DE2261804A1 - EPOXY COMPOUNDS - Google Patents

Description

Dr. Michael Hann December 13, 1972

Patent attorney H / W (507) 5065/5080

j -

63 Giessen * * . . ■

Ludwigstrasse 67 _t

PPG Industries, Inc., Pittsburgh, Pa., USA. EPOXY COMPOUNDS

Priority? December 20, 1971 / USA / Ser.No. 210.141

January 12, 1972 / USA / Ser.No. 217.278

Although electrical deposition has been known for some time, it has only recently come into being as coating process is of greater commercial importance. While many connections are electrically discharged. can be applied, result in most coating compounds, using electrodeposition processes, not commercially useful coatings. In addition, the electrical deposition of many coating materials, even if otherwise successful, is with various disadvantages, such as non-uniform coatings and insufficient Throwing power. Furthermore, the coatings obtained are lacking in the in most cases, of various essential peculiarities shafts when using them on traps

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for which the electrical deposit is otherwise suitable. Properties such as corrosion resistance and alkali resistance, are particularly difficult with the resins generally used in electrical Deposition processes are used to achieve. This is particularly true of the conventional ones electrically depositable masses, the polycarboxylic acid resins, which are soluble with a base. power to be contained, to. These are deposited on the anode and tend due to their acidic nature to be sensitive to general types of corrosive attack such as salt, alkali, etc. Many electrically deposited Anodic coatings are discoloration or staining due to the dissolution of metal ions subjected to the anode.

The most common resins for many purposes include the epoxy resins, which are excellent Possess corrosion resistance and other properties. They are used in many coatings, but were not water dispersible compositions useful for electrodeposition processes are suitable because they are not sufficiently dispersible in water the conditions required in such procedures. Esterified epoxy resins were also used, however, these worked similarly to the poly-

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carboxylic acid resins and, although they. many advantages over have such polycarboxylic acid resins, they have a number of disadvantages.

It has now been found that synthetic resins, which are non-gelled, water-dispersible epoxy resins are the epoxy groups and chemically bonded quaternary groups of a phosphonium or sulfonium base contain, and optionally also contain oxyalkylene groups, can easily be used to produce clear, or to give colloidal aqueous solutions. These compounds can, if made by ionizing the quaternary group and the acid counterion are solubilized, such as by a quaternary salt, preferably when the acid - counterion of an acid that has a dissociation constant of higher than about 1 χ 10-5, deposited by electrical deposition to give adhesive coatings with excellent properties. With the electric Deposits are deposited on the cathode. When the above resins in aqueous preparations for the. When electrical deposition is used, they form the main resinous ingredient of the mixture, either as the sole resinous component or with one or more other resinous or film-forming materials. The coatings made from these masses have the advantageous properties which are usually with electrodeposited resins; but also have coatings. this

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22618OA

Reaction products have unique advantages and properties. These include resistance to salt spray, alkali and similar corrosive Elements, even on unprimed metals and in the absence of corrosion prevention Pigments. They are also resistant to staining and discoloration, which is often the case Electrically depositable coatings based on anodic resins can be observed. These resins have a higher throwing power or a higher throwing power) and better film-forming properties when used with an acid that has a dissociation constant higher than 1 χ 10 ~ ->, are made soluble.

The resins according to the invention are non-gelled, water-dispersible epoxy resins which, in their Molecule contain at least one 1,2-epoxy group per molecule average, which optionally oxyalkylene groups and also salts of a chemically bonded quaternary onium base from the Group containing the salts of the sulfonium or phosphonium base, the salts of the quaternary Onium base are preferably salts of boric acid and / or an acid that have a dissociation constant, higher than boric acid, including organic and inorganic Acids. In solubilizing there is at least part of it

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of the salt is preferably a salt of an acid which has a dissociation constant higher than about 1 χ 10 ~~>. Especially in the absence of oxyalkylene groups; it is preferably a salt of an acid that has a dissociation constant greater than about 1 χ 10 " ^5. Preferably the acid is an organic carboxylic acid. The currently preferred acid is lactic acid. The resin preferably contains about 0.1 to about 35% by weight of phosphorus or sulfur and at least about 1% of said phosphorus or sulfur and preferably about 20%, more preferably about 50% and most preferably essentially all of the phosphorus or sulfur in the form of salt groups of chemically bound quaternary onium base.

The "resins of this invention include:

(a) Epoxy group-containing resins that additionally contain quaternary phosphonium or sulfonium groups and oxyalkylene groups, the resins containing chemically bound boron may or may not contain or wherein they may be dispersed for electrical coatings with and without the addition of a boron compound and especially boric acid or a precursor thereof; or

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(b) epoxy groups - containing resins that additionally quaternary phosphonium or sulfonium base salts an acid with a dissociation constant higher than 1 χ 10 "5, the resin only preferably contains oxyalkylene groups but / can also be free of such groups and wherein the resins may or may not contain chemically bound boron, or where the resin is used for the electrical deposition with and without the addition of a boron compound and especially boric acid or a Precursors thereof can be dispersed.

The epoxy compound can be any monomeric or polymeric compound or mixture of compounds which is a 1,2-epoxy equivalent of greater than 1.0, which means that the average number of 1,2-epoxy groups per molecule is greater than 1 is. It is preferred to use a resinous epoxy compound, that is, a polyepoxide sum Example that contains more than one epoxy group per molecule. The polyepoxide can be any well known Be epoxy provided that it contains enough epoxy groups so that some residual Epoxy groups after oxyalkylation for reaction with the phosphine, which will be described later w'will remain in the product. Examples of such Polyepoxides have been described in US Pat. Nos. 2,467,171; $ 2,615,007 2,716,123} 3,030,336} 3,053,855 and 3,075,999. A used

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The polyglycidyl ethers are the group of polyepoxides of the polyphenols, such as bisphenol A. These are produced, for example, by etherification of a polyphenol. with epichlorohydrin or dichloro. hydrin produced in the presence of an alkali. the phenolic compound can be bis (4-hydroxyphenyl) -2,2-propane, 3,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) 1,1-ethane, bis (4-hydroxyphenyl) 1,1-isobutanej

Bis (4-hydroxytert. Butylphenyl) 2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene or the like. Another very common one Group of polyepoxides is made in a similar way with the help of novolak resins or similar Polyphenolic resins produced.

Also suitable are the similar polyglycidyl ethers of polyhydric alcohols, such as ethylene glycol, Diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, Glycerin, bis (4-hydroxycyclohexyl) -2,2-propane and the like can be obtained.

It is also possible to use polyglycidyl esters of polycarboxylic acids which are obtained by reacting Epichlorohydrin or a similar epoxy compound with an aliphatic or aromatic polycarboxylic acid, such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthyldicarboxylic acid, dimer! -

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acidified linolenic acid and the like can be produced. Examples thereof are diglycidyl adipate and Diglycidyl phthalate.

It is also possible to use polyepoxides which result from the epoxidation of an olefinically unsaturated al! Cyclic Derive connection. Includes diepoxides, some of which are one or more monoepoxides contain. These polyepoxides are non-phenolic and are produced by the epoxidation of alicyclic olefins, for example with oxygen and selected metal catalysts, with perbenzoic acid, with acetaldehyde monoperacetate or with peracetic acid. Among such polyepoxides are the epoxyalicyclics Ethers and esters that are well known.

Another frequently preferred group of polyepoxides are those containing die.Oxyalkylengruppen in the epoxy molecule. Such oxy-alkyl groups are typical groups of the general formula

⁰ -

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in which R is hydrogen or alkyl, preferably lower alkyl (for example, from 1 to 6 carbon atoms) and in which mostly m is 1 to 4 and η is 2 to 50. Such groups can be from the main molecular chain depend on the polyepoxide or be part of the main chain itself. The ratio of oxyalkylene groups in the polyepoxide depends on many factors including the chain length of the oxyalkylene group, the nature of the epoxy and the degree of desired Water solubility. Generally, the epoxy will contain at least about 1 weight percent or more and preferably 5% by weight or more of the oxyalkylene groups.

Some polyepoxides that contain oxyalkylene groups are obtained by reacting some epoxy groups of a polyepoxide, for example those mentioned above Epoxy resins, with a monohydric alcohol containing oxyalkylene groups. Such monohydric alcohols are conveniently obtained by oxyalkylenes an alcohol such as methanol, ethanol or another alkenol, with an alkylene oxide, ethylene oxide, Are 1,2-propylene oxide and 1,2-butylene oxide particularly suitable alkylene oxides. Other monohydric alcohols can, for example, be those commercially available Ethylene glycol monoether (Cellosolve) and diethylene glycol monoether (Carbitol) and other monoalkyl ethers of polyalkylene glycols. The reaction

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the monohydric alcohol and the polyepoxide is generally in the presence of a catalyst executed. Formic acid, prostitute thy lethanolamine, diethylethanolamine, Ν, Ν-dimethylbenzylamine and »in In some cases, tin-II-chloride are suitable for this.

Similar polyepoxides containing oxyalkylene groups can by oxyalkylating the epoxy resin using other agents, for example by direct reaction with an alkylene oxide.

The polyepoxides that are used to make the aforementioned epoxides that contain oxyalkylene groups must have a sufficient number of epoxy groups so that the average number of remaining epoxy groups per molecule, which remain in the product after oxyalkylation is greater than 1.0. When oxyalkylene groups are present, the epoxy resin preferably contains about 1.0 to about 90 weight percent or more of oxyalkylene groups.

Other epoxy - containing compounds and resins include nitrogen - containing diepoxides such as them in US Pat. No. 3,365,471; Epoxy resins of 1,1-methylene-bis (5-substituted Hydantoin) as described in US Pat. No. 3,391,097; Bis-imide-containing diepoxides,

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as described in US Pat. No. 3,450,711; epoxidized aminomethyl diphenyloxides as described in XJS Patent 3,312,664; heterocyclic N, M ^e- diglycidyl compounds, as described in US Pat. No. 3,503,979; Amino epoxyphosphates as described in GB patent 1,172,916; 1,3,5-triglycidyl isocyanurates as well as other known epoxy-containing materials.

The phosphonium base - salt groups - containing resins according to the invention by implementing the Epoxy compound formed with a phosphine in the presence of an acid to give quaternary phosphonium base groups - To form containing resins.

The phosphine used can be any phosphine that does not contain interfering groups. The phosphine can be, for example, aliphatic, aromatic, or cyclic. Examples of such phosphines include Trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, phenyldimethylphosphine, phenyldiethylphosphine, Phenyldipropylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylpropylphosphine, Triphenylphosphine, tetramethyleneraethylphosphine and the like.

The acid used can be essentially any Be acid that forms a quaternary phosphonium salt. Preferably the acid is an organic car-

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boric acid. Examples of acids that can be used are boric acid, lactic acid, formic acid, Acetic acid, propionic acid, butyric acid, hydrochloric acid, phosphoric acid, and sulfuric acid. Preferably is the acid is an acid with a dissociation constant greater than about 1 χ 10 ".

The ratio of phosphine to acid is not overly critical. Because a mole of acid is used for this is to form one mole of the phosphonium group, it is preferred that at least about one mole the acid is present per mole of the desired conversion of phosphine to phosphonium.

The phosphonium / acid mixture and the epoxy compound react by mixing the components, sometimes at moderately elevated temperatures. The reaction temperature is not overly critical and will depend on the reactants and their Shares chosen. Often the reaction develops well at room temperature or temperatures up to 70 ° C, if wanted. In some cases, higher temperatures, such as 110 ° C or even higher, can be used will. A solvent is not necessary, although it is often used for better control to enable the reaction. Aromatic hydrocarbons, monoalkyl ethers of ethylene glycol and aliphatic alcohols are suitable solvents.

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The proportions of the phosphine and the epoxy compound and the optical ratio can be different the proportions depend on the individual reactants. Usually about 1 to 50 parts by weight are used Phosphine used per 100 parts by weight of epoxy compound. These proportions are generally with With respect to the amount of phosphine selected, which is typically from about 0.1 to about 35%, based based on the total weight of the phosphine and the epoxy compound. Since the phosphine salt with the Epoxy groups of the epoxy resin used reacts to create a resin containing epoxy groups, the stoichiometric amount of phosphine used must be less than the stoichiometric Equivalent of the epoxy groups present, making a final resin with an epoxy group is obtained per average molecule.

The resins containing sulfonium base groups according to the invention are formed by implementation. the epoxy compound with a sulfide in the presence an acid, resulting in resins with quaternary sulfonium base groups.

The sulfide used can be essentially any sulfide that reacts with epoxy groups and that contains no disturbing groups. The sulfide can, for example, be aliphatic, mixed aliphatic aromatic, be aralkylic or cyclic. At-

Games of such sulfides include: diethyl sulfide, dipropyl sulfide, dibutyl sulfide, diphenyl sulfide / Dihexyl sulfide, ethylphenyl sulfide, tetramethylene sulfide, Pentamethylene sulfide, thiodiethanol, thiodipropanol, thiodibutanol and the like.

The acid used can be essentially any acid including a quaternary sulfonium salt forms. The acid is preferably an organic carboxylic acid. Examples of acids that are used are boric acid, formic acid, lactic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, phosphoric acid and sulfuric acid. Preferably the acid is an acid with a dissociation constant greater than about 1 χ 10 "- *.

The sulphide to acid ratio is not excessive critical. Since one mole of the acid is required to form one mole of the sulfonium group, it is preferred that at least about one mole of the acid is present for the conversion of every mole of the desired sulfide to the sulfonium compound.

The sulfide / acid mixture and the epoxy compound react by mixing the components, im generally at moderately elevated temperatures, around 70 - 110 ° C. A solvent is not necessary, although one is often used to provide better control of the reaction.

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* Aromatic hydrocarbons, monoalkyl ethers
Ethylene glycol and aliphatic alcohols are suitable solvents. The proportions of the sulfide and the epoxy compound can be different
and the best proportions depend on the individual reactants. Usually from about 1 to about 50 parts by weight of the sulfide is used per 100 parts of the epoxy compound. The proportions are generally made with reference to the
Amount of sulfur indicated, which is typically from about 0.1 to about 35%, based on the total weight of the sulfide and the epoxy compound. Since the sulfide salt reacts with the epoxy groups of the epoxy resin used to form an epoxy group-containing resin ₉ the stoichiometric amount of sulfide that is used must be less than the stoichiometric equivalent of the epoxy groups present, so that a final resin with one epoxy group per average molecule is obtained.

If it is desired to incorporate boron into the resin molecule, one method is to incorporate the boron with Using an amine borate or an amino - containing boron ester, as in patent application P 21 63 143.6 dated December 20, 1971, to be incorporated. The boron compound reacts with available epoxy » groups to quaternary ammonium borate groups in the

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Resin molecule to form.

The reaction of the boron compound can take place simultaneously with the formation of the phosphonium or sulfonium groups because the reaction conditions for this reaction are similar.

The individual reactants, proportions and reaction conditions are in agreement selected with considerations well known in the art, for example to prevent gelation of the product during the reaction. So should for example, excessively strict reaction conditions are not applied. Furthermore, connections should that have reactive substituents cannot be used with epoxy compounds with which these substituents can react unfavorably under the desired conditions.

The product that forms the resin according to the invention, can be networked to a certain extent; however, it remains soluble in certain organic solvents and may further be hardened to a hard thermoset state. It's distinctive characterized by its epoxy content and its content of chemically bound quaternaries Onium groups.

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Aqueous compositions containing the above reaction products are well suited as coating compositions and can be prepared by any conventional method, for example, dipping, brushing, etc. can be applied. But they are special for them electrical deposition excellently suited.

The resins of the invention are "per se" in water dispersible, but, if desired, further acidic solubilizing agents can be added will.

The presence of a boron compound in the electrodeposited film is essential because Boron compounds obviously the hardening of the catalyze deposited film, grant lower curing temperatures and / or harder films. If the resin is initially made without boron and / or additional boron is desired when the resin is used is dispersed, a compound of boron may be added preferably boric acid or a precursor thereof.

The acid or acidic solubilizing agent is preferably any acid having a dissociation constant greater than Ix 10 "* 5. Preferably The acid or acidic solubilizing agent should seira an organic acid with a bucket Dissociation constant higher than about 1 χ 10 "^ |

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the currently preferred acid is lactic acid. The addition of acid helps stabilize the Resin, as the epoxy kaiin tend to continue when stored under highly alkaline conditions to polymerize; sometimes the acid also helps dissolve the resin more completely to obtain. It is also advantageous to make these coatings from an acidic or weakly basic one Electrically deposit solution (for example with a pH between about 3 and about 8.5) and the additive the acid is often suitable for the desired adjust pH.

The resin according to the invention changes its properties when placed in a water-containing medium will, as in a feedstock - concentrate for electrical deposition with high solids or the electric deposit bath. Since the boron often, when it is present and chemically bound, obviously is only weakly bound to the resin, it can be split off from the resin molecule. As the boron electrodeposits itself with the resin and is found in the electrodeposited film the boron from the water-containing medium can be wholly or partly with the help of Separation agents are removed, such as by electrodialysis or ultrafiltration, in the form of boric acid. As a result, the resin can be in the aqueous

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Medium referred to as a water-containing medium containing a non - gelled water - dispersible epoxy resin with at least one 1,2-epoxy group in the average molecule, and chemically - bound quaternary onium base - salt groups, selected from the group consisting of salts of the sulfonium or phosphonium base.

The resin contains from about 0.1 to about 35 weight percent phosphorus or sulfur, with at least about 1% of said phosphorus or sulfur and preferably about 20%, more preferably 50%, and most preferably substantially all of the phosphorus or sulfur in the form of salt groups of chemically bound quaternary onium base; containing said water In the preferred embodiment, medium contains about 0.01 to about 8% by weight of bot which is contained in Boric acid and / or a borate or a boric acid complex is included.

The concentration of the product in water depends on the process parameters that are used and is generally not critical. Usually, however, the main part of the aqueous preparation is Water, for example the compound can contain 1 to 25% by weight of the resin *

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The electrodeposable compounds according to the invention preferably contain a coupling solvent. The use of a coupling Solvent gives the deposited film a better appearance. These solvents include hydrocarbons, alcohols, esters, ethers and ketones. The preferred coupling Solvents include monoalcohols, glycols and polyols, as well as ketones and ether alcohols. Specific coupling solvents include isopropanol, butanol, isophorone, pentoxane (4-methoxy-4-methyl-pentanone-2), Ethylene and propylene glycol, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, 2-ethylhexanol and the hexyl monoether of ethylene glycol. This one preferred coupling solvent is 2-ethylhexanol. The amount of solvent is not overly critical, generally between about 0.1 and about 40 weight percent of the dispersant is used, preferably between about 0.5 and Wt%.

While the resins described above are essentially the only resinous constituent of the electrodepositable preparation can be electrodeposited, it is often desirable to improve or change the appearance of the film and / or other film properties, the

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- to incorporate various non-reactive and reactive compounds or resinous materials into electrically depositable preparations, such as plasticizing compounds, including N-cyclohexyl-p-toluenesulfonamide, ortho- and para-toluenesulfonamide, N-ethyl-ortho- and para-toluenesulfonamide, aromatic and aliphatic Polyether polyols, phenolic resins including allyl ether-containing phenolic resins, liquid epoxy resins, quadroles, polycaprolactones; Triazine resins such as resins based on melamine and benzoguanamine, particularly alkylated formaldehyde reaction products thereof; Urea-formaldehyde resins, acrylic resins, hydroxyl and / or carboxyl group - containing polyester wad hydrocarbon resins.

Other additives include esters, such as butyl benzyl phthalate, Dioctyl phthalate, methyl phthalyl ethyl glycolate, Butyl phthalyl butyl glycolate, cresyl diphenyl phosphate, 2-Ethylhexyldiphenylphosphate, Polyethylene Glycol * 200-Dibeti2iOate as well as polyester, 2,2,4-trimethylpentanediol monoisobiityrate (Texanol) a »

In most cases, a pigment compound and, if desired, numerous additives, such as antioxidants, surface treatment agents or crosslinking agents, for example Foam Kill 639 (a hydrocarbon oil, the inert J> i & tumeenerde

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contains) as well as glycollated acetylenes (e.g. Surfynol)), sulfonates, sulfated fatty acid anides, including the alkyl phenoxy polyoxyalkylene alkanols and the like. The pigment compound can be of any usual kind, including only For example iron oxide, lead oxide, strontium chromate, carbon black, titanium dioxide, talc, barium sulfate and color pigments such as cadraium yellow, Cadmium red, chrome yellow and the like.

In the electrodeposition processes using aqueous coatings as above described, are used, the aqueous preparation with an electrically - conductive Anode and an electrically conductive cathode associated, wherein the surface to be coated is the cathode. During the touch with the bath containing the coating composition, a firmly adhering film of the coating composition is created on the cathode deposited. This is in contrast to the known processes in which polycarboxylic acid Resins are used and the advantages listed are in large part due to these cathodic ones Attributed to deposit.

The conditions under which the electrodeposition is carried out are general 'Similar to those found in electrical debris other coatings can be used, © ie:>

The voltage applied can vary widely, for example as low as 1 volt or as high as several thousand volts, whether-. probably they are typically between 50 and 500 volts lies. The current density is generally between about 10.7 amps and 160 amps each cm ^ (1 ampere and 15 ampere per square foot) and tends to degrade during electrodeposition.

When the resin of the invention is freshly electrodeposited on the cathode, it contains quaternary onium base groups. The acid residue that forms the salt migrates at least partially after the anode. If the electrodeposition bath contains boron, the electrodeposited one contains Resin also boron, which is linked to the basic groups found in the film that is on The amount of bound boron in the electrically deposited film increases as the boron concentration in the bath increases to a saturation level, which depends on the number of basic groups in the concentration and the Basicity of the basic groups.

As long as the film can be crosslinked to a certain extent, it will remain in certain organic solvents soluble.

Per freshly seasoned, untreated electric depositable film can be characterized as follows: one on an electrically conductive substrate electrodeposited epoxy containing a non-gelled epoxy with average at least one 1,2-epoxy group in the molecule, chemically bound quaternary Onium base and, if boron is present in the electrodepositable mass, 0.01 to about 8 wt% boron.

The method of the invention is applicable to coating any conductive substrate and especially a metal such as steel, aluminum, copper, magnesium and the like. After the deposit the coating is cured, generally by heating to elevated temperatures. Temperatures from 121 ° C to 260? C for 1 to 30 minutes are typical curing conditions that are used will.

During the treatment, especially at elevated temperatures, at least a substantial part of the quaternary onium base in phosphines or phosphine oxides in case of. Phosphonium groups and sulphides, in the case of sulphonium groups decomposed, which is the case with Cross-linking of the coating helps, which after hardening is not - meltable and not - soluble. The presence: increased by boron salts and complexes in the film

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the degree of crosslinking, the temperature reduces the is necessary for adequate cure at commercially reasonable times and results in coatings with improved hardness and corrosion resistance.

Already mentioned above are the essential resin components.

(A) ¹ 'a resin which has epoxy groups and optionally oxyalkylene groups;

(B) quaternary onium groups as salts of acids, preferably with a vain dissociation constant greater than 1 χ 10 "* ^ and where applicable

(C) boron.,

All of these components can be determined qualitatively and quantitatively by numerous known methods will. . '. .

Epoxy groups. can by the well known pyridinium chlorohydrate process, which for example in Siggia, "QUANTITATIVE ORGANIC ANALYSIS VIA FUNCTIONAL GROUPS", John Wiley & Sons, Inc., New York (1963), page 242, can be determined. . .

All of the base groups present in the polymer, including quaternary groups,

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can be determined on a separate resin sample. In general, the resin sample is neutral; however, if the resin is basic, the sample must neutralized with a known amount of the acid present in the resin as a salt * If the acid that is present in the resin as a salt, it is a weak acid compared to HCl, the resin is titrated with HCl and with sodium hydroxide in an automatic titrator back-titrated. The HCl titration shows the total number of base groups present. To the For example, a typical analysis is performed as follows: a 10 ml sample of approximately 10% strength Solid-containing electrical deposition bath is dissolved in 60 ml of tetrahydrofuran pipe ttiert. The sample is titrated with 0.1000 normal HCl to the pH end point. The amount of used Standard acid is equivalent to the quaternary base present. The sample is then 0.1000 normal Sodium hydroxide back-titrated, showing a titration curve with multiple endpoints. In In a typical example, the first endpoint corresponds to excess HCl. From the HCl titration the second end point corresponds to the neutralization of the weak acid (for example lactic acid). The difference in volume between the two endpoints indicates the volume of the standard base that is equivalent to the weak acid of the sample

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If, on the other hand, a solvent such as propylene glycol is used with, for example, tetrahydrofuran, in order to maintain the homogeneity of the sample, the boron present is also titrated, because the boron in its existing form forms an acid complex with the propylene glycol. Among those mentioned Conditions can separate boric acid from weak acid (for example lactic acid) distinguish an additional inflection point in the pH titration curve.

For example, when acidic salts of strong acids are present, other methods must be used to remove the acid and any quaternary groups present to determine..If the resin is for example quaternary Contains hydrochloride groups, the resin can be dispersed, for example in a mixture of glacial acetic acid And tetrahydrofuran, the chloride with mercury acetate complex can be thought of and the sample with Perchloric acid can be titrated to give quaternary groups.

Boron can be determined as described by R. S. Braman in "Boron Determination", ENCYCLOPEDIA OF INDUSTRIAL CHEMICAL ANALYSIS, F. D. Snell and Hilton, editors, John Wiley & Sons, Inc., New York (1968), Volume 7, Pages 384-423. The boron can can be determined on a separate sample. To the

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Example by pipetting a 10 ml sample of a cationic containing approximately 10% solids electric deposition bath in 60 ml of distilled water. Sufficient HCl is then added to lower the pH to about 4.0. The sample is then back-titrated with 0.1000 normal sodium hydroxide to the first inflection point in the pH titration curve, using a Metrohm Potentiograph E-436 automatic titration device or equivalent apparatus is used. 7 g of mannitol are then added. The solution becomes acidic and the titration continues up to the second turning point in the pH titration curve. The amount of base consumed between the first and the second end point is a measure of the number of moles of the boric acid complex, formed in the sample.

The above description is only an example of the method used to create the existing Determine groups quantitatively and qualitatively. In a special case, the analytical method customized for the specific resin. However, there are known procedures for each case which enable an exact determination of the significant chemical units.

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The invention is accomplished by the following. Examples explained in more detail. All parts and percentages are weights, unless otherwise stated. .'.'_. "

example 1

A reactor equipped with a thermometer, a stirrer and devices for maintaining an inert gas blanket was charged with 100 parts of a commercially available epoxy resin (Epon.836) and 16 parts of monobutyl ethylene glycol ether. This mixture was heated to 45 ° C. with stirring and then 30 parts of tributylphosphine and 16 parts of 85% lactic acid were added. The reaction was exothermic and the temperature rose to 70 ° C. 10 parts of water were then added and the mixture was kept at a reaction temperature of 78 ° C. for a further 20 minutes. After a further 25 minutes at 800 g, 34 parts of water were added and the. Let the temperature drop to 72 ° - G. After a further 30 minutes the temperature increased to 90 ° C. and a clear resin solution was obtained. The reaction product would have the following values, calculated on 100% solids
Epoxy value: 3700

Hydroxyl value 118 '. .

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An electric deposition bath was prepared, by adding 52 parts of the above resin reaction product, 30 parts of monobutylethylene glycol ether and 350 Parts of water mixed. From this bath, steel sheets were electrically coated at 50 volts for 45 seconds. The film obtained was initially somewhat water-sensitive, but after curing for 30 minutes at 177 ° C. it became smooth and shiny and had a 3 H. Pencil hardness and thermoplastic properties. . ■

Example 2

A reactor with a thermometer, a stirrer and equipment for maintaining an inert gas blanket was fitted with 354 parts of a commercial epoxy resin (Epon 829) and 60 parts of bisphenol A charged. The reaction mixture was heated to 175 ° C and an exothermic reaction became observed at 186 ° C. The reaction temperature was then allowed to drop to 150 ° C, then 170 Parts of polypropylene glycol with a molecular weight of about 600 are added along with 1.1 parts of dimethylethanolamine. The reaction mixture was held at 140 ° C for 5.5 hours until they get a Gardner-Holdt viscosity of L -K was measured in a 50X solution of 90/10 isophorone / toluene. This 50X solution had a hydroxyl value of

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131 and an epoxy value of 1643 “It would be a low one Amount of formic acid added to the amine catalyst to neutralize.

At a reaction temperature of 53 ° C, 85
Parts of tetrahydrofuran and a slurry of 36.4 parts of tributylphosphine and 19.1 parts of 85% lactic acid were added. After 5 minutes, 20 parts of water were added and a further 18.2 parts
Parts of tributylphosphine and 9.55 parts of 85% lactic acid. After a further 5 hours, additional
18.2 parts of tributylphosphine and 9.55 parts of 85% strength * lactic acid were added. The reaction mixture was held for an additional 5 hours. The 81.2% solids · reaction product then had a hydroxyl value of 169 and an epoxy value of 4,390.

An electrodeposition bath was prepared by adding 61.5 parts of the above reaction mixture mixed together with 15 parts of monobutyl ethylene glycol ether and 423 parts of water. The electric deposition bath contained about 10% solids.

Aluminum and steel plates were at one tension Electrically coated between 100 and 150 volts for one minute at room temperature. After 30 minutes Hardening at 177 ° C, the plates showed a yellow film with a 3 H pencil hardness and a film

thickness from 0.0127 to 0.0152 mm. The film was thermosetting and acetone-resistant.

Example 3

A reactor equipped with a thermometer, a stirrer, a still, a reflux condenser, a water trap and means to create an inert gas blanket was equipped with 885 parts a commercially available epoxy resin (Epon 829) together with 151 parts of bisphenol A. The mixture was heated to 170 ° C and held at 185 ° C for 45 minutes. The reaction mixture was then on Cooled 160 ° C and there were 425 parts of polypropylene glycol 600 together with 2.7 parts of DimethyIaminoäthanol added. The reaction mixture was held at 135 ° C. until it had a Gardner-Holdt viscosity of R (about 6 hours) with the Gardner - Holdt viscosity being a 50% Solid solution in 90/10 isophorone / toluene was measured. The 50% solution was one epoxy equivalent from 1922 and a hydroxyl value of 143. 1.8 parts of 90% formic acid were then added, in order to neutralize the catalyst in the meantime.

75 parts of isopropanol were then added to the reaction mixture at 100.degree. To the reaction

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mixture was a solution of 104 parts of thiodiethanol in 90 parts of 85% lactic acid and at 80 ° C 80 parts of isopropanol were added.

This mixture was added over a period of 20 minutes as the temperature rose at 90 ° C. After the addition was complete, the reaction mixture was kept at 95 ° C. for 8 minutes held. There was then 488 parts of deionized water, 7.4 parts of a surfactant (Foam-Kill 639) and 95 parts of 2-ethylhexanol were added. The resulting 65% solids solution had an epoxy equivalent of 3199 and one hydroxy value of 70. This product is later referred to as the carrier resin.

In a manner similar to that described above, a dispersed carrier resin was prepared for addition made into pigment pastes, with the exception that after the addition of polypropylene glycol 600 and dimethylaminoethanol, the reaction mixture for approximately 4 hours to a Gardner-Holdt viscosity held by M, measured in the same way as above. The one containing 50% solids Product had an epoxy equivalent of 1649 and a hydroxyl value of 135.

After the addition of formic acid to neutralize the catalyst, it became a solution of 208 parts

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Thiodiethanol and 180 parts of 85% lactic acid in 80 parts of isopropanol were added. The mixture was added to the previous reaction mixture at 82 ° C over 20 minutes. the Temperature rose to about 90 ° C. The reaction mixture was kept at 91 - 95 ° C for 8 minutes, after the encore was over.

To this reaction product were added 488 parts ^T of deionized water, 7.4 parts of a surfactant (Foam - Kill 639) and 95 parts of 2-ethylhexanol. The resulting product was a 65% resin solution. This resin solution is referred to as the dispersed carrier resin for the pigment paste.

The pigment paste was prepared by adding 396 parts titanium dioxide, 4 parts

s

Carbon black and 143 parts of the above carrier resin ground together with 200 parts of deionized water. The pigment paste was applied to a Hegman No. 7 value crushed. . ·.

An electrodeposition bath was made by slowly adding 392 parts of the carrier resin, 160 parts of the above pigment paste and 3250 parts of deionized water were mixed.

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2 2 618 O

- 35 - ■ '· ■■ ·.

Zinc-phosphated steel plates became electrical coated using the above electric deposition bath at 29 ° G and 300 volts for 90 seconds. The resulting electrodeposited film became cured at 177 ° C for 25 minutes. The cured film had a thickness of 0.0140 mm smooth and shiny.

The electrically depositable preparation had a breakdown voltage of more than 500 volts at 29 ° C and a throw at 500 volts of 12.70 cm at 19 ° C as measured in the Ford throw test. "

Example 4 -

A reactor with a stirrer, a thermometer and facilities for maintenance

was equipped with an inert atmosphere, was charged with 500 parts of a commercially available epoxy resin (Epon 836) and then heated to 85 ° C. A solution consisting of 55 parts of thiodiethanol, 48.3 parts of 85% lactic acid and 10 parts of water was then added over a period of two minutes with stirring. The reaction mixture was kept at 85 ° C for 20 minutes, then a further 10 parts of water were added and the reaction mixture was stirred at a temperature between 85-88 ⁰ C for 5 minutes overall

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keep. Another 10 parts of water were then added. The above reaction mixture had one Epoxy value of 836 and a hydroxyl value of 215.

The above reaction product was diluted to 10% solids using an electrodeposition bath a pH of 6.4. Aluminum plates were at 100 volts for 1 minute at a bath temperature electrically coated at 24 ° C. Steel plates were electrically plated at 200 volts for one minute. The resulting films had good wet film strength. After curing at 177 ° C füif For 15 minutes the film exhibited high gloss and thermoplastic properties.

Example 5

In the same manner as in Example 4, 500 parts of a commercially available epoxy resin (Epon 836) and 50 parts of monobutyl ethylene glycol ether were placed in a reactor and heated to 82.degree. It then became a solution consisting of 55.5 parts of thiodiethanol, 28.2 parts of boric acid and 40 parts of 1,2-propanediol and 10 parts of water were added over a period of two minutes at 82 ° C. After 7 minutes a further 20 parts of water were added. The reaction mixture was warmed and became clear at a temperature of 102 ° C.

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The reaction mixture had an epoxy value of 644 and a hydroxyl value of 257. The resulting Resin could be deposited elastically.

Example 6

A reactor equipped with a stirrer, thermometer and inert gas blankets, was charged with 500 parts of Epon 836 and the reactor was heated to 95 ° C. Afterward was a solution of 55.5 parts of thiodiethanol, 52.4 parts of 85% phosphoric acid and 10 more Parts of water are added over a period of 4 minutes at 95 ° C. After 10 minutes it was a mixture of monobutyl ethylene glycol ether. and 10 parts of water over a period of 50% Minutes added. Then x 45 parts of water were added. At a temperature of 101 ° C a clear resin was obtained. A 10% solids solution of the resin was electrodeposable.

Example 7

A reactor with a stirrer, a thermometer and feeders was fitted with 165 parts of a commercially available epoxy resin (Epon 836) charged, and the mixture

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heated to 56 ° C. A solution of 22.5 parts of diethyl sulfide, 26.5 parts of 85% lactic acid and 5 parts of monobutylethylene glycol ether were in the Introduced into the reactor and the mixture was stirred for one hour, the temperature at 85 ° C was increased. Then 10 parts of water were added and after a further 40 minutes at one The fection temperature of 70 ° C was again 10 Parts of water added. The resulting water dispersible reaction mixture had a hydroxyl value of 110 and an epoxy value of 5723.

The reaction mixture was diluted to 10% solids with water and aluminum and Steel plates electrically plated at 100 to 150 volts for one minute to a .00508 mm - film to yield. After curing at 177 ° C for 30 minutes, the film had good flow, high gloss and thermoplastic properties.

Using other epoxy compounds, amines, phosphines, sulfides, acids, salts and Boron compounds can also be used to produce other reaction products in accordance with the invention. In Similarly, other conditions and additives and the like can be used to make coating preparations, to formulate and use as desired.

309826/1187

Claims (1)

Patent claims: 1. Non-gelled water dispersible Epoxy resin, characterized in that it contains in its molecule: (A) at least one 1,2-epoxy group and - (B) at least about 0.1% by weight of chemically bound phosphorus or sulfur, with at least some of the phosphorus or sulfur in the form of a salt one quaternary onium base is present. 2. Epoxy resin according to claim 1, characterized in that that it also contains boric acid or a compound which can be hydrolyzed to boric acid. 3. Non-gelled water-dispersible epoxy resin according to claim 1, characterized in that that it contains in its molecule: (A) at least one 1,2-epoxy group, (B) at least about 0.1% by weight of chemically bound phosphorus or sulfur, with at least some of the phosphorus or sulfur in the form of a salt one quaternary onium base is present and 309826/1187 (C) at least about 1 weight percent oxyalkylene groups. A. Epoxy resin according to claim 3, characterized in that that it also contains boric acid or a compound which can be hydrolyzed to boric acid. 5. Non-gelled water-dispersible epoxy resin according to claim 1, characterized in that that it also contains in its molecule: (A) at least about 1 weight percent oxyalkylene groups and (B) chemically bound boron. 6. Non-gelled water-dispersible epoxy resin according to claim 1, characterized in that that the quaternary onium groups it contains are chemically - bound phosphorus or Contain sulfur, with at least part of the phosphorus or the sulfur as a salt an acid with a dissociation constant higher than 1 χ 10 "^ is present. 30 98 2.6 / 1 187 7. epoxy resin according to claim 6, characterized in that that there is also boric acid or a compound hydrolyzable to boric acid contains. 8. Resin according to claim 6, characterized in that the resin molecule additionally at least contains about 1% by weight of oxyalkylene groups. 9. Epoxy resin according to claim 8, characterized in that it also contains boric acid or contains a compound hydrolyzable to boric acid. 10. Resin according to claim 6, characterized in that it is also chemically bound Contains boron. 11. Resin according to claim 8, characterized in that it is also chemically bound Contains boron. 12. A method for coating an electrically conductive substrate serving as a cathode, in that between an anode and a cathode in contact with an aqueous dispersion of electrical Electricity flows, characterized 309826/1187 that the aqueous dispersion is a non-gelled water-dispersible epoxy resin which contains in its molecule: (A) at least one 1,2-epoxy group; and (B) at least about 0.1% by weight of chemically bound phosphorus or sulfur, where at least a portion of the phosphorus or sulfur is in the form of a salt of a quaternary onium base. 1 * 3 .; "Method according to claim 12, characterized in that that the aqueous dispersion consists of a mixture that contains: (A) Non-gelled, water-dispersible epoxy resin, which in its molecule contains: (1) at least one 1,2-epoxy group and " (2) at least about 0.1% by weight of chemically bound phosphorus or sulfur, wherein at least a portion of the phosphorus or sulfur is in the form of a salt of a quaternary onium base is present and (B) boric acid or a compound which can be hydrolyzed to form boric acid. 309826/1187 14. The method according to ■ claim 12, characterized in that the epoxy resin additionally contains at least about 1 % by weight of oxyalkylene groups. 15. The method according to claim 14, characterized in that that the aqueous dispersion also has boric acid or one under formation Contains compound hydrolyzable by boric acid. 16. The method according to claim 12, characterized in that the aqueous dispersion of egg * nem non-gelled dispersible in water Epoxy resin, which contains in its molecule: (A) at least one 1,2-epoxy group; (B) at least about 0.1% by weight of chemically bound phosphorus or sulfur, where at least a portion of the phosphorus or sulfur is in the form of a salt of a quaternary onium base; (C) at least 1% by weight of oxyalkylene groups and (D) chemically bound boron. 309876/1187 17. The method according to claim 12, characterized in that that the aqueous dispersion consists of a non - gelled water - dispersible Epoxy resin, which contains in its molecule: (A) at least one 1,2-epoxy group and (B) at least about 0.1 wt% chemically - bound phosphorus or sulfur, wherein at least a portion of phosphorus or of sulfur in the form of a salt of a quaternary onium base and an acid having a dissociation constant higher than 1 χ 10 ~ ⁵ , is present. 18. The method according to claim 12, characterized in that that the aqueous dispersion consists of a mixture that contains: (A) ungelled water dispersible Epoxy resin, which contains in its molecule: (1) at least one 1,2-epoxy group and (2) at least about 0.1% by weight of chemically bound phosphorus or sulfur, where at least part of the phosphorus or sulfur is in the form of a salt of a quaternary onium 30 9 87R / 1V8 7. base and an acid that has a dissociation constant higher than 1 χ 10 "has 5; and (B) boric acid or a compound which can be hydrolyzed to form boric acid. 19. The method according to claim 12, characterized in that that the aqueous dispersion of a non-gelled dispersible in water * epoxy resin, which contains in its molecule: (A) at least one 1,2-epoxy group; (B) At least about 0.1 wt% chemically bound Phosphorus or sulfur, with at least part of the phosphorus or des Sulfur in the form of a salt of a quaternary oenium base and an acid, which has a dissociation constant higher than 1 χ 10 * 5 is present; and (C) at least about 1% by weight Öxyälkylengrüippen » 20, method according to claim 12j, characterized in that that the aqueous dispersion consists of a mixture * which contains 3Ö9S26 / 1 -. (A) non-gelled water-dispersible epoxy resin, which in its molecule contains: (1) at least one 1,2-epoxy group j (2) at least about 0.1% by weight of chemically bound phosphorus or sulfur, wherein at least a portion of the phosphorus or sulfur is in the form of a salt of a quaternary onium base and an acid that has a dissociation constant higher than 1 χ has, is present; and (3) at least about 1 weight percent oxyalkylene groups and (B) boric acid or a compound which can be hydrolyzed to form boric acid. 21. The method according to claim 12, characterized in that that the aqueous dispersion consists of a non - gelled water - dispersible Epoxy resin, which contains in its molecule: (A) at least one 1,2-epoxy group; (B) at least about 0.1% by weight chemically bound Phosphorus or sulfur, with at least part of the phosphorus or the 309826/11 «7 Sulfur in the form of a salt of a qttaternary onium base of an acid, which is a Has a dissociation constant higher than 1 χ 10 "" - * is present; and (C) chemically bound boron » 22. .The method according to claim 12, characterized. draws that the aqueous dispersion of a - 'no not - gelled dispersible in water Epoxy resin, which contains in its molecule: ■. · (A) at least one 1,2-epoxy group; (B) at least about 0.1% by weight chemically - bound, those phosphorus or sulfur, with at least some of the phosphorus or sulfur in the form of a salt one ,, quaternary onium base and an acid that has a dissociation constant of higher as 1 χ 10 ~~> is present; (C) at least about 1% by weight of oxyalkylene groups and (D) chemically bound boron. 309826/1187