JPH0345091B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to water-dilutable resin compositions. The composition of the present invention comprises H ₃ PO ₃ and the following general formula (a):
or (q) a mixture of the base-neutralized reaction products of polyether epoxides and optionally other types of mono- or polyfunctional epoxides. A preferred method of the invention is to react the polyether (E ¹ ) with an orthophosphoric acid source material and neutralize the resulting product with a base, preferably an unstable base. however,
The present invention also consists of a preparation process that combines the reaction products of separately prepared E ¹ and E ² with phosphoric acid.
If the base is unstable, such as ammonia or a volatile amine, the neutralized resin diluted with water will evaporate the water, decompose the ammonia base by heating, and decompose the ammonia (or amine) base. ) and can be converted into a water-insensitive, high performance, thermoset resin by removing the resin and curing. 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 metals, from aqueous dispersions of the compositions described above. A preferred method of the present invention is defined below as a method for producing a base-neutralized reaction product of orthophosphoric acid and a polyether epoxide, which method comprises: (1) a compound of the general formula (a); or general formula (q) [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( _CF3 ) ₂ , -CO-, _-SO2- , -S-, -O-
or a single bond, and R ₄ is -Br-, -Cl-
or _C1 - _C4 alkyl or alkenyl group), n is an integer from 0 to 40, r is 0, 1 or 2, ^R1 is H, methyl or ethyl, ^R20 is H or carbon polyether epoxide resin E 1 consisting of a polyether epoxide resin E ¹ consisting of each molecule of alkyl of number 1 to 12] and which can be converted into a water-dispersible material by reacting with orthophosphoric acid and neutralizing with a base. Consisting of The reaction is E ¹
and the orthophosphoric acid source material and the oxirane groups in E ¹ and optionally E ² converted with 0 to 25 molecules of water per ₄ molecules of H ₃ PO are water dilutable when the resulting mixture is contacted with a base. The amount of orthophosphoric acid contained in said phosphate source material or obtained therefrom by hydrolysis is at least 0.3 P per oxirane group. −
() contacting the resulting reaction product with at least a sufficient amount of base to render it dilutable with water; In one aspect, the compositions of the present invention are resinous mixtures that are water dilutable when neutralized with base. In another aspect, the composition of the invention is a water-dilutable product obtained by contacting said 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) 1,2 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 into glycol or beta-hydroxyphosphomonoester groups, the average EEW of the epoxy molecules from which the resin molecule is derivatized is from 172 to 5500. Any other molecule other than the epoxides of general formulas (a) and (b) which is derivatized by converting the oxirane group in the vicinal epoxide ^E2 into a 1,2-glycol or beta-hydroxyphosphonomonoester; It has an EEW of 90-2000 and the molar ratio of E1 ^- induced molecules to said E2 ^- induced molecules is
The ratio of glycol to monoester groups in each of said molecule types is within the range 0.1 to 100 and is within the range 0 to 18. (B) 0 to 85 parts by weight of orthophosphoric acid (H ₃ PO ₄ ) per 100 parts by weight of the E ^{1 -} derived molecules; (C) at least a sufficient amount of the P-OH groups in the E 1 and E ^2- derived molecules are neutralized; , are precisely defined as water-dilutable, resinous phosphate compositions consisting of an amount of one or more bases, thereby rendering them water-dispersible. In a preferred type of composition as described above, those molecules not derived from epoxides of general formula (a) or (q) can be derived from E ² epoxides as defined above, which E ² 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 the aforementioned compositions,
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 the dispersion is damaged at such a high rate that it is impractical for use as a coating. The mixture that makes up the composition can be formed in either of two ways. The E ¹ and E ² epoxides are co-reacted with the phosphate source material, or the products obtained by reacting the epoxides separately can be the same or separately before or after neutralization with base. Can be mixed. This latter type of making the composition is considered to be another method or embodiment of the invention. That is, the present invention provides separately formed E ¹ /
Combine _{the H3PO4} reaction product and a sufficient amount of base;
It consists of rendering the combination water-dispersible. 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 O). (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 broadly defined process, wherein the overall ratio of acidic hydroxyl to oxirane groups 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, hardening is
Catalyzed by known chemicals, ultrasonic vibrators, heat, high energy waves or particle radiation, etc. All epoxides of the E ¹ type represented by the general formula (a) are described as resins. A few lower epoxides, such as the diglycidyl ether of bisphenol A, are available as pure crystalline materials. However, most
DGEBA type epoxides are not normally available as pure compounds due to the practical methods used in their manufacture. That is, 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 diall 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. An epoxide of general formula (a) with an EEW of less than or equal to 5500 may be converted to a resin having an EEW not exceeding 5500 and consisting of a corresponding amount of product molecules that can be represented by general formula (q). can be pre-reacted with an amount of the phenol defined above. The reaction is usually (when used in this way)
Dissolve the E ¹ epoxide in the medium, add the acid source material and water as necessary to utilize the material or provide the desired product composition, and achieve the desired degree of oxirane conversion. This is done by refluxing the mixture at a predetermined temperature (and pressure) until achieved. The reaction mixture is cooled, neutralized with a selected base,
It is 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),
For example, pyrophosphoric acid and triphosphoric acid can be used. 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 should be allowed 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 neat reactants, but it is preferred to use an effectively inert reaction medium. Solvents suitable for this purpose are as follows, listed in order of performance: (1) mixtures of acetone and methylene chloride at 25% or less by weight; (2) acetone and ketones such as methyl ethyl ketone; (3) cyclic ethers such as dioxane; (4) linear ethers such as glycol ethers. (5) Esters such as 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
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, and this
Imposing an upper limit of 5500 on the EEW of E ¹ epoxide,
A lower limit of 0.3 is imposed on the ratio of P-OH groups (provided by the acid source material) to oxirane groups. Glycol groups (resulting from addition products of water and oxirane groups or hydrolysis of phosphodiester groups)
A ratio of phosphomonoester to phosphomonoester of 18:1 or less is a necessary requirement for water dilutability. This requires that the molar ratio of water to H ₃ PO ₄ in the reactants be less than 25:1. 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 absent or has low activity in the solvent, the oxirane can be converted preferentially to such diester groups, and ^one molecule of E is converted to the diester group to the extent that a gel results. They can then be joined together. 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 along 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 therefore 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 has no deleterious effect on the dispersibility of the product in water. That is, the amount of the acid salt material used during the reaction is such that 85 parts by weight of H ₃ PO ₄ per 100 parts by weight of E ¹ derived resin molecules are present in the product.
Even at high parts by weight, 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 ratios and conditions for E ¹ /acid reactivity 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
~1. Reaction temperature...110-130°C Contact time...3-6 hours Of course, a high 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. It 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 alkoxymethy 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 will be 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 lower than the required curing temperature, but higher than the maximum vessel temperature obtained during stripping, its (free acid or phosphoester P-OH). Ammonia and amines are examples of such preferred bases. Preferred bases are amines, especially amines of the formula NR ₃ where each R is H, methyl or ethyl. 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

Epoxides having 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 or Particularly preferred are the E ¹ epoxides of the general formula given above. Q is Also preferred is an E ¹ epoxide. 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 composed of one molecule of bisphenol A and two molecules of epichlorohydrin in the presence of a base such as sodium hydroxide.
It is formed by reacting with moles. 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 by substituting a mixture of epichlorohydrin and methylepichlorohydrin for chlorohydrin alone in the well-known process described in Handbook of Epoxy Resins, Lee and Nebiley, Matsugrow-Hill (1967). It can be formed by using it. Different bisphenols can likewise be used in known methods for the reaction of individual bisphenols with hychlorohydrin or diglycidyl ethers of the same or different bisphenols. The few commercially available DGEBA-type resins are biphenol-A substituted with bromine or chlorine.
derived from bisphenols other than epichlorohydrin or chlorohydrins other than epichlorohydrin. That is, commercially available DGEBA type resins are epoxides with the general formula E ¹ where R ¹ is H, n is 0 or 2, R ² is Br or Cl, and R ³ is (CH ₃ ) ₂ C. be. Examples of commercially available DGEBAs preferred in the practice of this invention are manufactured by The Dow Chemical Company and are as follows.

【table】

[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: Mononuclear dihydric phenols

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Dinuclear bisphenol Additional bisphenols are added to the chemistry of phenolic resins, Art D'Avrille Martin 64-79.
Page Wheley & Sons, Inc., New York, New York, Table 1. E ¹ epoxides of the type represented by general formula (q) can be prepared by adding one or more phenols to the corresponding epoxide of general formula (a) 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. Phosphate-providing materials that can be used in the practice of this invention include:
100% orthophosphoric acid, hemihydrate ( _2H3PO4.H2O ) and at _least 18% by weight _H3PO4 (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 phosphate supply material is of the condensation type, sufficient water must be supplied at some stage prior to curing of the resinous final product to ensure that no substantial amount of P-O-P bonds are present in the cured resin. No. 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 product are, of course, dependent on factors such as the water to acid ratio, the acid to oxirane ratio, the nature of the solvent, temperature and contact time. Depends on. It has been found that the reaction involves 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 of water and oxirane but also hydrolysis of the phosphodiester group is occurring. As a result of the previous reaction, some free phosphoric acid is 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. Generally exists. 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 compared to 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 material. 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 is easily accomplished by using some P-O-P group-containing acid donor (eg, pyrophosphoric acid or polyphosphoric acid) with 100% phosphoric acid. Esterification of alcoholic hydroxyl groups (and production of water)
can also be minimized by carrying out the reaction at relatively low temperatures, such as 60-80°C. If necessary, a suitable P-O- for later purposes.
The P group-containing acid supplying substance is P-O-P.
It can be easily prepared in situ by pre-reacting with a smaller amount of water than is needed to react all of the groups. The presence of chlorinated phosphonoester groups results in E ¹ /
Although essential for the water dilutability of the H ₃ PO ₄ reaction product, there is no need to report the high proportion of oxirane groups in E ¹ as ester groups rather than as glycols in the product. In contrast, esterification products of DER-667, where the ratio of the number of glycol to ester groups was between 18.3 and 1, were found to be 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 generally results in a heterogeneous reaction mixture unless a good solvent for the water is included. The presence of relatively high proportions of water does not necessarily result in an expectedly low ratio of phosphoester to glycol groups in the reaction product. Ester to glycol ratios such as 1:2.3 were obtained using DER-667 as the epoxide and acetone as the reaction medium at a water to acid molar ratio of approximately 2:1. 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 pose 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, less than 1/3 mole of H ₃ PO ₄ per equivalent of E ¹ (i.e. oxirane 1
It is preferable to maintain at most 1 acidic hydroxyl group per acid hydroxyl group, 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), then
It is highly preferred that H ₃ PO ₄ is present in an amount of 1 part by weight or less per 100 parts by weight of E ¹ . Higher amounts of acid can be used up to the point where the reaction mixture becomes unduly heterogeneous. However, sufficient
By using amounts of H ₃ PO ₄ or more, sufficient free phosphate can be included to have an undesirable effect on the properties of the uncured or cured resin. It is thus 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 able to dissolve 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 mixtures thereof. (The alcohols listed below are examples of inert solvents that do not have harmful reactivity to an unacceptable extent. These alcohols convert an aqueous solution of H ₃ PO ₄ to a dilute solution of E ¹ resin in dichloromethane alone. They are particularly useful as co-solvents where precipitation is likely to occur in the absence of these alcohols, such as in the case of alcohols that are susceptible to precipitation.) The nature of the reaction medium influences both the rate of reaction and the composition of the product. 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, solvents inferior (or non-) to water are linked together by diester groups:
E promotes the formation of highly polymeric chains consisting of ¹ epoxide residues. Thus, DER −667 can be converted to H ₃ PO ₄ (aqueous H ₃ PO ₄
1 wt% of (85% of) and ₁₀₀ % _CH2Cl2 at 60 °C
The reaction mixture gels in about 4 hours. Under these conditions, the chemical activity of water in solvents such as dichloromethane does not appear to be high enough for substantial hydrolysis of the oxirane or ester groups to occur. (However, the latter type of gel could be dissolved in more water-miscible solvents and hydrolyzed to fully useful products containing approximately equal numbers of glycol and monoester groups. ) Also, when the reaction medium contains 25% by weight of a water-miscible solvent such as ascentone - CH ₂ Cl ₂ , diester formation is still the predominant reaction (at 60° C.), but the product is not a gel. Water (included in the _H3PO4 ) in a medium consisting of 75% by weight of _CH2Cl2 and 25% by weight of _acetone at a temperature of 115 °C to ₁₂₀ °C
The activity of is substantial. Diester formation clearly proceeds 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. Obviously the direct addition of water on the oxirane group is the predominant reaction (at 115-120°C), but as the proportion of acetone in the CH ₂ Cl ₂ /acetone mixture increases, the increase in glycol versus monoester groups increases. The ratio 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 some instances for preparing a medium with a desired combination of solvent action and initial boiling point or azeotropic point (reflux temperature). Suitable reaction temperatures range from the lowest temperature at which P-OH addition with the oxirane group (in the E ¹ epoxide) proceeds at a useful rate, to higher temperatures.
(1) a harmful reaction (such as between an alcoholic reaction medium and phosphoric acid) occurs to an unacceptable extent; or (2)
up to 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 believed to be near optimal for commercial implementation of the process of the invention. The interdependent nature of temperature and solvent effects was shown in the previous discussion of reaction media. When reaction temperatures above the atmospheric boiling point of the reaction medium are used, pressure is an important factor in the reaction only when operation under high pressure - at least equal to the autogenous pressure of the reaction mixture is necessary. . 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. It is not necessary to add the reactants together gradually and/or at low temperatures unless highly reactive epoxides are used (which ^E2 epoxide often is). An example of a highly reactive E ¹ epoxide is the diglycidyl ether of bisphenol-A. In the latter case, it is desirable to operate initially at a temperature sufficiently low 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, the reactants (and medium) are
By pre-cooling, mixing and stirring at low temperatures (for example below 5° C.) for several days, the reactants can be mixed together as thoroughly as possible prior to the start of a given reaction. Thereafter, the mixture should be warmed gradually to prevent any tendency towards rapid exotherm. 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 drive one or more reactions to completion more rapidly. 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 maintained under heat until at least 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 the chlorinated (neutralized) resin may coagulate, it is generally desirable to add water gradually with good stirring. The reaction products of base neutralization H ₃ PO ₄ E ¹ and/or E ² are:
Any base may be used for neutralization so long as the resulting neutralized product is water dilutable.
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 phosphate group 1
It is generally preferred, and usually necessary, when the acid number of the product resin is relatively low that at least one equivalent of base is added per base. At the other extreme, an amount of base sufficient 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 lithium, sodium and potassium hydroxides. These bases should be used in the form of uncured salts (e.g. as surfactants) or with resins in which curing can be effected 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 may also be used as water-dispersible sealers or primers on materials such as green ceramic materials that are fired in subsequent steps. C Oxides or hydroxides of other metal groups such as copper and iron, or their hydrates, complexes with ammonia, etc., to form phosphates or acid phosphates with moderate water solubility. D Ammonia or ammonium hydroxide. E. Organic bases. This class of bases is particularly preferred and includes compounds such as: 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 those of classes b and f, which can be removed simply by heating below about 150°C. This is under a pressure of 760mmHg
It is generally possible to carry out with bases having a boiling point below 150°C. Most preferred of the latter bases is the formula NR ₃
These are amines represented by Note that each R can independently be H, methyl, or ethyl group, and 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, not only with respect to each of the aforementioned factors, but also because it is highly resistant to residual amounts in the cured coating and at high temperatures such as those found when processing canned foods. 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; the other R's are
Independently H, ethyl or 2-hydroxyethyl. In order of decreasing preference, the 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, triethanolamine presents no problems when added together with CYMEL 303 (hexamethoxymethylmelamine) to the coating formulation of the dispersion according to the invention. 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 make it satisfactorily easily stirrable and dispersing, and then adding the base. (or vice versa). If the acid is not removed from the epoxide/acid reaction mixture, a very advantageous method is to simply add 2 equivalents of base (e.g. 2 moles for amines) per mole of H ₃ PO ₄ (100%) added to the reaction system. ). 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 this condition is maintained 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. You should wait a sufficient amount of time after doing so. Normally, no change in PH value will be seen after about an hour. Dilution and utilization 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 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, Additional water is typically diluted 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 two separate liquid phases is avoided. However, in some cases,
It may be 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 undesired 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. . 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 hydration-miscible solvent. In another state of use, the neutralized reaction product can be converted, for example by spray drying, into powder form 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 draw bar. 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 water 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 will occur between the OH groups and groups reactive towards the above-mentioned functional groups in the additive hardeners (eg ureas, melamines and phenolic compounds). Product Identification Method 1 Acid Titration The relative amounts of phosphoric acid charged to the reaction, reported as free acid, as monoester groups, and as diester groups in the product mixture, are determined as follows. A sample of the reaction mixture sufficient to give approximately 1 milliequivalent (meq) of solids (based on acid present) was added to 66.7 wt/w of 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 a Mutrohm/Hersan
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
10 ml of 10% CaCl ₂ aqueous solution is added and allowed 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 the sum of the second (last) proton in the monoester and the second 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 _ep = 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 Resin DER-667 by reaction with 65% or 75% H ₃ PO ₄ and neutralization with trimethylamine
Solubilization of (trademark). EEP=~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 pass 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 H ⁺ ) per equivalent of resin.
An amount of 65% H ₃ PO ₄ (15.3 g) was used to give . The results of Experiments A and B are summarized in Table 1 below.

【table】

Table: Example 2 Solubilization of resin DER-664™ 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%, water 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 other hand, 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.
It was 0.013 equivalent. This ruffinate required 3 g (0.03 equivalents) of trimethylamine for neutralization. The total consumption for the reaction is therefore
0.076−(0.013+0.030)=0.033 equivalent, i.e.
There were 0.033/0.025=1.32 equivalents of H ⁺ per equivalent of oxirane. 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 number of the reaction mixture is low (108), and the acid content of the extract and raffinate are 0.009 and 0.009, respectively.
The amount of acid consumed in the reaction was 0.033 equivalent in this experiment as well. Both Ruffinates A and B gave (after stripping of residual dioxane) slightly cloudy but stable dispersions in water with a solids content of 41%. Example 3 Effect of EEP and H ⁺ /oxirane ratio on solubilization of DGEBA type epoxy resin by reaction with 85% H ₃ PO ₄ Four species with EEW varying from 190 to 2000
DGEBA type resins were reacted separately at 75% in dioxane with 85% H ₃ PO ₄ . 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] Example 4 Resin DER-667 produced by reaction with condensed phosphoric acid raw material
Solubilization of (8P-OH/oxirane) 100g (0.05 equivalent) in 200g 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 extracted repeatedly with water and the combined extracts were titrated. The proportion of oxirane groups in DER-667 converted to phosphoric acid _{monoester is}
(charged with H ₄ P ₂ O ₇ ) and the final content of free acid in the extract was calculated to be 71.4%. Therefore, the proportion of oxirane groups converted to glycol groups is 28.6% (due to the difference),
The ratio of glycol:monoester groups in the final product 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 to 8.0, stripped, and diluted with water to determine the content of non-volatile components.
The content was adjusted to 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 A 1 mole per equivalent (6 phr) of H ₃ PO ₄ (H ₃ PO ₄
99% aqueous solution) in methyl ethyl ketone at 80℃ for 15 hours.
DER −667/H ₃ PO ₄ products with ester content were created. There was no residual unconverted epoxide, and the glycol to ester ratio was 34/66 = 1/1.94. This product is successively added in smaller amounts than the previous one.
DER −684 solution (40% solids by weight in MEK)
and each resulting mixture was neutralized with 2 equivalents of triethylamine, diluted with 25 phr of methylene chloride, and mixed with 100 parts of water per 100 parts of total resin. The product after stripping (emulsion) contains 50% solids by weight,
It was evaluated as a dispersion. The results are as given in Table 3.

[Table] None
B Add 680 g of a 40% by weight solution of DER-684 in MEK.
3.72g of pyrophosphoric acid and its ₁₀₀ % _H3PO4
Heated to 78° C. for 24 hours with the amount of water (0.38 g) necessary to convert (~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 5050 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 appreciate that the (average) molecular weight of approximately 26,000
The advantages in cured film properties provided by the presence of DGEBA resin will be appreciated. Furthermore, the very slow conversion rate of oxirane observed in the Section B experiment suggests that most or all
DER −684 oxirane group is formed −684
It is clear that it is present in intact form in the dispersion. In the presence of both water- and acid-hydrolyzable amine phosphate groups (even DER −684
It would not have been expected that the latter group would remain unconverted for an unspecified amount of time (even if the latter group were not dissolved but dispersed). however,
Aqueous dispersions of neutralized mixtures of DER-684 (as such or reacted with H ₃ PO ₄ ) and DER-667/H ₃ PO ₄ reaction products are highly novel oxirane-containing materials. It seems reasonable to assume that the composition is the same. Example 6 Reduction of free acid content. Improved dispersion in the reaction product of high EEW DGEBA resin with ~6 phr H ₃ PO ₄ . 95 g (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 (water of the solution) 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 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 triphenyphosphonium 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 to 200
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 it 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
Fischer surface tension was measured using wire circles of the same diameter (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, evaluate it comprehensively using the visual criteria mentioned above and give it a rating of 1.
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] (3) Phenol 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 lbs. (~0.02 1 b. mol) of DER −667 to 100
Dissolved in 1 bs. of methylene chloride and 20 1 bs. of IPA, warmed to reflux for 2 hours at 41°C,
Reacted with 85% _{H3PO4 for} 24 hours. The oxirane content on a solids basis was less than 0.1%. The glycidyl ether of 1.6-bis(methylol)-4-t-butylphenol 30 1 bs. (~0.1 1 b. mol),
Next, the mixture was reacted at 41°C for 33 hours. The oxirane content was again less than 0.1%; the acid number was 14.5. 175 1bs. of distilled water, and then 80
1 bs. of triethylamine was added with stirring. After the solvent was stripped off, the residual dispersion had a pH of 8.5 and exhibited excellent stability and solution properties, ie, no sediment, low opacity, and no granularity. The composition was applied onto amrinium specimens in a proportion of 20% by weight of non-volatile components in water. At this time #10
A wire-wound rod was used, and the surface of the specimen was not pretreated. Good wettability and extremely excellent fluidity were observed, with 8 minutes at 380〓 and 5 minutes at 400〓.
It was found that sufficient hardening was achieved in 3 minutes at 440°C. The chemical resistance of this film was excellent; for the most part, a 50 acetone double rub was passed. Excellent wetting properties were also observed when applied onto tin-free copper 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 neutralizing sequential co-reaction products with various different amines. A masterbatch of acid/E ¹ /E ² products was prepared using a two-stage esterification process substantially as in Example 2. (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, 300 g (1.13 g mol) of the glycidyl ether of 1,6-bis-methylol-4-tert-butylphenol were reacted at 41 DEG C. for 16.5 hours. The oxirane content was less than 0.1% by weight; the acid value was 70. 2150 g of distillate was added with stirring and 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 trimethylamine 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 shows that the use of N,N-dimethylethanolamine or N,N-diethylethanolamine yields poor results, except that they tend to dry out.
It is clear from 12. Reference example 13 Nonyl-substituted monofunctional group type (b) E ² epoxide and bisphenol-F
_A series of reverse reactions between resin (E ¹ ) and _{H 3 PO 4} in ethanol.
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 and spaced 2 inches apart, were immersed in the dispersion to a depth of approximately 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. Reference example 14 Simultaneous co-reaction of DER −667 (E ¹ ) and type (m) E ² epoxide with phosphoric acid (=465
0.85P-OH/oxirane) DER-667 420 g (0.26 g mole) was dissolved in 900 g methylene chloride, 180 g and isopropanol. Heat-liquefied (~80-100℃) DEN (Dow Epoxy Novolak) −
Add 180 g (0.286 g mol; 1 equivalent) of 438 and stir.
Then 42 g of 85% H ₃ PO ₄ was added. The mixture was kept at room temperature for 1 hour, then heated to reflux temperature (41°) and reacted at reflux temperature for 16 hours. At this point the EEW (as a solid) is 49000 (oxirane% -
43×100/4900=0.09+%) and the acid number was 53. 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. 15 for those neutralized with NaOH
Both strip products were easily diluted with water to form stable, uniform particle-free dispersions, although it was difficult to strip to solids contents in excess of % by weight. DEN 438 has an EEW of about 180 and has an epoxide functionality of about 3.5 and is a polyglycidyl ether of a phenol-formaldehyde novolac. Water dilubility of the 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 no 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. Additionally, converting 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, and even at an average content of monoester groups well below 1 per molecule, it is possible to obtain an E ¹ resin with an EEW of less than about 3200. It is true that the neutralized product obtained is water diluted. 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, whereas the (neutralized) resins of this invention
It can be co-dispersed in water with the reaction products. Based on some experiments not detailed here, it is one order of magnitude smaller than DER −667.
It was found that the 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 compositions of the invention as defined in the introduction of this specification are characterized in that 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 consist of molecules that do not exceed about 10 times the average molecular weight of the molecules in (a). (DER −684 and DER −667
The ratio of EEW values is 13000/1550, or ~8.4. ) 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.

Claims (1)

[Claims] 1 (a) or (q) [Wherein, Q each independently represents [Formula] or [Formula]; n is an integer of 0 to 40; r is independently 0, 1 or 2; R ¹ is independently a hydrogen atom, methyl or an ethyl group; ^R2 is independently a bromine atom, a chlorine atom, a _C1 - _C4 alkyl group, or a _C1 - _C4 alkenyl group; ^R3 is independently a _C1 - _C4 alkylene group, a _C1-C4 alkylene group; ~ _C4 alkenylene group, C( _CF3 ) ₂ , -CO-, _SO2- ,
-S-, -O-, or a single bond; ^R4 is independently a bromine atom, chlorine atom, _C1 - _C4 alkyl group, or _C1 - _C4 alkenyl group; ^R20 is independently a hydrogen atom or a _C1 - _C12 alkyl group. ] 1, in which at least a part of the oxirane groups in the epoxide resin E ¹ represented by is neutralized with a base;
a resin molecule that has been converted to a 2-glycol phosphomonoester group or a base-neutralized beta-hydroxyphosphomonoester group, the average epoxy equivalent of the resin molecule being 172 to 5500; (b) the resin molecules 100; A water-dilutable resinous phosphate ester composition comprising 0 to 85 parts by weight of orthophosphoric acid (H ₃ PO ₄ ); and (c) a base. 2. A composition according to claim 1, wherein the number ratio of glycol groups to monoester groups in each type of molecule is from 0 to 18.