepared by means of

  conventional emulsion polymerization systems in a

  aqueous place. These emulsion resins are obtained from the aforementioned monomers. Unsaturated carboxylic acids and vinyl monomers are typically dispersed.

  copolymerizable in water using dispersing agents

  anionic or nonionic surfactants soluble in water. A fraction of the monomer mixture is preferably

  emulsified in the aqueous medium and a poly-

  free radical scavenging is added to the emulsion. The

  catalyst alone can be of the peroxide type and, if we

  If it is possible to operate under redox conditions, it is possible to incorporate reducing agents and / or metal promoters. We perform

  then the polymerization, preferably by gradually adding

  the residue of the monomer mixture at a rate

  allows the operator to adjust and maintain the temperature

  mass in the operating limits chosen. The

  polymerisation is usually carried out at temperatures

  res below about 1000C and may

kill continuously or discontinuously.

  Although solution-type vinyl addition resins and emulsion resins are described above as being essential components of the present coating compositions, it goes without saying that the various resins can be mixed when it is desired to obtain resins.

  compositions possessing all the characteristics

haitées.

  Resins modified with amines which are

  in combination with the vinyl addition resins described above.

- -. '-2473537

  The result is the reaction product of a polyepoxide resin with ammonia, a primary amine, a

  secondary amine or mixtures thereof. Several resins of.

  polyepoxide can be used as reaction

  departure time. Polyepoxide resins possess-plus

  an epoxy group per molecule. We know different

  epoxy sins of this type, examples of which are found in Handbook of Epoxy Resins, Lee and Neville, 1967, McGraw-Hill

Book Company.

  A preferred class of polyepoxides is polyglycidyl ethers of polyphenols, such as bisphenol. nol-A. They are obtained by etherification of a polyphenol '

  with epichlorohydrin in the presence of an alkali. Com-

  phenolic layer can be 1,1-bis (4-hydroxyphenyl) ethane,

  1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl)

  phenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-.

  dihydroxynaphthalene and 1,1-bis (4-hydroxy-3-allylphenyl) ethane. Another class of useful polyepoxides is obtained

  in the same way from polyphenol resins.

  Polyglycidyl ethers of similar polyalcohols, derived from polyalcohols such as ethylene glycol, diethylene glycol, triethylene glycol, are also suitable.

  1,2-propylene glycol, 1,4-butylene glycol, 1,5-penta

  nediol, 1,2,6-hexanetriol, leglycerol and 2,2-bis

(4-hydroxycyclohexyl) propane ...

  Cycloaliphatic polyepoxide resins can also be used in the present case. These resins

  are prepared by epoxidation of unsaturated cyclic polyenes

  with organic peracids, for example acid

peracetic.

  Another class of useful polyepoxides is that

  containing oxyalkylene groups in the epoxy molecule.

  Such oxyalkylene groups are typically groups of the general formula: ## STR2 ##

02 i} m3n.

  R in which R is hydrogen, an alkyl group, preferably a lower alkyl group (for example having

  1 to 6 carbon atoms) or a mixture of hydrogen and

  kyle, and where m is between 1 and 4 and n is included in

  2 and 50. These groups may be pendent with respect to the main molecular chain of the polyepoxide or be part of the main chain itself. The proportion

  of oxyalkylene groups in the polyepoxide depends on

  many factors, including the chain length of the group

  oxyalkylene, the nature of the epoxy and the degree of modification

desired cation.

  Hydantoin-based polyepoxide resins as described in U.S. Patent 4,110,287 and in an article in Die Angewandte Makromolekulare Chemie,

  flight. 63, (1977), pp. 63-104, by Jurgen Habermeier, (men-

  referred to herein) can also be used. The polyepoxide resins described above are reacted with ammonia, a primary amine, a secondary amine, or mixtures thereof. Examples of suitable primary and secondary amines are ethylamine,

  propylamine, butylamine, tert-butylamine, dimethyl

  mine, diethylamine and dipropylamine. This reaction essentially involves a ring opening reaction.

  the resulting ungelled product is the finished product.

  its amine of the polyepoxide resin. It is desirable that substantially all the 1,2-epoxy groups in the polyepoxide resin react with the ammonia or amine so as to avoid significant polymerization. This is how

  molar excess of ammonia or amine compared with

  The epoxy is preferably used in the reaction. Molar excess of ammonia or amine reaching about

  : 1 or even more can be used, excess ammonia

  that unreacted amine is subsequently removed

  is lying. The reaction of the polyepoxide resin with ammonia

  or amine occurs in a wide range of temperatures.

  preferably between about 30 ° C and about 100 ° C.

  The reaction time varies depending on the temperature used, but is generally between about 2 and 5 hours. The

  conditions described above are desirable for a minimum of

  bet the subsequent reaction of the primary amine produced with the epoxy groups to form a product strongly

polymerized or gelled.

  A solvent or a mixture of non-reactive solvents

  can be used during the reaction of the polyethylene resin

  poxide and ammonia. Specific examples of soil

  suitable solvents are ethanol, propanol, isopropanol,

  butanol, ethylene glycol monobutyl ether and

  ethylene glycol monoethyl ether. An organic solvent

  miscible with water is normally used.

  The coating compositions according to the invention contain a film-forming resin, said resin consisting essentially of about 15% to about 90%, preferably

  from about 20% to about 75% of the vinyl addition resin

  about 10% to about 85%, preferably in

  from about 25% to about 80% of the modified resin by

  nes. The solids content of the compositions ranges from about

  % to about 40%, the complement of the composition comprises

  water, an organic solvent or a mixture of water and organic solvent. For the reasons indicated above, the compositions are preferred where water is the liquid carrier.

main.

  The coating compositions are prepared according to

  various methods from the vinous additive resins

  and amine-modified resins described above. According to one variant, the vinyl addition resins

  and the amine-terminated resins are prepared separately.

  NEET. The vinyl addition resin is neutralized with a suitable base either before or after mixing with the amine-terminated resin and water is then added

  to form the coating composition. Appropriate bases

  required are ammonia and primary amines, secondarily

  for example, ethanolamine, diethanolamine,

  laminate, N-methylethanolamine, dimethylethanolamine,

  methylamine, ethylamine, diethylamine, trimethylol

  mine, triethylamine and morpholine. Usually, the pH of the final aqueous dispersion is adjusted to a value

between about 7.5 and 11.

  An alternative route for the preparation of the coating compositions is to mix the vinyl addition resin with the polyepoxide resin.

  and then reacting the epoxy groups with the ammonia

  that or amine. Once the epoxy groups have almost

  all reacted, additional organic amine can be added.

  silent. To obtain a more sustainable film, it is often

  advantageous to add an external cross-linking agent to the composi-

  coating compositions described above. Examples are aminoplast resins, phenoplast resins and blocked polyisocyanate resins. The level of crosslinking agent used as part of the film-forming resin is about 1% and is preferably between about 5% and about 1% of the film-forming resin. Although the vinyl addition resins derived from N-alkoxymethylmethacrylamide and Nalcoxymethylacrylamide are capable of crosslinking without

  an external crosslinking agent, such agents may nevertheless

less to be added.

  Aminoplast resins are the products of

  densification of an aldehyde, for example formaldehyde, acetaldehyde

  aldehyde, crotonaldehyde and benzaldehyde, with a substance containing an amino or amido group, for example

  urea, melamine or benzoguanamine. We pre-

  products obtained from the reaction of alcohols and formaldehyde with melamine, urea or

  benzoguanamine in aqueous coating compositions.

  its, because of their good dispersibility in the water. of the

  useful alcohols used in the preparation of

  are the monoalcohols, salts that methanol, ethanol

  propanol, butanol, hexanol, benzyl alcohol and

  than, cyclohexanol and ethoxyethanol. A melamine resin

  Etherified formaldehyde is the preferred aminoplast resin.

  U.S. Patent 4,075,141 contains a description of

  Useful aminoplasts are mentioned here for reference. Phenolic resins include the condensation product of an aldehyde with a phenol. Leformaldéhyde

  and acetaldehyde are preferred aldehydes. Various phi-

  can be used, such as phenol

  so-called, cresol, p-phenylphenol, p-tert-butyl-.

  phenol, p-tert-amylphenol and cyclopentylphenol. The methylolphenol ethers described in U.S.

  2,597,330 (described herein by reference) are particularly

useful.

  A number of blocked polyisocyanates are satisfactory crosslinking agents. These agents are well known to those skilled in the art. In general,

  organic polyisocyanates are blocked with a volatile alcohol

  til, epsilon-caprolactone or a ketoxime. These polyiso-

  blocked cyanates unblock at elevated temperatures, for example above about 100 C. "The Chemistry of Organic Film Formers" by Robert E. Kreiger Pub. Co., rights

  reserved in 1977, by D.H. Solomon, contains on pages 216-

  217 a description of many blocked isocyanates likely to

  can be used here. The description of this publication

  This is mentioned here for reference.

  The coating compositions can usually

  Other optional components include pigments, fillers, antioxidants, tensides and surfactants. Agents of

  coalescence can also be incorporated into

  positions for their well-known role of promoting the training of

  a durable film from emulsion resins. The compositions can be applied by any convenient coating method on a variety of substrates including wood,

  glass, fabric, plastics and metals. The components

  are particularly useful for

  dull containers for food and drink. These containers can be either steel or aluminum. They are

  found that the compositions provide a sensitive coating

  Sibly void free which protects the container itself

  while at the same time not communicating an undesirable taste

the contents of the container.

  The following examples illustrate the invention described but do not limit it in any way. Examples A to E illustrate the preparation of vinyl addition polymers

  useful in the coating compositions according to the invention.

  Examples I to VII illustrate the coating compositions.

is lying.

EXAMPLE A

  A vinyl addition resin is prepared, as

  acrylic acid, styrene and N-methyl-

* lolacrylamide. A 12 liter reaction flask is equipped with a condenser, stirrer, thermometer and addition ampoules. Starting from the flask is a mixture of 1392.8 parts of ethylene glycol monobutyl ether,

  1963.3 parts of butanol and 225 parts of deionized water

  See. This mixture is heated to 10 ° C. until the reflux conditions are reached. At this stage, we perform

  three separate additions, for a period of five hours.

  Addition 1 consists of 2004.8 parts of acrylic acid and 1884.5 parts of styrene. Addition two consists

  in 285.3 parts of a 60% aqueous solution of N-methyl

  lacrylamide and 250 parts of deionized water. Addition three consists of 96.8 parts of benzoyl peroxide (78% active ingredient), 157.5 parts of ethylene glycol monobutyl ether and 562.5 parts of toluene. The temperature of the reaction mixture is 990C. After the end of the three additions, 56 parts of ethylene glycol monobutyl ether are used to rinse the addition funnel and a 112.5 initiator solution is then added.

  parts of toluene and 16 parts of benzoyl peroxide.

  The mixture is kept for one hour. The same amount of initiator solution is added again, followed by holding at temperature for one hour. The temperature of the mixture is 93 ° C. A final addition of the same initiator solution is then carried out, and the temperature is maintained for two hours. The resin-final has a rate of

  51.5% solids at 105 C and an acid number of 115.5.

EXAMPLE B

  This example illustrates the preparation of a vinyl addition resin of acrylic acid, styrene and N- (ethoxymethyl) acrylamide. In a reactor equipped as in Example A, 950 parts of deionized water, 300 parts of ethanol, 50 parts of isopropanol, 819 parts of solution of N- (ethoxymethyl) acrylamide (36% in ethanol), 163

  parts of acrylic acid and 75 parts of styrene. This

  The mixture is heated to 86 ° C (reflux). Two reactant streams are then delivered to the reactor. One stream consists of 3190 parts of the solution of N- (ethoxymethyl) acrylamide

  described above, 651 parts of acrylic acid, 302 parts

  styrene and 800 parts of deionized water. The second stream consists of 63.8 parts of benzoyl peroxide (78% active ingredient), 128 parts of toluene, 46 parts of ethanol and 160 parts of methyl ethyl ketone. At the end of the additions, the temperature of the flask is 83 ° C. Fifty eight parts of ethanol are used for the monomer introduction ampoules. This rinse is followed by an initiator charge consisting of 10.6 parts of benzoyl peroxide in 118.2 parts of toluene and then held for 1 hour. Two additional additions are made

  of the same initiator solution (separated from

  1 hour). After a final hold for two hours at 78 ° C., the resin is found to have a solids level

  30.8% and an acid value of 75.6.

EXAMPLE C

  A vinyl addition resin based on acrylic acid

  of styrene and N- (ethoxymethyl) acrylamide is

in this example.

  In a reactor equipped as in Example A, 124.4 parts of tertiary butyric alcohol and 35.5 parts of deionized water are initially charged. The mixture is heated to 760C until reflux. At this point, two streams are introduced for a period of five hours. Run one consists of 154.4 parts of a 36% solution of N- (ethoxymethyl) acrylamide in ethanol, 83.5 parts of acrylic acid and 89.8 parts of styrene. Stream Two consists of 6.5 parts of benzoyl peroxide (78% active ingredient), 32.9 parts toluene and 9.9 parts

  ethanol. After introducing currents 1 and 2, 4.5 parts

  additional amounts of tertiary butyl alcohol and 1,4

  Part of ethanol is added for rinsing the monomers.

  Three separate initiator solutions each consisting of 1.1 parts of benzoyl peroxide and 12.1 parts of toluene are then added according to the sequence of Example A. The final resin has a solids level of 40%.

1500C and an acid number of 118.

EXAMPLE D

  This example illustrates the preparation of a resin

  as in Example C by another procedure.

  In a reactor equipped as in Example A, 746 parts of ethanol and 213 parts of deionized water are charged.

  Once the reflux is reached (750C), two currents are

  introduced separately for three hours. A current

  It consists of 926 parts of a 36% solution of N- (ethoxynryl) acrylamide in ethanol, 501 parts of acrylic acid and 539 parts of styrene. The second stream consists of 39.2 parts of benzoyl peroxide, 202.4 parts of toluene and 103.2 parts of ethanol. The temperature is at 780C at the end

  additions. At this point, we add three solutions of amorphous

  separated, each addition being separated from the next

  by holding at temperature for one hour. Each solution

  tion consists of 6.5 parts of benzoyl peroxide (78%

  active ingredient) and 73 parts of toluene.

  The resulting vinyl addition resin has a

  2473537 - .. DTD: solids content of 38.4% at 150 C, an acid number of

  109.7 and a viscosity of 6.9x10 m2 / s.

EXAMPLE E

  A vinyl addition resin based on methacrylic acid

  Crylic, styrene and ethyl acrylate is prepared according to the general procedure of Example A. In a five-liter reaction flask,

  initially 800 parts of butanol and 100 parts of butoxy-

  ethanol. This mixture is heated to 1160C until a reflux. At this point, two streams of reagents are introduced for a period of three hours. One stream consists of 416 parts of butanol, 50 parts of butoxyethanol, 576 parts of methacrylic acid, 461 parts of styrene and 115 parts of ethyl acrylate. The second stream consists of 355 parts of butanol, 52 parts of butoxyethanol and 30 parts of tert-butyl perbenzoate. At the end of the additions,

  the temperature of the reaction mixture is 118.degree.

  Initiating solutions of initiator solutions are then made as in Example D. Each solution consists of 4 parts of tert-butyl perbenzoate and 25 parts of butanol. The vinyl addition resin has a solids level of 37.9% at 1500 ° C., an acid number of 122 and

viscosity of 175x10-4 m2 / s.

  The following paragraphs illustrate the preparation of amine-modified resins and coating compositions containing resins and addition resins.

previously described vinyl.

EXAMPLE I

  A 12 liter reactor is equipped with an agitator, a condenser, a thermometer, a dip tube and

  of introductory bulbs. In the balloon, we charge

  2640 parts of an epoxy solution. The solution

  530 parts of ethylene glycol monobutyl ether, 526 parts of butanol and 1584 parts of an epoxy resin having an epoxy equivalent of 1440. The epoxy resin is prepared from EPON 829 (a condensation product of epichlorohydrin and bisphenol A) and bisphenol A. Ce

  mixture is added 336.8 parts of a solution of hy-

  28% aqueous ammonium hydroxide below the surface of the epoxy solution. The above mixture is heated at 55 ° C. for a period of one hour and held there for another two hours. At the end of this time, the mixture is heated to 103 C for the elimination of 261 parts

distillate.

  The above reaction mixture is then cooled

  at 81 ° C and added 1030.4 parts of the resin

  glossy in Example A, 77.5 parts of the resin

  in Example B, 329.6 parts of triethylamine and 211.8 parts of an aminoplast resin (available from

  from American Cyanamid Co. under the name Cymel 370).

  A dispersion of the above constituents is then

  prepared by adding 4,200 parts of deionized water pre-

  heated (75 C) for 40 minutes. The temperature is

  This temperature is lowered to 60 ° C and the dispersion is maintained for four hours. At the end of this time, a mixture of 538 parts of diethylene glycol monoethyl ether and 538 parts of tertiary butyl alcohol is added over 30 minutes. The final coating composition has a solids level of 26.5% at 105 ° C, a viscosity of 38 seconds at Ford Cup No. 4, 0.348 milliequivalents of acid per hour.

  part of the sample, 0.397 milliequivalent base per

sample size and a pH of 9.1.

EXAMPLE II

  In a 5 liter reactor equipped as in the example

  I, 1045 parts of an epoxy resin solution are charged.

  The solution consists of 200 parts of butanol, 218 parts of ethylene glycol monobutyl ether, 44 parts of ethylene glycol monohexyl ether and 627 parts of a solid epoxy resin (as used in Example 1). This

  The mixture is heated to 70 ° C, after which 118 parts of a mixture

  28% aqueous ammonia solution is added below

  the surface for 20 minutes. The mixture is maintained

  for two hours and is heated to 100 C for the removal of 113.2 parts of volatiles. The reaction mixture is then allowed to cool

  up to 70 C. 540 parts of the resin illustrated in the example

  ple C are then added. After five minutes, 96 parts

  of triethylamine are added and stirred for 20 minutes.

  your. After that, 1628 parts of deionized water are added to form a dispersion. This product is then aged

  thermally at 60 C for three hours.

  The resulting product has a solids content of 28.2% at 105 C, a viscosity of 40 seconds at the Ford cut

  number 4, 0.355 milliequivalents of acid per part of sample

and a pH of 7.8.

EXAMPLE III

  In a reactor, 164.2 parts of the solution are

  epoxy composition of Example I. 18.9 parts of ammonia were

  The mixture is heated to 55 ° C. at 28 ° C. and the mixture is heated to 55 ° C. for 2 hours and 13.7 parts of distillate are removed at this time. After

  cooling at 80 ° C., 85.7 parts of an additive resin

  as illustrated in Example A and 15.2 parts of a vinyl addition resin as illustrated

  in example B are added; we introduce 22 parts of

  aqueous monkey, followed by the addition of 12.7 parts of an aminoplast resin (available from American Cyanamid

  Co. under the name Cymel 1116).

  The reaction mixture is then heated to 71 ° C. The above mixture is then dispersed by adding 382.7 parts of deionized water for 50 minutes. The temperature is set at 60 ° C. and the dispersion is maintained for four hours at this temperature. We add 73 parts

  additional deionized water to adjust the viscosity.

  The composition has a solids content of 21% at 105 ° C., a viscosity of 30 seconds at the Ford Cup number 4 and a

pH of 8.8.

EXAMPLE IV

  In a reactor of the type described in Example I, 1045 parts of an epoxy solution (as used in Example I) and 44 parts of ethylene glycol monohexyl ether are charged. The mixture is heated to 6 ° C. and 114 parts of 28% aqueous ammonia are added thereto. The aqueous ammonia is added in 20 minutes and below the surface of the mixture. The reaction mixture is maintained for two hours and then heated to 950C for removal of 120.1.

  parts of volatile matter. We then cool the

  lange at 700C and add to it 540 parts of the resin de-

  in Example C. After a holding time of 20 minutes

  Afterwards, a mixture of 75 parts of aqueous ammonia and parts of deionized water is added over 10 minutes and maintained for a further 10 minutes. The above mixture is dispersed by adding 1960 parts

deionized water.

  The composition has a solids level of 21.9%

  at 1500C, a viscosity of 29 seconds

  ro 4, a pH of 9.7 and 0.295 milliequivalents of acid per

sample.

EXAMPLE V

  2616 parts of an epoxy solution of the type described in Example I and 110.4 parts of monohexyl ether

  ethylene glycol are introduced into a reactor. The solution

  The mixture is heated to 70 ° C., after which 293 parts of aqueous ammonia are added below the surface. The reaction mixture is heated to 6 ° C. and kept there for two hours. Then heated to 1020C to extract 282 parts of volatile matter. After cooling to 730C, 1351 parts of a vinyl addition resin as described in Example D are added and the mixture is maintained for 20 minutes. 240 parts of triethylamine are then

  added and maintained for 15 minutes at 68 ° C.

  persion is carried out by adding 4788 parts of deionized water for 20 minutes and the mixture is maintained

for three hours at 61 C.

  The coating composition contains 22.6% of solids at 150 ° C, has a measured viscosity of 19 seconds.

  Ford Cup number 4 and has a pH of 8.6.

EXAMPLE VI

  In a reactor of the type described in Example I,

  240 parts of ethylene glycol monobutyl ether are charged

  and 575 parts of a solid epoxy resin having an epoxy equivalent weight of 1450 (prepared from EPON 829 and bisphenol A). The mixture is heated to dissolve the epoxy resin and is then cooled to 70 ° C. 104 parts of a 28% aqueous ammonia solution are introduced below the surface and the mixture is maintained for 2 hours. at 62 ° C. The resulting product is then heated to 112 ° C to remove 91.2 parts of volatiles. The contents of the reactor are then cooled to 70 ° C. and 542 parts of the vinyl addition resin described in Example E are added. The contents are mixed for 20 minutes. A mixture of 53 parts of an aminoplast resin (available from Monsanto Co. under the name Resimene 735) and 95 parts of triethylamine is added thereto. After 15 minutes, add 2600 parts of water. The resulting dispersion is maintained

at 58 C for three hours.

  The coating composition has a degree of

  19.7% at 150 C, a measured viscosity of 27 seconds

  the Ford Cup number 4, a pH of 8.2 and 0.295 milliequiva-

  slow acid per part of sample.

EXAMPLE VII

  In a 5-liter reactor equipped as in Example I, 1045 g of the epoxy solution of this type are charged.

  Example and 44 parts of ethylene glycol monohexyl ether.

  ,. The contents are heated to 70 ° C and a mixture of 33 parts of butylamine and 85 parts of deionized water is added below the surface. The reaction mixture is maintained for three hours, after which 540 parts of the resin of Example C are introduced by mixing.

in 20 minutes.

  The reaction mixture is neutralized with a solution of

  75 parts ammonia aquewe at 28% and 150 parts deionized water. The temperature is raised to 670C and the product is held there for 10 minutes. At this stage, 1960 parts of deionized water are added in 15 minutes. This final dispersion is then heated at 60 ° C for three hours. The final coating composition has a solids level of 26.9% at 1500C, 0.294 milliequivalents of acid per gram of sample, a viscosity of 34 seconds at the

  Ford coupe number 4 and a pH of 10.

  The compositions as illustrated above are particularly useful for providing the beverage containers

an internal coating.

R E V E N D ICATIONS

  1. Coating composition, characterized in that

  the film-forming resin contained therein consists essentially of

  in a) from about 15% to about 90% of a vinyl addition resin having an acid number of about 100 to about 700; and b) from about 10% to about 85% of an amine-modified resin resulting from the ring opening reaction

  a 1,2-epoxy group with ammonia, a primary amine

  mayor, a secondary amine or a mixture thereof.

  2. Composition according to claim 1, characterized

  in that the vinyl addition resin is obtained by

lymérisation:

  1) from about 15% to about 85% carboxylic acid;

  alpha, beta-ethylenically unsaturated; and

  2) from about 15% to about 85% of at least one mono-

copolymerizable vinyl mother.

  3. Composition according to claim 2, characterized in that the copolymerizable monomer is chosen from

  group consisting essentially of N- (alkoxymethyl) acryl-

  lamide, N- (alkoxymethyl) methacrylamide, N-methylolacrylamide,

  N- (methylol) methacrylamide, styrene, alkyl esters of a-

  acrylic acid with 1 to 12 carbon atoms in the alkyl group, alkyl esters of methacrylic acid with 1 to 12

  carbon atoms in the alkyl group, and mixtures thereof.

  4. Composition according to claim 3, characterized in that the alpha, beta-ethylenically unsaturated carboxylic acid is acrylic acid, methacrylic acid or

their mixtures.

  5. Composition according to claim 4, characterized

  in that at least one of the vinyl monomers copoly-

  merisables is an N- (alkoxymethyl) acrylamide o the group

  alkoxy contains 1 to 4 carbon atoms.

  6. Composition according to claim 4, characterized

  in that the vinyl addition resin is a resin blend comprising a polymerized resin

  of the carboxylic acid alpha, beta-ethylenically unsaturated

  and a copolymerizable vinyl monomer o at least

  one of the copolymerizable vinyl monomers is an N- (alkoxy)

  methyl) acrylamide, and a second resin obtained by poly-

  merification of the alpha, beta-ethylenically unsaturated carboxylic acid and a copolymerizable vinyl monomer, at least one of the copolymerizable vinyl monomers being

N-methylolacrylamide.

  7. Composition according to claim 6, characterized in that the N (alkoxymethyl) acrylamide is N- (ethoxymethyl) acrylamide.

  8. Composition according to one of claims 5 or

  6, characterized in that the polyepoxide resin is a

  polyglycidyl ether of polyphenol.

  9. Composition according to Claim 8, characterized in that the polyphenol is bisphenol A. 10. Composition according to Claim 8, characterized in that a molar excess of ammonia or amine is used.

  in the reaction with the polyepoxide.

  Composition according to claim 1, characterized in that the film-forming resin consists essentially of from about 20% to about 75% of the vinyl-addition resin and from about 25% to about 80% of the modified resin.

  an amine and in addition the vinyl addition resin pos-

  has an acid number of about 110 to about 350.

  12. Composition according to claim 11, characterized

  in that the vinyl addition resin is derived from about 20% to about 70% of the alpha, beta-ethylenically unsaturated carboxylic acid and from about 30% to about

  80% of the copolymerizable vinyl monomer.

  13. Composition according to claim 1, characterized

  in that it further comprises an amount of a crosslinking agent of up to about 40% with respect to the film-forming resin.

  14. Composition according to claim 13, characterized

  in that the crosslinking agent is an amino resin

  plastid, a phenolic resin, a polyisocyanate resin

  blocked or a mixture thereof.

  15. Composition according to claim 14, characterized

  in that the level of crosslinking agent is between

  about 5% and about 20% of the film-forming resin.

  16. Composition according to one of claims 1 or

  , characterized in that it comprises a solid resin content of about 15% to about 40% and the composition is

water base.

  17. Composition according to claim 11, characterized in that the resin modified with an amine is derived from a resin.

polyepoxide and ammonia.

  18. Composition according to claim 1, characterized in that the vinyl addition resin is a mixture of a

  solution type resin and an emulsion resin.

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