JPS623857B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a water-dilutable resin composition. The composition of the present invention comprises the reaction product of base-neutralized H ₃ PO ₃ with a polyether epoxide of general formula (a) or (q) below and optionally other types of mono- or polyfunctional epoxides. It is a mixture of things. A preferred method of the invention is to react the polyether (E ¹ ) and optionally the other epoxide (E ² ) with an orthophosphoric acid source material and react the resulting product with a base, preferably an unstable base. It is to neutralize it. However, the present invention also
It consists of a preparation method in which separately produced reaction products of E ¹ and phosphoric acid and reaction products of E ₂ and phosphoric acid are combined. If the base is unstable, such as ammonia or a volatile amine, diluted with water,
The neutralized resin is made into a water-insensitive, high-performance, thermoset resin by evaporating the water, decomposing the ammonia base by heating, removing the ammonia (or amine), and curing. Can be converted. Common curing agents capable of reacting with acidic and/or alcoholic hydroxy groups can be mixed with the uncured resin. The term "volatile" means that it can be removed by heating at normal pressure to an extent that does not adversely affect the cure rate or properties of the cured resin. Ammonia driven off during or after water evaporation can be easily recovered as a non-volatile acid salt by known methods. The coatings of the present invention are coatings formed on various substrates (preferably metal) from an aqueous dispersion of the composition described above. A preferred method of the present invention is defined below as a method for producing a reaction product of base-neutralized orthophosphoric acid and polyether epoxide, which method comprises: (1) a reaction product of the general formula or general formula [In the formula, Q is independently

[Formula] or

[Formula] In the formula, R ² is Br, Cl, or an alkyl group having 1 to 4 carbon atoms, or an alkenyl group, and R ³ is an alkylene or alkenylene group having 1 to 4 carbon atoms, C(CF ₃ ) ₂ , -CO- , _-SO2- , -S-, -O-
or a single bond, and R ₄ is -Br, -Cl or a C ₁ -C ₄ alkyl or alkenyl group), n is an integer from 0 to 40, r is 0, 1 or 2, and R ¹ is H, methyl or ethyl;
^R20 is H or alkyl having 1 to 12 carbon atoms]
A polyether epoxide resin E ¹ and optionally (2) a vicinal epoxide E ² other than general formulas (a) and (q), which has an EEW (epoxy equivalent weight) of 90 to 2000 and has an orthophosphoric can be converted into a water-dispersible substance by reacting with an acid and neutralizing with a base. until the oxirane groups in the converted E ¹ and optionally E ² are in sufficient quantity to render the resulting mixture product dilutable with water when contacted with a base.
The reaction consists of E ¹ and any E ² , the phosphate source material and (provided by the phosphate source material)
This is carried out by contacting 0 to 25 moles of water per molecule of H ₃ PO ₄ . The amount of orthophosphoric acid contained in said phosphoric acid source material or obtained therefrom by hydrolysis is:
the amount to provide at least 0.3 P-OH groups per oxirane group, and the molar ratio of E ¹ to E ² epoxide is from 0.1 to 100 when E ² is present;
and () contacting the resulting reaction product with at least a sufficient amount of base to render it dilutable with water. The composition of the invention comprises phosphoric acid, E ¹ and optionally
When made by reaction with E ² and neutralized with a base,
It is a resinous mixture that is water dilutable. The composition of the invention is a water-dilutable product obtained by contacting the resinous product with a base. Aqueous dispersions of the neutralized products constitute a preferred embodiment of the compositions of the invention. The neutralized epoxide/acid reaction product of the invention comprises: (A) one or two of the oxirane groups in the E ¹ epoxide represented by one of the general formulas (a) and (q);
- a resin molecule derivatized by converting it into a glycol or beta-hydroxyphosphomonoester group, the epoxy molecule from which the resin molecule is derivatized has an average EEW of 172-5500. The oxirane group in vicinal epoxide ^E2 other than the epoxides of general formulas (a) and (b) is
glycol or any other molecule derivatized by converting it to a beta-hydroxyphosphomonoester E ₂ , the molecule of which is between 90 and 2000
has an EEW, the molar ratio of E ^1- derived molecules to said E ^2- derived molecules is within the range of 0.1 to 100, and
The ratio of glycol to monoester groups in each of the _E2 's is within the range of 0-18. (B) 0 to 85 parts by weight of orthophosphoric acid ( _{H 3} ^PO ₄ ) per 100 parts by weight of said E 1 and E ² derived molecules; (C ⁾ at least a sufficient amount of the P-OH groups in said E ¹ and E 2 derived molecules are are precisely defined as water-dilutable, resinous phosphate compositions consisting of an amount of one or more bases which are combined together, thereby making them water-dispersible. In compositions of the preferred type described above, those molecules which are not derived from epoxides of general formula (a) or (q) can be derived from ^E2 epoxides as defined above, which ^E2 epoxides are methylol or lower alkoxymethyl. group (i.e. R
is an alkyl group having 1 to 4 carbon atoms or 2 to 4 carbon atoms
It consists of a benzene ring substituted with an alkenyl group (R-O-CH ₂ -). In other preferred types of compositions mentioned above,
Molecules that cannot be derived from E ¹ epoxide are derived from E ² epoxide, which consists of epoxy novolak molecules. The base component of the composition as defined above is preferably unstable. As used herein, the term "water dilutable" means that the product so formed, when diluted with a substantial amount of water, forms a substantially homogeneous solution and the resulting dispersed This means that the product does not settle or suffer damage at such high speeds that the dispersion is impractical for use as a coating. The mixture that makes up the composition can be formed in one of two ways. One method is
One method is to co-react the E ¹ and E ² epoxides with a phosphate source material; another method is to react each of the epoxides, E ₁ and E ₂ , with a phosphate source material separately. The resulting products are mixed before or after neutralization with the same or different bases. The latter type of making the composition involves combining the separately formed E ¹ /H ₃ PO ₄ and E ² /H ₃ PO ₄ reaction products and a sufficient amount of base to make the combination water-dispersible. consists of doing. The following embodiments of the invention are also preferred as they have particular advantages as coatings. (1) The product of the foregoing process, where E ₁ is a diglycidyl ether as defined in general formula (a) above, bisphenol A and the diglycidyl ether of bisphenol A, where R ³ is

and r is 0). (2) The product of example (1) made water dilutable by neutralization with ammonia or amines (3) The product of example (2) when diluted with water to 50% by weight or less Neutralized composition. (4) Thermoset resin coating made from the water-diluted product of Example (3). (5) A product of the process broadly defined above with an EEW of ³²⁰⁰ or less. (6) Embodiments of the process, broadly defined, wherein the overall ratio of acidic hydroxyl to oxirane groups of the phosphate source material is within the range of 0.4 to 1.0. (7) A specific example of the above method in which the amount of H ₃ PO ₄ used in the reaction is 1 part or less per 100 parts of E ¹ . (8) A specific example of the above broadly defined process in which the phosphoric acid is provided to the reaction as 70-90% aqueous H ₃ PO ₄ . The cured resin of embodiment (4) above is derived from an aqueous composition of the invention in which the neutralized epoxide/H ₃ PO ₄ reaction product is the only resinous component diluted with water, or Other water-dispersible resins, reactive diluents and/or hardeners can also be derived from similar existing compositions. In either case, curing is catalyzed by known chemicals, ultrasonic vibrators, heat, high energy waves or particle radiation, and the like. All epoxides of the E ¹ type represented by the general formula (a) are described as resins. Lower epoxides such as the diglycidyl ether of bisphenol A are available as pure crystalline solids. However, most DGEBA type epoxides are not normally available as pure compounds due to the practical methods used in their manufacture. Thus, DER-331, an inexpensive type of diglycidyl ether of bisphenol A, is prepared by a two-step reaction of epichlorohydrin and bisphenol A. The products of this reaction include the desired diether as well as Contains small amounts of by-products such as. The presence of such impurities in commonly occurring amounts has no substantial deleterious effect in the products of this invention. Epoxides of general formula (a) with an EEW of less than 5500 are converted into resins having an EEW of not more than 5500 and can be represented by general formula (q) by pre-reacting with phenols as defined above. can. The reaction typically involves dissolving the E ¹ epoxide in the medium, adding the acid source material and the necessary water to give the desired product composition, and until the desired degree of oxirane conversion is achieved. This is done by refluxing the mixture at a predetermined temperature (and pressure). The reaction mixture is cooled and
It is neutralized with a selected base, diluted with water (often in an amount equal to the weight of solids present), and stripped. Phosphoric acid source materials that can be used in the E ¹ /acid reaction include 100% phosphoric acid, semihydrated 2H ₃ PO ₄ .H ₂ O and at least 18% by weight H ₃ PO ₄ (relative to 25 moles of water).
1 mole of H ₃ PO ₄ ). Various condensed phosphoric acid types (poly, partially anhydride) can be used, such as pyrophosphoric acid and triphosphoric acid. When the acid source material is of the condensation type, a sufficient amount of water is supplied before curing the resinous end product so that no substantial amount of P-O-P bonds remain in the cured resin. Make it. Generally, aqueous phosphoric acid solutions, especially 70-90% solutions, are preferred. When condensed type phosphoric acid is utilized as the acid source material, the stage in the process at which P-O-P hydrolysis occurs depends on whether minimizing water content is desired during the reaction. In the reaction, sufficient time is required for complete P-O-P hydrolysis to occur if the condensed acid source material is to be fully utilized _{as H3PO4} . The epoxide/acid reaction can be carried out with the reactants alone, but it is preferable to use an effectively inert reaction medium. Solvents suitable for this purpose are as follows, listed in order of performance: (1) 75% by weight or more of acetone and methylene chloride
(2) Ketones such as acetone and methyl ethyl ketone; (3) cyclic ethers such as dioxane; (4) linear ethers such as glycol ethers; (5) lower alkyl acetates. (6) Mixtures of lower alcohols and chlorocarbons such as methylene chloride (7) Lower alcohols (8) Chlorocarbons such as methylene chloride. The parameter that preferentially determines the water dilutability of the neutralized E ¹ /acid reaction product is the E ¹ epoxy
EEW, ratio of P-OH to oxirane, water to P-OH
(H ₃ PO ₄ ), its solubility of water in the reaction medium,
temperature and contact time. In order to be water dilutable when neutralized, the reaction product must have at least a minimum content of phosphomonoester groups. A ratio of glycol groups (resulting from addition products of water and oxirane groups or hydrolysis of phosphodiester groups) to phosphomonoesters of 18 to 1 or less is a necessary requirement for water dilutability. . This is the same requirement as the molar ratio of water to H ₃ PO ₄ in the reactants being 25 to 1 or less. The extent to which water participates in the reaction depends on the water to acid ratio as well as the activity of the water, which in turn depends on the nature of the reaction solvent and the temperature. In general, the activity of water is reduced by poor solvents and low temperatures for water. The addition products of P-OH and oxirane groups seem to proceed somewhat rapidly in less polar solvents;
In such a solvent, the β・β′-dihydroxyphosphodiester group Formation occurs to a substantial extent at least in the early stages of the reaction. If water is not present or has low activity in the solvent, the oxirane can be converted preferentially to such diester groups, and ^one molecule of E will convert the diester to the extent that a gel results. Can be linked together by groups. The diester is easily hydrolyzed (to glycol and monoester groups), and therefore the diester group generally constitutes an important component of the final product derived from the reaction mixture where the water activity is substantial. Not configured. In even more polar solvents, the acid-catalyzed addition product of water and oxirane groups is quite effectively complete with the P--OH addition. Of course, addition and hydrolysis reactions proceed more rapidly at elevated temperatures, and shorter contact times are required to achieve the desired degree of oxirane conversion or to reach equilibrium conditions. If the activity of the water present is significantly higher at higher temperatures, the proportion of glycol groups in the product will increase. Free H ₃ PO ₄ is generally present in the reaction product even when the ratio of P-OH to oxirane in the reactants is substantially less than 1 as a result of direct conversion of oxirane to glycol. However, the presence of free acid (as a base salt) in the neutralized product normally does not have a significant detrimental effect on the dispersibility of the product in water. That is, the amount of the acid source material used during the reaction is such that the amount of ^E1 derived resin molecules in the product is
Even when as high as 85 parts by weight of H ₃ PO ₄ are present, water-dispersible products are obtained in some cases. However, such high acid content results in poor hydrolytic stability in the cured coating; of course, high acid content is preferably tolerated by extraction before the product is neutralized. can be reduced to the level of The water dilutability of the E ¹ /acid product was found to be sensitive to the nature of the solvent, which is associated when the neutralized and water diluted reaction mixture is stripped. The reaction solvent that is also suitable for forming the product of the desired composition is not the best solvent from which to form the aqueous dispersion. However, the reaction mixture can be stripped and replaced with a more suitable solvent before or even after neutralization and dilution with water. Methyl ethyl ketone has been found to be advantageous for the latter purpose. Alternatively, very good results are obtained using acetone containing small amounts of methylene chloride as the solvent in the reaction and in the dispersion step. Preferred reactant proportions and conditions for the E ¹ /acid reaction are as follows. Acid source substance: Aqueous 70-90% H ₃ PO ₄ solution Amount of acid source substance: P-OH0.8 per 1 oxirane
of course, a pressure at least equal to the autogenous pressure of the reaction mixture is maintained at a temperature above the boiling point of the solvent at atmospheric pressure. There must be. (Temperatures up to about 150° C. can be used.) The foregoing discussion is also generally applicable to the reaction of E ² epoxide with a phosphate source material to form a water-dilutable product when neutralized. Generally E ¹ and
It is also generally applicable to the co-reaction _of ^E2 epoxide with _H3PO4 . However, when the epoxide (E ² or E ¹ ) is easily polymerized and/or susceptible to substitution with inherent reactive functional groups such as methylol or lower alkoxymethyl groups, lower reaction temperatures may be used or other It is desirable to moderate the reaction by Most of the E ² type epoxides used are
It is also noted that it has a substantially lower EEW value than the most important E ¹ epoxides (in general formula (a) or (q), where the average value of n is 9 or more). Therefore, when using E ² epoxy alone, it is not always necessary to fall within the various ratio numerical limits set forth above for the E ₁ /acid reaction product. Generally, however, the best dispersions of E ² products or mixed E ¹ and E ² products are obtained by staying within these numerical limits. The base component of the neutralized and mixed E ¹ and E ² acid reaction product preferably consists of one or more labile bases. That is, those bases present are volatile and when the neutralized product is heated to a temperature equal to or below the required curing temperature (but above the maximum vessel temperature obtained during stripping). , dissociates from its acid (free acid or phosphoester P-OH). Ammonia and amines are examples of such preferred bases. Preferred bases are amines, especially those of formula NR ₃
(R is H, methyl or ethyl, respectively). The most preferred base is triethylamine. E ¹ used to facilitate understanding of the invention
and E ² epoxide types are described in detail. Suitable E ¹ epoxides for use in the present invention are defined by general formula (a) or (q). Q in all cases

Epoxies of the formula are preferred among such epoxides. That is, E ¹ is Commonly difunctional epoxides or general formulas of Preference is given to normally monofunctional monoepoxides derivable therefrom by 1:1 addition with phenols, where R ² , r and R ²⁰ are as defined above. Q is

[expression] or Particularly preferred are the E ¹ epoxides of the general formula given above. Q is It is also preferred that E ¹ epoxide has . The particular epoxide considered best for the practice of this invention is DER-667 (i.e. in general formula (a) where n is 10 to 13 (1500 to 2000
EEW) is DGEBA resin). The most widely used resin of the type mentioned above is
DGEBA (diglycidel ether/bis-phenol-A) resin, i.e. bisphenol-A and diglycidyl ether of bisphenol-A is a polyether diepoxide derivable from a polymer adduct with. The glycidyl ether is formed by reacting one molecule of bisphenol A with two moles of epichlorohydrin in the presence of a base such as sodium hydroxide. However, in the latter reaction, the resulting diether molecule reacts with the bisphenol molecule in situ.
carried out in such a way as to form DGEBA resin. In the latter case, the reaction product has the general formula It tends to be a mixture consisting mainly of polymers of different molecular weights corresponding to various values of n. Because it contains certain monofunctional epoxides,
Such mixtures exhibit an average epoxide functionality of somewhat less than 2. The epoxide equivalent weights given in the examples for the aforementioned types of epoxides are generally somewhat higher than the theoretical values for the nominal compounds. The practice of this invention sometimes involves the use of one of the E ¹ epoxides.
The use of two types or epoxides in which all R ¹ , R ² , R ³ or R ²⁰ groups are the same throughout the molecule is not limited. Two or more different E ¹ epoxides are combined in a single reaction product with phosphoric acid. Similarly, a given E ¹ epoxide has an R ¹ group (H, -CH ₃ , or -
_C2H5 ), ^R2 or ^R4 group (-Br, _-Cl or _-CH3 ),
Of the many different types of R ³ groups (C ₁ -C ₄ alkyl, alkylene, -SO ₂ or -O-) or R ²⁰ groups (H or C ₁ -C ₁₂ alkyl), the aforementioned wide range of It is synthetically possible to include it in individual molecules of the general formula given in the definition. Thus, for example, polyether diepoxides can be prepared using a mixture of epichlorohydrin and methylepichlorohydrin instead of chlorohydrin alone in the well-known process described in Handbook of Epoxy Resins, Lee and Neviito, Matsugrow-Hill (1967). It can be formed by using Different bisphenols can likewise be used in known methods for the reaction of individual bisphenols with epichlorohydrin or diglycidyl ethers of the same or different bisphenols. The few commercially available DGEBA-type resins are bisphenol-substituted with bromine or chlorine.
Derived from bisphenols other than A or chlorohydrins other than epichlorohydrin. That is, commercially available DGEBA type resin has R ¹ in the E ¹ general formula.
is H, n is 0 or 2, R ² is Br or Cl, and R ³ is

It is an epoxide with the formula: An example of a commercially available DGEBA preferred in the practice of this invention is manufactured by The Dow Chemical Co., Ltd.
Manufactured by the following companies:

[Table] The epoxide functionality of DGEBA resins is generally less than the theoretical value of 2, and from the theoretical value calculated for a molecular weight where the value of n for the resin listed above is equal to twice the value of EEW given. small. A typical DGEBA resin has an EEW of about 190 (theoretical value n=0) according to Lee and Nebille:
About 88% of molecules with n=0, 10% of molecules with n=1, n=2
It was discovered that 2% of molecules of It is also used for solution coating and has an EEW of about 540 (n=2
A typical high molecular weight DGEBA resin with a theoretical value of n=3 was found to have the following composition:
More than 50% of molecules with -5, about 15% of molecules with n=2, n=
15% of molecules with n=4 and 20% of molecules with n=4. Examples of bisphenols from which E ¹ epoxides of general formula (a) are made are:

[Table] Phenoh
Le〓A
Additional bisphenols were added to the phenolic resin Chemistry R.D. Martin 64-79.
Pages of Wiley & Sons, Inc., New York, New York. E ¹ of the type represented by general formula (q)
Epoxides can be prepared by combining the corresponding epoxide of general formula (a) with one or more phenols in a manner known to those skilled in the epoxy resin industry. (wherein R ² , r and R ²⁰ are as defined above). It has been discovered that the wettability of the resin can be varied in this way to ensure good wetting to a given substrate. It is of course recognized that general formula (q) is representative of products captured as average structures. i.e. its phenolic and type (a)
Even though the epoxides were reacted in equimolar amounts, some of the product molecules were not capped and others reacted with both oxiranes. The epoxide and the phenol can be reacted in a ratio other than 1:1 as long as the EEW of the product does not rise above 5500. A suitable ^E2 epoxide for the practice of this invention is
Epoxides other than formulas (a) and (q) which have EEW values between 90 and 2000 and which can be converted into water-dispersible products upon reaction with orsonic acid and subsequent neutralization with base. With the description provided herein, one skilled in the art can determine whether the E ² epoxide requirements are met by a given epoxide. Typical examples of ^E2 epoxides are types (b) ~
(p) is a 1-5 functional epoxide and is as follows. (a) General formula [wherein Y is H or a _C1 - _C4 alkyl or alkenyl group, each _YOCH2- group is ortho or para to the glycidyl group, x is 1, 2 or 3, p is 0 or 1, and a is 1 or 2, R ¹ is H, methyl or ethyl, R ⁵ is C ₁ -C ₁₂ alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl, phenoxy, - Br,−
Cl group or (wherein y is 0, 1 or 2, Y and R ¹ are as defined above) T is C ₁ -C ₄ alkylene or alkenylene;

[Formula] -SO ₂ -, -O- or a bonding group, R ⁶ is -Br, -Cl
or a _C1 - _C12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenakyl or phenoxy group, and n is 0 or 1), in which case x+a does not exceed 4 and (x+a) is 2 ~4] (C) Methylol or alkoxymethyl-substituted (2,3-epoxide)propylbenzene having the following formula, provided that in the formula, b is 1 to 3, d is 0 or 1, R ⁷ is C ₁ to C ₁₂ alkyl or

[Formula] Y' is H or a C ₁ to C ₄ alkyl or alkenyl group, R ¹ is H, methyl or ethyl, provided that (b+
d) does not exceed 3. (d) _C4 to _C28 hydrocarbons containing acrylic or cyclic di- and trioxides, two or three non-aromatic carbon-carbon dipolymer bonds and optionally -Br, -Cl or -F or hydroxy substituents. or an ester; (e) an epoxy ester of the formula R ⁸ -O-R ⁹ with the proviso that
R ⁸ and R ⁹ are each the same or different monovalent radical derived by hydrogen abstraction from a C ₃ to _{C 12} aliphatic, cycloaliphatic or phenyl alkylene oxide; (f) 2,3-epoxypropyl halide, alcohol or ester, where A is -Cl, -Br, -
OH or

[Formula] R ¹ is -H, -CH ₃ or -C ₂ H ₅ and R ²¹ is C ₁ -
is a C ₁₅ hydrocarbyl group; (g) formula Glycol monoether and formula glycol diether, provided that R ¹ is -H, -
CH ₃ or -C ₂ H ₅ , R ¹⁰ is -H or -CH ₃ , X is -H, -CH ₃ or -C ₂ H ₅ , g is 1, 2 or 3, and h is an integer from 2 to 10. Yes; (h) formula diglycidyl ether or ester of
R ¹¹ is a C ₂ to C ₂₀ divalent hydrocarbon group, R ¹ is -H, -
_CH3 or _-C2H5 and i and j are independently 0 or 1 _. (i) Eq. Mono- or diglycidyl ether of (j) Mono-, di- or triglycidyl ether of glycerin; (k) Formula or trifunctional aromatic epoxide; where Z is

[Formula] ^R12 is _C1 - _C2 alkoxy, _C1 - _C6 alkyl or _C2 - _C6 alkenyl, ^R13 is H, _C1 - _C12 alkyl or _C2 - _C12 alkenyl, ^R14 is C ₁ −C ₈
is an alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl group in the ortho or para position to the Z-CH ₂ - moiety of the benzene ring to which they are bonded, R ¹ is as defined above, R ¹⁵ is a C ₁ -C ₄ alkylene or alkenylene group or -SO ₂ -; (l) Formula tetraglycidyl ether, where R ¹⁶ is C ₁
~ _C6 divalent aliphatic hydrocarbon group,

【formula】

[Formula] -SO ₂ -, -S-, -O-, or a single bond and Z are

[Formula] (m) Formula 3-5 functional epoxy novolac, but store p
is 1 to 3, p is 1 to 3, R ¹⁷ is H or -CH ₃ , R ¹⁸ is a C ₁ to C ₄ alkylene group, and Z is (n) expression methylol-substituted oligomeric monoepoxide in which u is 0, 1, 2 or 3, R ¹ is independently H, methyl or ethyl, and R ¹⁹ is each independently C ₁ -C ₁₂ alkyl, alkenyl, cycloalkyl , phenyl, phenalkyl or alkyl phenyl groups; (o) epoxidized triglycerides of unsaturated fatty acids of up to 18 carbon atoms; and (p) the formula an adduct of a phenol substituted with a diglycidyl ether of a substituted bisphenol, provided that
R ¹ , R ² , R ³ and r are as previously defined in formula (a), Y, R ⁵ and p are as defined in formula (b), v is 1, 2 or 3, and w is independent. is 0, 1 or 2. Typical examples of types (a) to (m) and (o) are ^as follows:

【table】

【table】

[Table] Theory of epoxidation of all double bonds in oil
EEW is approximately 200. Type (b), (c), (d), (g), (m), (n), (o)
, and (p) are preferred among the above-mentioned E ² epoxides. Particular preference is given to types (b), (c), (n) and (p), since these are methylol or lower alkoxymethyl substituted which facilitate thermal conversion of the E ¹ /E ² /H ₃ PO ₄ product mixture. This is because it contains a group. Types (d), (g) and (o) have been found to improve film forming properties, dry film adhesion and/or cured film flexibility. Epoxides of type (m) have been found to improve film formation, cured film adhesion and solvent resistance, but reduce cured film flexibility. The most preferred ^E2 epoxide is Y is H or -
CH ₃ , X is Z, p is 1 and R ⁵ is a C ₁ -C ₁₂ aliphatic hydrocarbon group, an epoxide of formula (b). Examples of epoxides of formula (b) used in the present invention are methylol-substituted glycidyloxybenzene compounds derived from the methylol-substituted phenols and bisphenols described below by known methods. (See e.g. U.S. Pat. No. 3,859,255, column 5-
7)

[Formula] Q is Br, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl or nonyl. The methylol-substituted monomolecular diepoxide of formula (b) disclosed in U.S. Pat. No. 3,925,315 is It is. A specific example of a bimolecular type (b) diepoxide is
The following "APOGEN" resin is commercially available from Schaefer Chemicals Inc. as well as Mixed glycidyl ethers of mono-, di-, and trimethylol phenols are available from General Electric Co.
It is prepared by "epoxidation" of the corresponding mixture of allyl ethers, commercially available as "METHYLONResin 75108" from (See US Pat. No. 2,965,607 for epoxidation methods.) These mixed ethers are representative of monomolecular monoepoxides of type (b) substituted with 1 to 3 methylol groups. A typical example of E ² epoxide of formula (c) is:

[Formula] and and the precursor compound -1-allyl-2,4,6
- Trimethylolbenzene (U.S. Patent No.
3906126) and 1-allyl-2-methoxy-3.
5-Dimethylolbenzene (U.S. Patent No.
No. 2,707,715) by the "epoxidation" method of Example 12 of US Pat. No. 2,965,607. Some or all of the methylol groups present in epoxypropylbenzene compounds of the type described above, or in glycidyl ethers derived from methylol-substituted phenols as described above, are well known in the preparation of benzyl ethers. It is converted to the corresponding alkoxymethyl group by the following method. The epoxide of formula (n) may be regarded as an oligomer of methylol-substituted phenyl glycidyl ether. They heat a methylol-substituted phenyl glycidyl ether to a temperature (approximately 165°C) at which the methylol groups interact with the oxirane groups at a reasonable rate, and the EEW of the resin is adjusted to a value commensurate with the desired u value. by maintaining this temperature until the temperature increases to . In formula (n), the average value of u is approximately 1.5, R ¹ is H and R ¹⁹
A particular oligomer in which is t-butyl has an EEW of about 940, and the corresponding monomer at 165°C has an EEW of about 2.3
Obtained by heating for hours. Some or all residual methylol groups within the oligomer are, of course, converted to alkoxymethyl groups in well known manner to form various types of ^E2 epoxides. An example of an epoxide of formula (p) is as well as and is produced by reacting the corresponding 4-alkyl-2,6-dimethylrophenol with bis-A-type diphenol in the presence of a catalyst such as ethyl or triphenylphosphorium acetate in a conventional manner. Ru. The practice of this invention is not limited to the use of particular E ² epoxides or to the use of epoxides in which the groups Y, R ¹ , R ² , R ³ , R ⁶ , Z, etc. are identical within the molecule. Two or more specific E ² epoxides of any or all of formulas (b) to (p) above can be combined into a single reaction product with phosphoric acid. A given epoxide may consist of as many different substituents as it is synthetically feasible to incorporate into each molecule of formulas (b)-(p). If the mixture according to the invention is to be prepared by co-reaction of the phosphate source material with the E ¹ and E ² epoxides, the reaction can be carried out in one or two ways.
Either the E ¹ and E ² epoxides are mixed and then contacted with an acid, or the two types of epoxides are first reacted with one of the epoxides and the phosphate source material, and then the remaining epoxide is reacted with the phosphate source material. . The second method of implementation is expected to result in the presence in the final product of a molecule consisting of E ¹ and E ² residues linked to a phosphodiester.
However, this is only the case if the water has been removed from the mixture and the free acid remaining after the first reaction is removed before the second epoxide is added. Furthermore, such diester groups tend to undergo hydrolysis whenever the product is brought into contact with water. It has generally been found that it is better to react the acid with the E ¹ and E ² epoxides in sequence. in this case,
Various reaction temperatures can be employed to convert the two epoxides sequentially. Generally, E ² is the more reactive of the two and is best introduced after at least a portion of the E ¹ epoxide has been converted. Phosphate-providing materials that can be used in the practice of this invention include:
100% orthophosphoric acid, hemihydrate (2H ₃ PO ₄ H ₂ O) and at least 18% by weight H ₃ PO ₄ (1/25 moles of water)
H ₃ PO ₄ ). Various phosphoric acid condensates (eg polyphosphoric acid, partial anhydrides), pyrophosphoric acid and triphosphoric acid can also be used. If the phosphoric acid feed material is of the condensation type, sufficient water must be provided during the pre-curing stage of the resinous final product to ensure that no substantial amount of P-O-P bonds are present in the cured resin. . Generally, aqueous phosphoric acid solutions, especially 70 to 90% strength aqueous solutions, are preferred. When a condensate of phosphoric acid is used as feed material, the stage at which P-O-P hydrolysis is carried out depends on whether it is preferred to minimize the water content during the reaction. If the condensation feed is to be fully utilized as H ₃ PO ₄ during the reaction, sufficient time must be allowed for complete P-O-P hydrolysis to occur. The rate at which the oxirane groups are converted in the E ¹ /H ₃ PO ₄ reaction and the composition of the resulting products depend, of course, on
water to acid ratio, acid to oxirane ratio, nature of solvent,
Depends on factors such as temperature and contact time. The reaction was found to include reactions other than the addition of P-OH and oxirane groups. Unless steps are taken to ensure the presence of water in the reaction mixture, the product will contain substantial amounts of molecules in which at least one oxirane group has been converted to an α/β-dihydroxy group, i.e. a glycol group. Probably. This clearly shows that not only H ⁺ catalytic addition between water and oxirane but also hydrolysis of the phosphodiester group is occurring. As a result of the previous reaction,
Some free phosphoric acid is generally present in the reaction product even when the acid used is in such an amount that there is substantially no more than one P-OH per oxirane group. It is clear that the presence of water has a more important effect on the composition of the epoxide/H ₃ PO ₄ reaction product than what has been achieved so far. The introduction of water into the reaction mixture makes it possible to avoid using 100% phosphoric acid as the sole acid feed. However, it has been found that esterification of secondary alcoholic hydroxyl groups in DGEBA type epoxides tends to occur to a low extent. Since water is produced by this reaction, operations must be performed to remove any water produced if it is desired to achieve a fairly low ratio of glycol to ester groups in the product. This means that some P-O-P group-containing acid-providing substances (e.g.
This is easily achieved by using pyrophosphoric acid or polyphosphoric acid) with 100% phosphoric acid. Esterification of alcoholic hydroxyl groups (and water formation) is also minimized by carrying out the reaction at relatively low temperatures, such as 60-80°C. If necessary, to prevent esterification of the alcoholic hydroxyl groups, a suitable P-O-P group-containing acid donor may be used in an amount less than that required to react all of the P-O-P groups with pyrophosphoric acid. It can be easily prepared by pre-reacting it with a certain amount of water on the spot. The presence of a chlorinated phosphomonoester group is
Although essential for the water dilutability of the E ¹ /H ₃ PO ₄ reaction product, the high proportion of oxirane groups in E ¹ is not necessary to count as ester groups rather than as glycols in the product. . On the contrary,
The ratio of the number of glycol to ester groups is 19.3 to 1
It has been found that the esterified products of DER-667 are water dilutable and produce useful coatings when cured. (See Example 11) The findings described above are most unexpected and surprising findings, and have important consequences for the suitability of the compositions of the present invention as food container linings. Another result is that when unstable bases are used, the amount of base released before or during curing is lower and recovery problems are correspondingly reduced. Yet another very important result is that the amount of labile base retained in the cured coating is virtually zero. That is, in the range of 50 parts per billion to an undetectable amount. The amount of water provided by the acid epoxide reaction can vary from 0 to 25 molecules per molecule of H ₃ PO ₄ provided by the acid feed. An excess of about 2-4 moles of water per mole of acid will generally result in a heterogeneous reaction mixture unless a good solvent for the water is included. This does not necessarily result in an unexpectedly low ratio of phosphoester to glycol groups. Ester to glycol ratios such as 1:2.3 were obtained using DER-667 as the epoxide and acetone as the reaction medium at approximately 2:1 molar water to acid. The resulting resin is generally diluted with water, and it is usually preferred that water be present in the mixture before removing the solvent. Therefore, the presence of relatively large amounts of water during the reaction does not cause any serious problems for these reasons. It was found that long reaction times are essential to achieve high oxirane conversions at high water concentrations. However, it is extremely advantageous from an economic point of view to be able to recycle the recovered solvent, which contains substantially water. Therefore, it will be necessary to determine the optimum water content for any particular E ¹ epoxide reaction. This does not require undue experimentation, and the method will be clarified by the Examples below. The amount of acid introduced into the reaction by the acid donor is
The amount should be such as to provide about 0.3 or more acidic hydroxyl groups (hydroxyl groups attached to phosphorus) for each oxirane group present in the E ¹ epoxide reactant. However, per equivalent of E ¹
Up to 1/3 mole of H ₃ PO ₄ (i.e. oxirane 1
It is preferred that the number of acidic hydroxyl groups (or less than 1 acidic hydroxyl group per hydroxyl group) is maintained, thereby avoiding a substantial reduction in the water resistance of the cured product. If E ¹ is DER−667 (or a similar DGEBA type epoxide),
It is highly preferred that H ₃ PO ₄ is less than 1 part by weight per 100 parts by weight of E ¹ . Large amounts of acid can be used up to the point that the reaction mixture becomes unduly heterogeneous. However, oxirane 1
The use of H ₃ PO ₄ in amounts greater than sufficient to provide about 4 acidic hydroxides per unit result in the inclusion of free phosphates which have an undesirable effect on the properties of the uncured or cured resin. . Thus, it is necessary to remove at least some of the excess acid, preferably before introducing the base. The epoxide/acid reaction can be carried out in the absence of water and a reaction medium is not necessarily required.
However, as mentioned above, the use of a medium is essential for the homogeneity of the reaction mixture when the amount of water and/or H ₃ PO ₄ is high compared to the amount of epoxide. Good results are obtained if the reaction mixture is homogeneous, so it is generally preferred to use a reaction medium in all cases. Suitable reaction media in the present invention are inert substances that form a solution or dispersion that is fluid at the reaction temperature used as a mixture with the reactants. The term "inert" as used herein refers to a medium that does not react adversely with any substances present to such an extent that at least one object of the invention cannot be achieved. Preferred media are inert organic compounds or mixtures thereof that are liquid at ambient temperature, have a boiling point below 150° C., and are solvents for the epoxide and the phosphoric acid feed material used. The medium must also be capable of dissolving water sufficiently to achieve the desired ratio of dissolved water to acid (or oxirane groups). Examples of such media include dioxane, glycol ethers, lower alkyl acetates, methyl ethyl ketone, acetone,
Ethanol, isopropanol, methylene chloride and any mixtures thereof. (The alcohols are examples of inert solvents that do not have an unacceptable degree of harmful reactivity.) These alcohols are suitable for use when adding an aqueous solution of H ₃ PO ₄ to a dilute solution of E ¹ resin in dichloromethane alone. like,
These alcohols are particularly useful as co-solvents when precipitation is likely to occur in their absence. ) The nature of the reaction medium influences both the reaction rate and the composition of the products. As a general rule,
If a poor solvent for water is used as the reaction medium, the rate of oxirane conversion by P--OH addition and the proportion of diester groups in the reaction mixture are higher. At about 60°C, E ¹ linked together by diester groups (or nonsolvents,
Promotes the formation of highly polymeric chains consisting of epoxide residues. Thus, DER−667 can be converted into H ₃ PO ₄ (aqueous H ₃ PO ₄
(as 85%) of 1 wt% and ₁₀₀ % _CH2Cl2 at 60 °C
The reaction mixture gels in about 4 hours. Under these conditions, the chemical activity of water in a solvent such as dichloromethane does not appear to be high enough for substantial hydrolysis of the oxirane or ester groups to occur. (However, the gel could be dissolved in a more water-miscible solvent and hydrolyzed to a fully useful product containing approximately equal numbers of glycol and monoester groups.) When _the reaction medium contains a water-miscible solvent like acetone (75% by weight) - 25% by weight of _CH2Cl2 ,
Diester formation is still the predominant reaction (at 60°C), but the product is not a gel. 115℃～
At a temperature of 120° C., the activity of water (included in the H ₃ PO ₄ ) in a medium consisting of 75% by weight of CH ₂ Cl ₂ and 25% by weight of acetone is high. Diester formation clearly does not proceed and hydrolysis of all the diester groups formed takes place. However, as the proportion of acetone increases further, the diester formation decreases and the monoester content in the final product increases. Direct addition of water at the oxirane group is clearly the main reaction (at 115°C to 120°C)
However, as the proportion of acetone in the CH ₂ Cl ₂ /atocene mixture increases, the ratio of glycol to monoester groups decreases. The nature of the medium in which the neutralization reaction products are formed is also important. That is, the medium that is best for producing the desired reaction product is not necessarily the medium in which the most stable or highest solids content dispersion can be obtained in water. Thus, although a higher monoester content is obtained from the above reaction of DER-667 with 85% H ₃ PO ₄ in acetone alone than in the acetone/CH ₂ Cl ₂ solution,
Tests have shown that the presence of small amounts of dichloroethane aids in the dispersibility of the neutralized product formed when water is added and the organic medium is removed. Also, in general, the product particles formed by stripping the neutralized epoxide/acid reaction mixture exhibit less tendency to agglomerate when obtained from solutions in dioxane or methyl ethyl ketone, especially the latter solvent. These solvents can therefore be used particularly advantageously as a medium for the production of neutralized acid/epoxide products which are inherently difficult to disperse in water. If extractive removal of excess phosphoric acid is intended in the pre-neutralization stage, it is of course possible to include in the reaction medium an appropriate amount of a solvent which is immiscible with water or has a tendency to emulsify thereby. be. Also, if more than stoichiometric amount of base is used for neutralization,
Base-labile solvents such as acetone must be removed first. Mixtures of two or more solvents are preferred in providing a medium with the desired combination of solvent action and initial boiling point or azeotropic point (reflux temperature). The appropriate reaction temperature is (for E ¹ epoxide)
From the minimum temperature at which P-OH addition with oxirane groups proceeds at a useful rate to (1) high temperatures at which deleterious reactions (such as between an alcoholic reaction medium and phosphoric acid) occur to an unacceptable extent; or (2) in a range of temperatures such that excessively high solvent vapor pressures occur. Although temperatures within the range of 50°C to 150°C are generally satisfactory, it is preferred to maintain the reaction temperature within the range of 70°C to 135°C. A range of 100°C to 125°C is particularly preferred, and a range of 110°C to 120°C is considered near optimal for commercial implementation of the process of the invention. The interdependent nature of temperature and solvent effects was shown in the discussion of the reaction medium. When reaction temperatures above the atmospheric boiling point of the reaction medium are used, pressure is critical to the reaction only if operation under high pressure (operation at least equal to the autogenous pressure of the reaction mixture) is necessary. This is an important element. Of course, the reaction can be carried out under reduced pressure if desired. Contact time is an important factor in this process, as the reaction is generally allowed to proceed until less than 1%, preferably less than 0.5%, of the oxirane groups initially present are consumed. It is only necessary to convert as much epoxide as is necessary to produce a reaction product having essentially the properties of the more highly reacted epoxide/acid products of this invention. That is, it is only necessary that the epoxide conversion be essentially complete. In accordance with known principles, the rate of some reactions that tend to occur will be faster at higher reaction temperatures, and the contact times required will be shorter at such temperatures. As a general rule, longer contact times tend to result in a higher degree of diester hydrolysis. In most instances, contact times of about 1 hour (at temperatures around 150°C) to about 24 hours (at 60-70°C) are satisfactory. Typically, essentially complete conversion of the E ¹ epoxide to a product that is water-thinnable upon neutralization is achieved in a contact time of 3 to 6 hours at a temperature of 125°C to 100°C. can be done. Operation The reaction of the epoxide with the orthophosphoric acid feed material (and optionally water) is carried out immediately in conventional equipment. The first step in the operation is to add 1% to the reaction medium (or its components that are the best solvents for the epoxide).
It usually consists of dissolving one or more epoxides. For high molecular weight (E ¹ ) epoxides, at least in most solvents, dissolution is somewhat slow under normal temperatures, generally requiring stirring of the resin/solvent mixture for 8 hours or more. The acid feed material, typically an 85% aqueous H ₃ PO ₄ solution, may be predissolved in or diluted with one or more components of the reaction medium to facilitate mixing with the epoxide solution. In either case, it is generally more advantageous to add the acid material to the epoxide solution than vice versa. Highly reactive epoxide ( ^E2
It is not necessary to add the reactants together gradually and/or at low temperatures, unless epoxides are used (which is often the case). highly reactive
An example of an E ¹ epoxide is bisphenol.
There is diglycidyl ether of A. When using highly reactive E ¹ epoxides, it is desirable to operate initially at temperatures low enough to allow the reaction to proceed at a satisfactory rate. In this way (and by dilution) reactions that lead to gelation can be minimized.
Therefore, in simultaneous or sequential reactions, certain reactions can be controlled by precooling, mixing, and stirring the reactants (and the medium) at low temperatures (e.g., below 5°C) for up to a day or so. The reactants can be mixed together as thoroughly as possible prior to the start of the reaction. Then gradually warm the mixture,
The tendency for rapid fever to occur should be discouraged. After most of the more reactive epoxides have been converted, i.e., the oxirane content has been sufficiently reduced, the temperature of the mixture can be raised further to allow one or more reactions to proceed more quickly to completion. let However, temperatures substantially above about 150°C should generally be avoided during the reaction period as well as during subsequent solvent removal. In general, the mixed reactants are heated to the desired reaction temperature, preferably with stirring, in a vessel suitably equipped with a reflux condenser, pressure seal, or other suitable equipment. The contents of this vessel are kept under heat at least until sufficient oxirane conversion has taken place to yield a water-reducible product (by addition of base). The reaction mixture is cooled, then "neutralized" as described below, diluted with water, and driven off low boiling materials. If a reaction medium consisting of or containing a solvent with a boiling point higher than that of water is used, the addition of water can be delayed until the high-boiling solvent has been replaced by a lower-boiling solvent. The low boiling solvent is then driven off after adding water. Since there is a risk that the chlorinated (neutralized) resin will coagulate, it is generally desirable to add water gradually with good stirring. Base Neutralization The reaction products of H ₃ PO ₄ , E ¹ and/or E ² may be neutralized with any base such that the resulting neutralized product is water dilutable. good. Complete neutralization may not be necessary in all cases, depending on factors that will be apparent to those skilled in the art. That is, it is sufficient to react the acid/epoxide reaction product with as much base as necessary to provide the chloride ester P-OH groups to the extent necessary to provide water-reducibility. However, the addition of at least one equivalent of base per phosphate ester group is generally preferred and usually necessary when the acid number of the product resin is relatively low. In extreme cases of the reaction, a sufficient amount of base to completely neutralize all of the acidic hydrogen present in the acid/epoxide reaction product, including any free H ₃ PO ₄ if present. may be added. Examples of suitable bases for practicing the invention include: A Alkali metal hydroxides, such as hydroxides of lithium, sodium and urium. These bases should be used in the form of uncured salts (e.g. as surfactants) with resins or resins whose curing can be carried out using the reactive functional groups present (secondary alcoholic hydroxyls). May be used. B. Oxides or hydroxides of alkaline earth metals, such as beryllium or calcium, which produce phosphates or acid phosphates with moderate water solubility. Again, curing of these salts requires the presence of the aforementioned reactive functional groups. These salts can also be fired in subsequent steps as water-dispersible sealers or primers. Materials such as green ceramic materials may also be used. C Oxides or hydroxides of other metals such as copper and iron, or hydrates thereof, complexes with ammonia, etc., to form phosphates or acid phosphates with suitable water solubility. D Ammonia or ammonium hydroxide. E. Organic bases. This class of bases particularly preferably includes the following compounds. a choline and guanidine; b aliphatic mono- and polyfunctional amines, such as methylamine, n-butylamine, diethylamine, trimethylamine, diethylenetriamine, n-hexylamine, ethylenediamine, allylamine, etc.; c cycloaliphatic amines, such as cyclohexylamine , cycloheptylamine, etc.; d Aromatic amines, such as aniline, N/N-
dimethylaniline, diaminobenzene, etc.; e heterocyclic amines, such as ethyleneimine, piperazine, morpholine, pyrrolidine,
pyridine, hexamethyleneimine, etc.; and f alkanolamines and alkylalkanolamines, such as ethanolamine, dimethylaminoethanol, diethylaminoethanol, diisopropanolamine, triisopropanolamine, 4-hydroxy-n-butylamine, 2-dimethylamino, 2-methyl, 1-propanol, etc. Within each of these classes a-f, preferred compounds require only heating to a temperature below that necessary to achieve a satisfactory rate of cure, while removing water by evaporation or It can then be removed from the neutralized resin dispersion. Particularly preferred organic bases are class b
and f, which can be removed simply by heating to below about 150°C. This is 760mm
It is generally possible to carry out with a base having a boiling point below 150° C. under pressure of Hg. Most preferred of the latter bases are amines of formula _NR3 . Note that each R can independently be H, methyl or ethyl group,
One R is H. In order of decreasing preference, various factors such as curing time (including the time required to perform deneutralization and amine removal), viscosity of the neutralization reaction mixture and ease of stripping, particularly Preferred amines are triethylamine, dimethylamine, trimethylamine and diethylamine. Triethylamine is particularly preferred because it does not flake with respect to each of the aforementioned factors, even at high temperatures such as those found when processing canned foods, even in small amounts that remain in the cured coating. This is because it was found that it does not easily leach out depending on the water. The next most preferred is R′ ₂ N−CH ₂ −CH ₂ OH
An alkanolamine represented by
R′ is H, methyl or ethyl;
R' is independently H, ethyl or 2-hydroxyethyl. In order of decreasing preference, more preferred alkanolamines are N.N.
-dimethylethanolamine, N-methylethanolamine, ethanolamine and diethanolamine. It turns out that triethanolamine is not suitable for use in neutralizing the high molecular weight acid/E ¹ epoxide reaction products of this invention. DER-667/
Neutralizing the H ₃ PO ₄ reaction mixture with triethanolamine, diluting with water, and then stripping (to approximately 50% solids) does not yield a dispersion.
However, the coating formulation of the dispersion according to the present invention
Triethanolamine presents no problems when added with CYMEL303 (hexamethoxymethylmelamine). Furthermore, the point obtained as a finding is that the high molecular weight E ¹ /
The acid product has the formula: Neutralization with dimethylaminomethylpropanol gives the acid/epoxide reaction
Good dispersion is obtained only when the amount of H ₃ PO ₄ is greater than or equal to about 1 part per 100 parts of resin (DER-667). Of course, suitable mixtures of the above amines and alkanolamines can also be used for special purposes. Similarly, the reaction products E ¹ and E ² with H ₃ PO ₄ prepared separately may be neutralized using separate bases and then mixed, or they may be mixed first and then mixed with the same base. You can use it to neutralize it. Neutralization is carried out by first diluting the acid/epoxide reaction mixture (including the solvent used) with enough water to form a satisfactorily easily stirred dispersion, and then adding a base. (or vice versa). If no acid was removed from the epoxide/acid reaction mixture, a very advantageous method is to simply add H ₃ PO ₄ (100%) to the reaction system.
2 equivalents of base per mole (e.g. moles for amines)
It is to add. However, the amount of base required can be determined by the predetermined acid content of the substance to be neutralized. Alternatively, litmus or PH paper or a PH meter may be used to determine when to stop adding base. Another method, which is satisfactory as normal operation, is to simply add the base in portions, with sufficient stirring, as is known, until the desired degree of neutralization has been achieved. There is a method in which stirring is continued until the appearance and properties of the dispersion being stirred change significantly. However, generally between 6 and 10 (preferably
A certain PH value within the range of 6.5 to 9) is selected in advance as the end point of neutralization. Since the rate of neutralization decreases as fewer unneutralized acidic hydroxyl groups are present, each addition of base is necessary to ensure that the apparent endpoint is actually the true endpoint. After that, you should give it enough time. Normally, no change in PH value will be seen after about an hour. Dilution and action of the neutralized H ₃ PO ₄ /epoxide reaction product with water Unless the neutralized product is to be used without transport, it is common practice to use as little water as possible in its preparation. to keep transportation costs low. However, prior to application to the substrate to be coated, the neutralized (and stripped) product must be prepared in accordance with the amount of additives and hardeners to be dissolved, the intended mode of application, the desired viscosity, It is common to dilute with additional water based on factors such as the thickness of the coating to be formed. (It is generally preferred to produce an aqueous product dispersion at a solids level of 50%;
No difficulties were experienced in further diluting such a dispersion with water). The energy requirement for water evaporation is of course another issue to be considered. Water, commonly used as a diluent, is added at a relatively low rate with good agitation.
The formation of metastable mixtures of one separate liquid phase is avoided. However, in some cases,
It is also possible to add in reverse or sometimes all at once. Stripping of the neutralized mixture is carried out in common practice at a pressure appropriate to the normal boiling point of the solvent to be removed. Care should be taken to avoid excessive heating temperatures during stripping that would result in undesirable hydrolysis of the ester groups. Undesirably high stripping temperatures are most likely to occur during the later stages of the stripping process, especially when relatively high boiling water-miscible solvents are used in or as the reaction medium. be. In the latter case, using a relatively low stripping speed or
Or other means should be resorted to, such as the addition of a solvent which forms a low-boiling azeotrope with the water-miscible solvent. In another mode of use, the neutralized reaction product can be converted into powder form, for example by spray drying, which can later be dissolved in water or applied directly to a substrate by known powder coating methods. The aqueous solution of the neutralized reaction product can be applied to a variety of substrates by known methods such as spray coating, dipping, roller coating, brushing, or using a drawbar. Removal of water from the resulting aqueous film is as follows:
This can be readily accomplished by known methods such as passing a flow of air at a controlled rate of controlled temperature and humidity over the film, passing the film through a vacuum zone, heating, etc. If the salt moiety present in the neutralized reaction product (i.e. resin) is of such a nature that it is easily decomposed by heating, and the base produced by the decomposition is volatile, All or at least most of the base may be removed during the water removal operation. The base remaining after water removal can be substantially removed by further heating under normal pressure or reduced pressure. The removed base is usually recovered by, for example, condensation methods or acid scraping methods. As mentioned above, curing of the resin after removal of moisture and base can be performed by an appropriate action. When an auxiliary chemical hardener is used, the hardener can be introduced prior to or after moisture removal (eg, by spraying it as a solution in a volatile solvent onto the uncured film). Generally, the most convenient and economical curing method is to simply apply heat (e.g., by baking) to remove reactive functional groups in the unneutralized coating, such as secondary hydroxyl, P-
Cross-linking between the OH groups and groups reactive towards the above-mentioned functional groups in additive hardeners (eg ureas, melamines and phenolic compounds) could be effected. Product Identification Method 1 Acid Titration The relative amounts of phosphoric acid charged to the reaction to be reported as free acid, monoester groups, and diester groups in the product mixture are determined as follows: Desired. A sample of the reaction mixture sufficient to give approximately 1 milliequivalent (meq) solids content (based on acid present) was prepared by adding 66.7 wt% 2-butanone,
Dissolve in 35 ml of a solvent consisting of 16.65 wt% methanol and 16.65 wt% water. This solution was prepared using Metrohm/Herisan.
Titrate with approximately 0.3N methanolic tetrabutylammonium hydroxide using an automatic titrator until a second abrupt point (kink) appears in the measured conductivity vs. titrant volume curve. 10ml of water and
Add 10 ml of 10% CaCl ₂ aqueous solution and allow to react for about 10 minutes, thereby converting all phosphoric acid mono- and di-ester groups into neutral calcium salt groups. Free phosphoric acid is converted to monobasic phosphate _CaHPO4 . All calcium-containing products precipitate, but by doing so, further neutralization of the protons in _CaHPO4 with the quaternary hydroxyl base allows titration without interference from the second monoester proton. A third inflection point is observed on the curve. The amount of base required to obtain the first inflection point is the amount consumed by the single acidic proton in the diester and the first proton in both the monoester and the free acid. The amount of additional base required to reach the second inflection point is determined by the amount of additional base needed to reach the second (last) proton in the monoester and the second (last) proton in the free acid.
This is the amount consumed by protons. The amount of additional base required to reach the final bending point is
It is the amount consumed exclusively by the last proton in the calcium salt derived from the free acid. The total volumes of base solution required to reach these subsequent inflection points are U ₁ and U _{2 ,} respectively.
and U ₃ , the relative amounts of phosphoric acid (salt) present as mono- and di-ester groups and as free acid can be calculated from the relationship below. Free H ₃ PO ₄ = U ₃ −U ₂ Monoester = 2U ₂ −U ₁ −U ₃ Diester = 2U ₁ −U ₂ of consumed epoxide groups reported as glycol groups in the product (result of hydrolysis reaction). The proportion can be calculated from the relationship below (assuming that the conversion products are only glycol, monoester or diester groups). %eg=100−M _A /eo−ep [%m+2(%d)](
1) where e _p = epoxide equivalent weight present in the product itself (usually zero). e _p = equivalent weight of epoxide charged to the reaction. e _g = epoxide equivalent converted to glycol group. M _A = number of ₄ moles of H ₃ PO charged to the reaction. %m = mole % charged acid reported as monoester. %d = mole % charged acid reported as diester. 2 Oxirane group titration Using a 25% solution of tetramethylammonium bromide in glacial acetic acid, perchloric acid 0.1N in glacial acetic acid
A standard analytical method by back titration against crystalline violet in solution was found to be suitable and was used for all determinations of oxirane content given in the examples below. 3. Viscosity Measurements As an indicator of crosslinking and/or molecular weight change, the viscosity of some of the reaction mixtures described in the following examples was measured by the well-known Gardner method. Example 1 Solubilization of resin DER-667™ by reaction with 65% or 75% H ₃ PO ₄ and neutralization with trimethylamine. EEW = ~2000; 3H ⁺ /oxirane A The resin was dissolved in an equal weight of dioxane and the solution was mixed with 75% H ₃ PO ₄ at room temperature. The weight ratio of acid/resin at this time was (13.26/200 g), so as to give 3.0 equivalents of H ⁺ per equivalent of oxirane. A sample of the resulting mixture (No. 0) was immediately quenched and stored at low temperature as an analysis control sample. the rest of the mixture,
Put it in a glass bottle with 7 consecutive numbers.
Placed in an oven at 70°C. Each vial was removed from the oven in numerical order at the elapsed times shown in the table below and rapidly cooled to stop the reaction underway within the vial. A sample of each content was then titrated for oxirane (EEW), free H ₃ PO ₄ , phosphoric monoester, and phosphoric diester. The Gardner viscosity of each reaction mixture was measured and the dispersibility in water was tested after neutralization with trimethylamine. B Experiment A above was repeated, but with 3 equivalents of acidic hydroxyl groups (3 equivalents of acidic hydroxyl groups per equivalent of resin).
(15.3 g) of 65% H ₃ PO ₄ to give H ⁺ )
was used. The results of Experiments A and B are summarized in Table 1 below.

【table】

Table Example 2 Resin DER-664™ solubilization by reaction with 85% or 99% H ₃ PO ₄ in dioxane at reflux temperature and neutralization with trimethylamine. EEW
=~1000; H ⁺ /oxirane ratio 3:1 A 25 grams (0.025 equivalents) of DER-664 were dissolved in 25 grams of dioxane. To the resulting solution was added 25 grams (~0.076 equivalents) of a 10% solution of 100% H ₃ PO ₄ (99%, moisture absorbed during handling) in dioxane. The mixture solution was heated to reflux temperature (~101°C), refluxed for 3 hours, and cooled to room temperature. The acid value of this reaction mixture was 124.05. (On the contrary,
The theoretical value when one oxirane group is added per molecule of H ₃ PO ₄ is 102). No unreacted epoxide could be detected. The reaction mixture was extracted with 50 ml of water and the acid content of the extract was titrated with dilute KOH to be 0.013 equivalents. This ruffinate was neutralized with 3 g (0.03 equivalents) of trimethylamine.
required. The total acid consumption for the reaction is therefore 0.076 - (0.013 + 0.030) = 0.033 equivalents, or per equivalent of oxirane.
0.033/0.025=1.32 equivalents of H ⁺ . B Experiment A was repeated, but instead of the acid solution used in Experiment A, 2.94 g (0.076 equivalents) of 85% H ₃ PO ₄ was added.
A dioxane solution containing . The acid value of the reaction mixture is low (108), and the acid content of the extract and raffinate are 0.09 and 0.09, respectively.
The amount of acid consumed in the reaction was 0.033 equivalent in this experiment as well. Both Ruffinates A and B (after stripping of residual dioxane) gave slightly cloudy but stable dispersions in water with a solids content of 41%. Example 3 Effect of EEW and H ⁺ /oxirane ratio on solubilization of DGEBA type epoxy resin upon reaction with 85% H ₃ PO ₄ Four species with EEW varying from 190 to 2000
DGEBA type resin was reacted separately with 85% H ₃ PO ₄ in dioxane at 75°C. The amount of H ₃ PO ₄ was such as to provide 0.5 to 3.0 equivalents of H ⁺ per equivalent of oxirane. The dispersibility of the reaction mixture itself and when it was neutralized with trimethylamine and stripped of solvent was examined. The results are summarized in Table 2 below. From the results in the table,
It can be seen that the object of the present invention cannot generally be achieved when the H ⁺ :oxirane ratio is as low as about 0.5. These data also indicate that a ratio of about 1.0 or greater is necessary for the dispersibility of only resins with an EEW of about 1000 or greater.

【table】

【table】

【table】

【table】

【table】

[Table] Example 4 Solubilization of resin DER-667 by reaction with condensed phosphoric acid raw material (8P-OH/oxirane) 100 g (0.05 equivalent) in 200 g of dioxane
A solution of DER-667 was added to 17.8 g (0.1 mol) of pyrophosphoric acid.
(equivalent to 0.2 mol of H ₃ PO ₄ ) was gradually added dropwise into a stirred solution of the same weight of dioxane.
The temperature of the reaction mixture was maintained at 80-100°C.
A soft gel was formed in about 0.5 hours. When an additional 270 g of dioxane was added, the gel only partially dissolved, but the resulting mixture was stirrable. After a further 3 hours of reaction, no unreacted epoxide was detected (in the continuous liquid phase). Titration of gel phase sample (17%
When dissolved in a mixed solvent of H ₂ O, 17% methanol and 66% methyl ethyl ketone), it was found to consist primarily of DER-667 with the oxirane groups converted to phosphodiester groups. 10 g (0.56 mol) of water was added to the reaction mixture, and the mixture was stirred and heated for 3 hours to transform it into a homogeneous liquid. Titration of this final solution showed that all diester groups and P-O-P bonds were hydrolyzed. Since the amount of free phosphoric acid could not be determined well by titration, a portion of the reaction mixture was repeatedly extracted with water and the combined extracts were titrated. The proportion of oxirane groups in DER-667 converted to phosphoric acid monoester is calculated from the difference between the amount of charged H ₃ PO ₄ (prepared with H ₄ P ₂ O ₇ ) and the final content of free acid in the above extract. , calculated to be 71.4%. The proportion of oxirane groups converted to glycol groups is therefore (by difference) 28.6%, and the ratio of glycol:monoester groups in the final product is:
It was 0.4. Although the liquid phase formed with the gel did not separate, the titration curve for this phase indicates that it contains only about 10% or less of the 667-derived product as diesters and the remainder as monoesters. was estimated. Dispersions were prepared from final reaction mixture samples that were substantially free of and contained (by water extraction) H ₃ PO ₄ . The sample was neutralized with triethylamine to a pH of 7.5-8.0, stripped, and diluted with water until the non-volatile component content was 16.
% by weight. The sample without extraction gave a viscous, cloudy white dispersion with good film-forming properties. The extracted sample yielded a water-thin, transparent blue dispersion, but the film-forming properties of this dispersion were unfavorable. Example 5 Utility of _the Neutralized Reaction Product of DER-667 and _H3PO4 as a Dispersant for DGEBA Epoxides with EEW of ~13000 or Less DER-667 (EEW ~1550) 1 mole per equivalent (6 phr) of H ₃ PO ₄ (H ₃ PO ₄
(as a 99% aqueous solution) in methyl ethyl ketone at 80 °C for 15 hours.
DER-667/H ₃ PO ₄ products with “high” ester content were created. There is no residual unconverted epoxide, and the glycol to ester ratio is 34/66 = 1/
It was 1.94. This product was mixed with successively smaller amounts of DER-684 solution (40% solids in MEK), each resulting mixture was neutralized with 2 equivalents of triethylamine, diluted with 25 phr of methylene chloride, For every 100 parts of total resin, 100 parts of water were mixed. The product after stripping (emulsion) contained a total of 50% solids by weight and was evaluated as a dispersion. The results are as given in Table 3.

[Table] No sedimentation B 680g of 40% by weight solution of DER-684 in MEK
, 3.72g of pyrophosphoric acid and its 100%
It was heated to 78<0>C for 24 hours along with the amount of water (0.38 g) required to convert to _H3PO4 (~ _1.5 phr). The EEW of the resin did not rise above 50,000 (~74% oxirane conversion) and the neutralized final product did not become a dispersion upon addition of water. Somewhat poorer dispersion was observed when 50,000 EEW resin product was used in place of DER-684 in the Part A mixture. The dispersion mixture obtained in the experiment of section A
A composition having a DER-684 content of 50 phr or less can be said to specifically demonstrate the unique and excellent composition of the present composition invention. A person skilled in the art will understand that the (average) molecular weight of approx.
One will appreciate the advantages in cured film properties provided by the presence of 26000 DGEBA resin. Furthermore, from the very slow oxirane conversion rate observed in the Section B experiment, most or all of the DER-684 oxirane groups are
It is clear that it is present in intact form in the -684 dispersion formed. water and acid
It is not expected that in the presence of both hydrolyzable amine phosphate groups (even if DER-684 is not dissolved but dispersed), the latter group will remain unconverted for an unspecified amount of time. It would not have been possible. However, DER−684 (as is or reacted with H ₃ PO ₄ ) and DER
The aqueous dispersion of the neutralized mixture with _the -667/ _H3PO4 reaction product appears justified in being considered a highly novel oxirane-containing material composition. Example 6 Reduction of free acid content. In the reaction product _of high EEW DGEBA resin and ~6phr _H3PO4 ,
Improved dispersibility 95g (0.0198 equivalents) of DER-669 in MEK
(EEW4800) and 5.88 g of 85% H ₃ PO ₄ (0.051 mol H ₃ PO ₄ ; 7.73 P-OH per oxirane) was refluxed at 80° C. for 15 hours. The reaction mixture was cooled and samples were taken for analysis: unreacted oxirane concentration, 0; oxirane converted to phosphomonoester,
40%; oxirane converted to glycol, 60%; glycol/ester group ratio 3/2; free H ₃ PO ₄ in the product, 4.31 g or 4.27% by weight of non-volatile components present. It was divided into parts. A portion of it was neutralized to pH 7 with triethylamine, neutralized with water, and then stripped. This stripped material was not a stable dispersion. The second portion was mixed with sufficient water (equal volumes of water) to precipitate the polymer. The liquid phase portion was removed by decantation, and the precipitate was finely loosened with water, followed by further decantation to remove water. The polymer was captured in MEK and the solution was collected for analysis. It was found that 30% of the free acid was removed by washing. _{H3PO4 present}
accounted for approximately 3% by weight of the resin-like product. A stable, opaque, non-granular dispersion (50% solids) was obtained by neutralizing the product with triethylamine to pH 7, diluting it with water, and stripping off the MEK. Example 7 Effect of Substituents on Substituents on Phenols Used to Cap DGEBA Resins on Substrate Wettability DER-664 was separately added to phenols, 0.5 molecular weight per equivalent of oxirane,
It was reacted with p-t-butylphenol and p-nonylphenol. 1 gram mole of phenol reactant, 0.3 g of A-1 catalyst (ethyl triphenylphosphonium acetate) and 15 ml of xylene were combined into 250 g (0.13 g mole) of molten (~120°C)
Add to DER-664 and stir the mixture for 200 min.
C. and refluxed until the EEW was approximately equal to the sum of the molecular weight of the phenol and twice the initial EEW of the resin. The xylene was stripped off, a retained sample was taken, and an equal weight of MEK was stirred and added to the remaining capped resin. The resulting solution was heated to reflux and 0.5 mol of
Equal weight of H ₃ PO ₄ (as 85% acid aqueous solution)
It was diluted with MEK and added drop by drop. EEW is approx.
Refluxing was continued until the temperature reached 60,000 or maintained a constant value. The solution was cooled, neutralized with 1 molar triethylamine, and diluted to retain the solids therein. The diluted mixture was stripped at 70° C. with stirring under reduced pressure until no more MEK came off. The product after stripping is (as analyzed)
It was a stable aqueous dispersion containing about 50% solids by weight. Each part of this dispersion is divided into several parts,
Diluted with water to give solids of 30, 35 and 40% by weight, respectively. Using #4 spindle at 100 rpm,
The Bruckfield RVT viscosity was determined for each of the four dispersions (12 total). Also, 5990cm
Surface tension was measured with a Fischer surface tensiometer using a diameter wire cable (average of 5 replicates each). Place a small amount of each of the dispersions to be compared on the same panel and stretch them simultaneously and parallelly with #18 wire-wound rods to determine the continuity, "crawling," spreading or shrinkage, and "beading" of the resulting film pieces. ”, “fisheye” and flatness were observed. For each set, the overall rating is 1 based on the visual criteria described above.
We decided to rank them numerically from (best) to 3 (worst). When the pH of all dispersions was checked, it was consistently within the range of 8.45 to 8.55. The results of evaluation of viscosity, surface tension and wettability are shown in Table 4.

[Table] When R ²⁰ (in general formula (q)) changes from nonyl to t-butyl or H, wettability decreases.
This is clear from Table 4. The difference is most noticeable when tested on a clean aluminum substrate (35 or 40% solids) and least noticeable when tested on uncleaned cold rolled steel (35% or 40% solids). %in the case of). These effects are roughly correlated to the somewhat higher viscosity and relatively low surface tension of nonylphenol-derived dispersions. Example 8 Sequential co-reaction of H ₃ PO ₄ with DER-667 and phenyl glycidyl ether substituted with methylol group (type (b) E ² epoxide) (=
720; 0.935P-OH/oxirane): 70 1 bs. (~0.02 1 b. mol) of DER-667
Dissolved in 100 1bs. of methylene chloride and 20 1bs. of IPA, warmed to reflux for 2 hours, and heated to 41°C for 5.0 1bs.
React with 85% _{H3PO4 for} 24 hours. The oxirane content on a solid basis was less than 0.1. Glycidyl ether of 1,6-bis(methylol)-4-t-butylphenol 30 1 bs. (~0.1 1 b. mole)
was then reacted at 41°C for 33 hours. The oxirane content was also less than 0.1%; the acid value was
It was 14.5. 175 lbs. of distilled water and then 80 lbs. of triethylamine were added with stirring. The PH of the residual dispersion after the solvent was stripped off was 8.5, indicating excellent stability and solution properties, i.e. no sediment, low opacity, no granularity and Ta. The composition was applied onto an aluminum specimen at a non-volatile content of 20% by weight in water. At this time, a rod wrapped with #10 wire was used to pre-treat the surface of the test piece. Good wettability and extremely excellent fluidity were observed, and sufficient curing was observed in 8 minutes at 380〓, 5 minutes at 400〓, and 3 minutes at 440〓. The chemical resistance of this film was excellent; the body passed a 50 acetone double rub. Excellent wetting properties were also observed when applied onto tin-free steel coupons. No brushing was observed in the coatings applied to either type of surface, even after immersion in boiling water for 30 minutes. When 1% P-toluenesulfonic acid (solid basis) is included in a dispersion diluted with water,
The aforementioned curing time was cut in half. The film properties were not impaired. Examples 9-12 Effect on viscosity, cure rate, and film properties when sequentially co-reacting products are neutralized with different amines Two-stage esterification process substantially the same as in Example 2 A master batch of acid/E ¹ /E ² products was created. (EEW of E ¹ +E ² = 720; 1.32P-OH/oxirane). In the first stage, 700 g (0.2 g mol) of
DER-667 was added to 1000 g of methylene chloride and
Warm and reflux in 200g of IPA for 2-1/2 hours.
It was reacted with 70 g of 85% H ₃ PO ₄ at 41° C. for 41 hours. The acid number was 95; the oxirane content was less than 0.2%. In the second step, 1,6-bis-methylol-4-
Glycidyl ether of t-butylphenol 300
g (1.13 gmol) were reacted for 16.5 hours at 41°C. Oxirane content less than 0.1% by weight; acid value 70
It was hot. Add 2150g of distilled water while stirring.
The resulting homogeneous dispersion was divided into four equal portions. Example 9 Approximately 27 g of trimethylamine was added to 1000 g of acidic product dispersion. After stripping, the PH is
It was 7.4. The properties of a coating prepared and tested similarly to the coating of Example 5 were essentially the same. Example 10 1000g of the dispersion was mixed with triethylamine at pH 9 and dimethylaminoethanol before stripping.
34 g of a 50:50 mixture (weight ratio) was added. The resulting mixture was a highly viscous gel but could be easily stripped with solvent. The stripped dispersion was not highly viscous and gave a coating different from that of Example 9 at the same level of non-volatiles as follows: cure at 204°C (400〓) takes 3 minutes rather than 5 minutes; less tendency to dry out before curing; 1% P-toluenesulfonic acid has no different effect on cure rate; dispersions diluted with water are more viscous. Example 11 40 g of dimethylaminoethanol was added to 1000 g of the dispersion. A highly viscous but easily stripped gel resulted. Dilute remaining dispersion to 20% with water
diluted to a solids content of . The paint prepared similarly to the paint of Example 4 differs in the following respects; it cures slowly (5 minutes at 204°C (400〓), the other 3 minutes); it is somewhat less resistant to acetone; There is little tendency to dry out; much higher viscosity and 1% P-toluenesulfonic acid has less effect on accelerating cure. Example 12 To 1000 g of the dispersion was added 35.5 g of diethylaminoethanol. A highly viscous but easily stripped gel resulted. After stripping, the remaining dispersion is still quite viscous and soluble in water.
Diluted to 15% solids (instead of 20%). The differences between the coating prepared from the resulting solution and the coating of Example 9 are as follows: The viscosity of the solution is much higher; there is no tendency to dry out before curing; the curing is slow (204°C (400〓) And 7
5 minutes for Example 9; P-toluenesulfonic acid (1%) does not improve the curing rate at all. A comparison of Examples 2 and 4 showed that trimethyl and triethylamine were generally equivalent for neutralizing co-reaction products. Similarly,
No substantial differences were observed between N·N-dimethylethanolamine and N·N-diethylethanolamine (Examples 11 and 12). Example 8
Comparing (or 9) and 10, the 1:1 mixture of triethylamine and N·N-dimethylethanolamine has features such as faster non-catalytic curing rate, higher viscosity of the dispersion and lower tendency to dry the uncured film. I learned how to give. However, Example 11 showed that the use of N·N-dimethylethanolamine or N·N-diethylethanolamine gave poor results, except for a decrease in drying tendency.
It is clear from 12. Example 13 Series of reverse reactions of nonyl-substituted monofunctional type (b) E ² epoxide and bisphenol-F resin (E ¹ ) with H ₃ PO ₄ in ethanol 11.25 g of 84% H ₃ PO ₄ aqueous solution ( 0.096g mole) to 5
g of ethanol-B and 38.75 g (0.0965 g mole)
of glycidyl ether of 2,6-dimethylol-4-nonylphenol at room temperature. A slight fever developed. 5g of ethanol
A mixture of B and 31.8 g (0.096 g mole) of the experimental resin (probably the diglycidyl ether of bisphenol F) was then added. This caused an exotherm and raised the temperature of the final mixture to approximately 100°C. The reaction mixture was cooled and allowed to stand at room temperature during the weekend. 67 g of product (89% non-volatile) was stirred with 33 g of water and the resulting dispersion was neutralized (to PH 6.0) with 5.6 g of diethylamine. 10g or more of ethanol and
More than 18.4 g of water was added to obtain a dispersion containing 50% by weight non-volatiles. This dispersion was used to deposit a film on tin-free steel by electrocoating. 1~1/each
Two steel coupons, 2 inches by 4 inches, spaced 2 inches apart, were immersed in the dispersion to a depth of about 3 inches, and a 100 volt DC voltage was applied between the coupons (electrodes). The current, which was initially 150 milliamps, rapidly (30 seconds) decreased to 50 milliamps. The anode (cathode) electrode appeared to be covered by a cohesive coating of the resin. After baking at 175°C for 15 minutes, the obtained membrane showed good resistance to boiling water. Films of this dispersion were drawn onto tin-free steel coupons (not treated to remove oil) and showed excellent wettability. 10 at 185℃
After baking, the membrane was resistant to acetone, showed excellent resistance to boiling water, and did not buckle when bent into a 1 inch radius curve. When a portion of this dispersion was diluted with water to a non-volatile content of 5% by weight, the diluted dispersion was approximately the same in appearance and performance as the original solution.
Films of this diluted dispersion electrodeposited very well on aluminum and cold-rolled steel;
After baking at 175°C for 10 minutes, it exhibited excellent acetone resistance and withstood 50 inch pounds in a reversible impact test. Example 14 Simultaneous co-reaction of DER-667 (E ¹ ) and type (m) E ² epoxide with phosphoric acid (EEW=465
0.85P-OH/oxirane) 420 g (0.26 g mole) of DER-667 was dissolved in 900 g of methylene chloride and 180 g of isopropanol. Heat liquefied (~80~100℃) DEN (Dow Epoxy Novolak)
180 g (0.286 g mole; 1 eq.) of -438 was added and stirred, followed by the addition of 42 g of 85% H ₃ PO ₄ . The mixture was kept at room temperature for 1 hour and then brought to reflux temperature (41°).
and reacted at reflux temperature for 16 hours. At this point, the EEW (as a solid) is 49000 (oxirane% - 43 x 100/4900 = 0.09 + %) and the acid number is 53.
It was hot. 800 g of distilled water was added and stirred, and the resulting dispersion was divided into two equal parts. 25% of 50g of one side
One was neutralized with an aqueous NaOH solution, and the other was neutralized with 30.5 g of triethylamine. Both stripping products can be easily diluted with water to form stable, uniform, particle-free dispersions, although the NaOH-neutralized version was difficult to strip to solids contents above 15% by weight. did it. DEN438 has an EEW of about 180, an epoxide functionality of about 3.5, and is a polyglycidyl ether of a phenol-formaldehyde novolac. Water dilutability of product composition Analysis by gel permeation chromatography shows that only a very small amount of oxirane is present in water or P-OH.
It was found that the triester group was essentially not formed because it was consumed in reactions with other substances. Also, if the reaction medium does not consist of more than about 75% by weight of a solvent such as dichloromethane, very small amounts of polyfunctional diesters (an epoxide molecule bound to more than one other epoxide molecule through a phosphodiester group) may be present. ester) is formed in the reactant. From the data given in the examples above, it is clear that glycol group formation not only from the hydrolysis of oxiranes but also from the hydrolysis of ester (phosphodiester) groups proceeds to a limited extent, but at higher It progresses significantly at the reaction temperature and when using more dilute H ₃ PO ₄ . Direct esterification of alcoholic hydroxyl groups, such as those present in E ¹ (i.e., formed by P-OH/oxirane adductation), has an effect on the total number of phosphomonoester groups in the final product (i.e. after 3-6 hours of reaction). is small. It is particularly surprising that solubilization (water reducibility) of resins such as DER-667 can be achieved by a reaction in which up to about 95% of the oxirane groups are converted to glycol groups rather than acidic salt-forming groups. . Although DGEBA resin is already polyfunctional in the alcoholic hydroxy groups, it is clearly hydrophobic. In general, converting one oxirane per molecule to a glycol group would not be expected to significantly reduce the overall hydrophobicity of the molecule. moreover,
Conversion of the remaining oxirane groups (on average somewhat less than 1 per molecule) to alpha hydroxyphosphomonoester groups appears to eliminate sufficient salt (neutralized) groups for solution. Furthermore, the oxirane groups in the resin are almost entirely converted to glycol and (mono)ester groups, with 1
It is true that the neutralization products obtained from E ¹ resins having an EEW of less than about 3200 even at a much smaller average content of monoester groups are water dilute. Even more surprisingly, DGEBA with an EEW as high as 5500 can be made water-dispersible by the method of the invention. This product is produced by the reaction of an amount of phosphodiester groups (each one molecule of phosphoric acid with an oxirane group present on each of two different epoxide molecules) such that up to about 10% of the phosphorus present in the product. Even if it further contains (obtained), it will retain its original properties. Although higher proportions of diester groups may be present at some stages of the invention, such groups tend to hydrolyze to monoester and glycol groups. Even at room temperature, this hydrolysis reaction will generally continue until very few diester groups remain (as long as water is present). Since neutralization is usually carried out in the presence of water, the subsequent content of diester groups is usually very low. Neutralizes acid/epoxide reaction products containing relatively large amounts of free phosphoric acid; particularly when neutralized with an inorganic base, the amount of free acid derived salt present in the neutralized product is reduced to salt form. It may be contemplated that the dispersibility of the resin is actually higher in brine than in water. However, to avoid this problem and if the amount of base in the neutralized product is at least the sum of that consumed by the free acid and sufficient ester P to make the resin molecules dispersible in water, There are obvious expedients in whatever amount is required to form the -OH moiety into the salt form. The usefulness of this invention is as high as 13,000
It is clear from Example 5 that this extends indirectly to DGEBA type epoxides with EEW values.
That is, the latter type of resin, such as DER-684, does not produce water-dilutable products when neutralized by reaction with phosphoric acid, but will co-disperse in water with the (neutralized) reaction products of this invention. be able to. Based on some experiments not detailed here, it is one order of magnitude smaller than DER-667.
It was found that products obtained from DGEBA resins with EEW values were not effective dispersants for DER-684. However, all of the neutralization products of this invention are as high as the neutralization products derived.
It is clear that a significant proportion of unconverted DGEBA molecules containing at least EEW can be dispersed.
Neutralized products of this invention in which less than about 54% of the original oxirane groups remain unconverted can be dispersed in water and become useful coatings. When considering the statistical distribution of unconverted oxirane groups in resin molecules, it is clear that a significant proportion of molecules with all of the original intact oxiranes are present in such molecules. Thus, the composition of the invention as defined in the introduction of this specification provides a composition in which both oxiranes are intact or one of them is intact and one is substituted with a glycol or β-hydroxyphosphomonoester group. Molecules of formula (a) whose average molecular weight is such that both oxiranes are substituted with glycol or β-hydroxy ester groups;
It may also consist of molecules that do not exceed about 10 times the average molecular weight of the molecules in (a). (DER−684 and DER−
The ratio of EEW values of 667 is 13000/1550, or ~8.4
It is. ) The proportion of molecules having such oxiranes may be such as to provide about one oxirane per glycol or ester group in the composition. That is, the number of oxirane groups may be the same as the total number of glycol and β-hydroxyphosphomonoester groups. Can be derived from epoxides of formulas (b) to (p)
E ² type resins are highly preferred for the practice of this invention. Epoxides in which R ⁵ is a C ₃ -C ₁₀ alkyl group are particularly preferred for forming E ² -derived resins.
Among the latter, compounds in which p is 1 and R ⁵ is t-butyl or n-nonyl have an E ¹ and a resistance to wet hydrophobic supports such as oil-containing aluminum materials. It is most preferred as it provides superior performance of mixed dispersions of E2 ^- derived resins. The diglycidyl ether of 2,6,2',6'-tetra(methoxymethyl)bisphenol-A is the preferred alkoxymethyl substituted epoxide.
(Equation (1) for the production of E ² -derived resins (dispersions)) The relative proportions of E ¹ and E ² -derived resins (chlorinated) in the compositions of the invention are determined by the final product (cured coating, sealer). , surfactants, primers, etc.) can vary widely depending on the properties desired. In most cases, the characteristics are essentially
A final product that is characteristic of E ¹ derived resins is desirable. Therefore, the molar ratio of ^E1 -epoxide-derived species to ^E2 -epoxide-derived species will have a value of about 100 or less.
However, in other applications, the E ¹ epoxide can function more as a modifier than as the epoxide base. Therefore, E ¹ in the final product
The molar ratio of induced species to ^E2 induced species takes values down to about 0.1. If the E ² epoxide, or the low molecular weight E ¹ epoxide, undergoes some oligopolymerization during reaction with acid, each monomer unit in the oligomer is individually treated during the assessment of the E ¹ /E ² ratio. is counted as a numerator of The content of free (non-esterified) phosphoric acid in the mixed product ranges from 0 to 100 parts of epoxide-derivatable molecules.
It can vary within a range of 85 parts by weight. however,
If the intended ultimate use of the chlorinated mixture product does not require high flammability or the ability to release substantial amounts of separable base, i.e. against highly acidic environments or when heated A "free" acid content of more than about 5% by weight is generally undesirable unless the properties sometimes sought are required. Therefore, epoxide-derivatable (or derivatizable) molecules
The H ₃ PO ₄ content per 100 parts is about 1 part by weight or less.

Claims (1)

[Scope of Claims] 1. A method for producing an acidic resin neutralized with a water-dilutable base, which can be converted into a hydrophobic, high-performance thermosetting resin, comprising: (i) substantially orthophosphoric acid; In, the following formula, or [In the formula, each Q is independently n is an integer from 0 to 40; r is each 0, 1 or 2; R ¹ is a hydrogen atom, methyl or ethyl group; R ² is a bromine atom, a chlorine atom, C ₁ - A _C4 alkyl group or a _C1 - _C4 alkenyl group; ^R3 is a _C1 - _C4 alkylene group, a _C1 - _C4 alkenylene group, [Formula] -CO-, _-SO2- , -S-, -O- or a single bond; ^R4 is a bromine atom, a chlorine atom, a _C1 - _C4 alkyl group or a _C1 - _C4 alkenyl group; ^R20 is a hydrogen atom or a _C1 - _C12 alkyl group; be. ), and the reaction is ^{such that when the amount of oxirane groups in the converted E 1 resin} is brought into contact with a base, the resulting reaction product is reacted with water. From about 0 to about 0 per molecule ratio of H 3 PO 4 derived from the orthophosphate source material and the H ₃ PO ₄ derived from the phosphate source material to at least sufficient extent to permit dilution of the E ¹ resin.
25 molar ratio of water, the amount of orthophosphoric acid contained as such in said phosphate source material or obtained from said material by hydrolysis per oxirane group. and () combining the reaction product with at least enough base to make the resulting reaction product dilutable with water. The said manufacturing method is characterized by contacting. 2. Claim 1, characterized in that dioxane, methyl ethyl ketone, acetone, or a mixture of dichloromethane and acetone (the content of dichloromethane is 25 wt% or less) is used as the medium for the phosphoric acid/epoxide reaction. Method described. 3. The base according to claim 1, wherein the base is an amine of the formula NR ₃ (wherein each R is independently a hydrogen atom, a methyl group, or an ethyl group). Method. 4. In a method for producing a water-dilutable base-neutralized acidic resin that can be converted into a hydrophobic, high-performance thermosetting resin, () orthophosphoric acid is converted into (i) substantially the following formula: or [In the formula, Q is n is an integer from 0 to 40; r is each independently 0, 1 or 2; R ¹ is a hydrogen atom, methyl or ethyl group; R ² is a bromine atom, a chlorine atom, C _{1 -C4} alkyl group or _C1 - _C4 alkenyl group; ^R3 is _C1 - _C4 alkylene group, _C1 - _C4 alkenylene group, [Formula] -CO-, _-SO2- , -S- , -O-, or a single bond; ^R4 is a bromine atom, a chlorine atom, a _C1 - _C4 alkyl group, or a _C1 - _C4 alkenyl group; ^R20 is a hydrogen atom or a _C1 - _C12 alkyl group; It is the basis. ], and (ii) a polyether epoxide resin E ¹ consisting of a molecule represented by
a vicinal epoxide resin E ² having an epoxide equivalent weight of , the molar ratio of ^{E 1} to E ² is from ^0.1 to 100; When the amount is brought into contact with the base,
The E ¹ and E ² resins are combined with an orthophosphate source material and the H ₃ PO ₄ 1 molar ratio derived from this phosphate source material to at least sufficient extent to make the resulting reaction product dilutable with water. the amount of orthophosphoric acid contained in the phosphoric acid source material as such or obtained from the material by hydrolysis is and () at least enough base to enable the resulting reaction product to be diluted with water. The above-mentioned manufacturing method, which comprises contacting the reaction product with the reaction product. 5. Claim 4, characterized in that dioxane, methyl ethyl ketone, acetone or a mixture of dichloromethane and acetone (the content of dichloromethane is not more than 25 wt%) is used as the medium for the phosphoric acid/epoxide reaction. Method described. 6. The base according to claim 4, wherein the base is an amine of the formula NR ₃ (wherein each R is independently a hydrogen atom, a methyl group or an ethyl group). Method. 7 Resin E ² has the following formulas (b) to (p): (b) The following formula, [wherein Y is a hydrogen atom, a _C1 - _C4 alkyl group, or a _C1 - _C4 alkenyl group; each YO- _CH2- group is either ortho or para to the glycidyloxy group; x is 1, 2 or 3; p is 0 or 1; a is 1 or 2; R ¹ is each independently a hydrogen atom, a methyl group or an ethyl group; R ⁵ is a _C1 - _C12 alkyl group, alkenyl group, cycloalkyl group, phenyl group, alkylphenyl group, phenalkyl group, phenoxy group, bromine atom, chlorine atom or the formula [In the formula, y is 0, 1 or 2; T is a C ₁ to C ₄ alkylene group, a C ₁ to _{C 4} alkenylene group, [Formula] -SO ₂ -, -S-, -O-, or a single is a bond; ^R6 is a bromine atom, a chlorine atom, a _C1 - _C12 alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, an alkylphenyl group, a phenalkyl group, or a phenoxy group; t is 0 or 1; Yes; however, (x+a) cannot exceed 4, and (x+y) is between 2 and 4. ). ] phenyl glycidyl ether substituted with a methylol or alkoxymethyl group; (c) the following formula, (In the formula, b is 1 to 3; d is 0 or 1; R ⁷ is C ₁ to C ₁₂ alkyl or [Formula]; Y' is a hydrogen atom, a C ₁ to C ₄ alkyl group, or C _1
-C4 alkenyl group; ^R1 is a hydrogen atom, methyl group or ethyl group; provided that (b+d) cannot exceed 3. ) (2,3-epoxy)propylbenzene substituted with methylol or alkoxymethyl; (d) having 2 or 3 non-aromatic, carbon-carbon double bonds and optionally bromine; , having a chlorine or fluorine atom or a hydroxy substituent,
(e) Di- or tri-oxides of acyclic or cyclic _C4 - _C28 hydrocarbons or esters; (e) ^R8 -O- ^R9 , where each ^R8 and ^R9 is _C3 ~ _C12 aliphatic, _C3 ~
The same or different monovalent radicals can be derived by abstracting hydrogen from a _C12 alicyclic group or a _C3 to _C12 phenalkylene oxide. ); (f) Epoxy ethers represented by the following formula, (wherein, A is a chlorine atom, a bromine atom, a hydroxy group, or [Formula] (where R ²¹ is a C ₁ to C ₁₅ hydrocarbyl group); R ¹ is a hydrogen atom, a methyl group, or an ethyl group. ) 2,3-epoxypropyl halides, alcohols or esters; (g) the following formula, Glycol monoethers represented by or the following formula, [In each of the above formulas, R ¹ is a hydrogen atom, a methyl group or an ethyl group; R ¹⁰ is a hydrogen atom or a methyl group; X is a hydrogen atom, a methyl group or an ethyl group; g is 1, 2 or 3; h is an integer from 2 to 10. ] Glycol diethers represented by; (h) the following formula, (In the formula, R ¹¹ is a C ₂ to C ₂₀ divalent hydrocarbon group; R ¹ is a hydrogen atom, a methyl group, or an ethyl group; i and j are each independently 0 or 1.) diglycidyl ethers or esters represented by; (i) the following formula, [formula] and Mono- or diglycidyl ethers of the following formula; (j) Mono-, di- or triglycidyl ethers of glycerin; (k) [Formula] or [Formula] (wherein Z is [Formula]; R ¹² is a C ₁ to _{C 12} alkoxy group, a C ₁ to _{C 6} alkyl group, or a C ₂ to C ₆ alkenyl group; ¹³ is a hydrogen atom, a _C1 - _C12 alkyl group, or
is a _C2 - _C12 alkenyl group; ^R14 is a _C1 - _C8 alkyl group, an alkenyl group,
It is a cycloalkyl group, cycloalkenyl group or aralkyl group, and R ¹⁴ is present in the ortho or para position to the Z-CH ₂ - group on the benzene ring to which it is attached; R ¹ is hydrogen, methyl or ethyl. Yes; ^R15 is a _C1 - _C4 alkylene group, a _C1 - _C4 alkenylene group, or _-SO2- . ) trifunctional aromatic epoxides; (l) the following formula; (In the formula, R ¹⁶ is a C ₁ to C ₆ divalent aliphatic hydrocarbon group [Formula] C(CF ₃ ) ₂ , -SO ₂ -, -S-, -O- or a single bond; Z is [formula].) Tetraglycidyl ethers represented by (m) the following formula, (In the formula, p is 1 to 3; R ¹⁷ is each independently a hydrogen atom or a methyl group; R ¹⁸ is a C ₁ to _{C 4} alkylene group; Z is [formula]) tri- to penta-functional epoxy novolacs; (n) the following formula, (wherein u is 0, 1, 2 or 3; R ¹ is each independently a hydrogen atom, methyl group or ethyl group; R ¹⁹ is each independently a C ₁ -C ₁₂ alkyl group,
It is an alkenyl group, a cycloalkyl group, a phenyl group, a phenalkyl group or an alkylphenyl group. ) low polymerizable monoepoxides substituted with methylol; (o) epoxidized triglycerides of unsaturated fatty acids each having 18 or less carbon atoms, and (p) the following formula, (wherein r is each independently 0, 1 or 2; ^R1 is a hydrogen atom, methyl or ethyl group; ^R2 is a bromine atom, a chlorine atom, a _C1 -C4 alkyl group or _{a C1} - _C4 alkyl group; is a C ₄ alkenyl group; R ³ is a C ₁ to _{C 4} alkylene group, a C ₁ to _{C 4} alkenylene group, [Formula] -CO-, -SO ₂ -, -S-, -O-, or a single bond; Yes, Y is a hydrogen atom, a C ₁ - C ₄ alkyl group, or
is a _C1 - _C4 alkenyl group; p is 0 or 1; ^R5 is a _C1 - _C12 alkyl group, alkenyl group, cycloalkyl group, phenyl group, alkylphenyl group, phenalkyl group, phenoxy group, Bromine atom, chlorine atom or formula [In the formula, y is 0, 1 or 2; T is a C ₁ to C ₄ alkylene group, a C ₁ to _{C 4} alkenylene group, [Formula] -SO ₂ -, -S-, -O-, or a single is a bond; ^R6 is a bromine atom, a chlorine atom, a _C1 - _C12 alkyl group, an alkenyl group, a cycloalkylene group, a phenyl group, an alkylphenyl group, a phenalkyl group, or a phenoxy group; t is 0 or 1; Yes; however, (x+a) cannot exceed 4, and (x+y) is between 2 and 4. ). phenyl glycidyl ether substituted with methylol or alkoxymethyl; v is 1, 2 or 3; w is each independently 0, 1 or 2; ) of diglycidyl ethers of substituted bisphenols and substituted phenols shown in
The manufacturing method according to claim 4, wherein the manufacturing method is one or more of the following: