JPH0428700B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polymerizable monomer and a method for producing the same. In particular, the present invention provides the formula:

The present invention relates to a polymerizable monomer containing a cyclic urenoid group of the formula and a method for producing the same. The above groups are also known as ethylene urea groups or imidazolidinone groups. As used herein, the term "cyclic ureido" group refers to the above structure unless a more precise definition is required for a particular monomer. For example, UK Patent Nos. 1061492 and 1072894
It is known from the patent that polymerizable monomers containing ureido groups are useful for producing polymers that exhibit good adhesion to substrates, especially under humid conditions. However, many of the monomers previously proposed for use in making such polymers require lengthy and complex manufacturing methods; some are sensitive to hydrolysis conditions; Yes; these monomers are “clean”
These monomers cannot be produced in a "clean" state, and it is not easy to remove impurities generated during their production from these monomers. Some of the impurities of conventional monomers, such as non-polymerizable water-soluble impurities, can even reduce the properties of the polymer specifically sought when using the above monomers. The present invention has advantages over previously known monomers,
A polymerizable monomer containing a cyclic ureido group is provided. The novel monomers of the present invention can be prepared in high yields using simple reaction conditions;
Furthermore, these monomers do not contain harmful impurities. These monomers can be used to prepare polymers, polymer dispersions and coating compositions with superior properties. The structure of the new monomers can be varied widely to include other types of functional groups in addition to the desired type of polymerizable ethylenically unsaturated groups. HLB (new hydrophilic-lipophilic balance) can also be broadly modified, resulting in monomers becoming water-soluble on the one hand,
On the other hand, they can be rendered water-insoluble. Unlike many conventional monomers containing amino groups, the monomers provided by the present invention yield polymers that do not exhibit undesirable yellowing during use. Furthermore,
The monomers of the invention may be made particularly stable against hydrolysis and aminolysis. According to the invention, therefore, the formula: [In the formula, A represents a group,

【formula】 B is a group:

[Formula], R ₃ is Y-(CH ₂ ) _o - (n is 0 to 16),

[Formula] or

[Formula], R ₄ is a C ₁ -C _a alkyl group, and V is OH or -
CH and T is

[Formula] or CH ₂ = CH −CH ₂ −, W is −H or −CH ₃ , and Y
is -H or -OH] is provided. The polymerizable monomer of the present invention has the formula: (wherein the groups A' or B' are respectively identical to the groups A or B as defined above, and the remaining groups A' or B' are addition polymer residues of the groups A or B as defined above, or , both groups A' and B' are the groups A and B described above.
is an addition polymer residue of ). The polymerizable monomers of the present invention having the above structure are used to prepare addition polymers by polymerizing the monomers, and the monomers are It is used to prepare addition copolymers by polymerizing monomer mixtures containing at least 0.1% by weight. The polymerizable monomer of the present invention has the formula: (wherein A has the meaning given above). The presence of cyclic ureido groups can impart greater water resistance to polymers or polymer mixtures, and cyclic ureido groups can be introduced into polymers by the use of copolymerizable monomers containing this group. It is well known that it can be obtained. Surprisingly, in view of the problems associated with the conventional production of many such monomers, the monomer of formula () above can be easily produced at relatively low temperatures by the method described below. This was recognized. HLB as mentioned above,
In order to vary the solubility, functionality and polymerization properties, the nature of the groups A and B can be varied over a wide range by carrying out variations of this process. Certain monomers of the invention can be polymerized to produce homopolymers or copolymerized with other specific monomers of the invention. Alternatively, monomers of the invention may be copolymerized with other polymerizable ethylenically unsaturated compounds to produce copolymers. Such copolymers contain at least 0.1% of monomers of formula () according to the invention, and suitable comonomers include, for example, allyl alcohol, allyl glycidyl ether, allyl methacrylate, acrylonitrile, acrylamide, methyl or Higher alkyl acrylates or methacrylates, maleic anhydride or maleic esters, styrene or substituted styrenes, vinyl acetate, vinyl chloroacetate, vinyl chloride, vinylidene chloride, vinyl bromide,
Vinyl methyl ether, vinyl propyl ether, vinyl butyl ether, vinyl benzoate, vinyl laurate, vinyl methoxyethyl ether, vinyl benzyl ether, vinyl sulfonic acid, vinyl pyrrolidone, vinyl pyridine, methacrylonitrile, methacrylamide, ethylene and higher olefins. I can list it. It will be appreciated that the homopolymers and copolymers of the invention may be used in admixture with other polymers. The intermediate of the above formula () is of the formula: can be produced by reacting a primary amine with a substance containing an epoxide group and having a structure that provides group A when reacted with a primary amino group. The intermediate of the above formula () can further be of the formula: It can be produced by reacting a primary amine with a substance having an activated double bond by a Michael addition reaction. The inventors have found that secondary amines () can be easily and conveniently prepared using any of these methods, which are exemplified below. The aminoethyl imidazolidinone is dissolved in a solvent, preferably water or C _1-14 alkanol and stirred at ambient temperature. The monofunctional epoxide compound is added; the mixture is stirred and kept below 40°C for 3 hours. Usually two phases are initially present, but depending on the composition of the monofunctional epoxide, the product is either a clear, homogeneous solution or a micellar dispersion. usually,
Monofunctional epoxides are insoluble in water, and unreacted epoxide in the reaction product can be detected by diluting a portion with excess water. Although other solvents or solvent mixtures may be used, water or C _1-14 alkanols are preferred solvents because the reaction proceeds quickly and can be easily monitored. The inventors have determined that secondary amines with various functional groups, including optionally olefinically unsaturated groups, are
It has been found that it can be produced by selecting a reactive substance having a functional group in addition to the epoxide group. Secondary amines () with one or more additional functional groups can be prepared and compounds with one or more epoxide groups can be used.
Alternatively, we have used secondary amines ()
It has been found that can be easily prepared by adding a substance having an activated double bond to an aqueous solution of aminoethylimidazolidinone. Preferred secondary amines are prepared by selecting materials that do not contain ester bonds. The present inventors found that when such an ester bond exists, the resulting secondary amine is unsuitable for the production of monomer () because a cyclic ureido compound containing no unsaturated olefin group is formed. I found out that. For example, preferred secondary amines are ethylene oxide,
It can be produced using propylene oxide, butylene oxide, allyl glycidyl ether, glycidol, epichlorohydrin, acrylonitrile, methacrylonitrile. Alternatively, the secondary amines can be glycidyl acrylate, glycidyl methacrylate, glycidyl “versatate”
(“Versatate”), allyl methacrylate, methyl acrylate and other esters of acrylic or methacrylic acid, acrylamide or methacrylamide. According to the invention, furthermore, the formula: A method for producing a monomer of formula (), which comprises reacting an intermediate material with a material containing an epoxide group and having a structure for providing group B when reacted with an amino group. provided. Preferably, the substance having the epoxide and having the structure for providing the group B is selected from glycidyl (meth)acrylate or allyl glycidyl ether. The inventors have discovered that this process can be carried out easily and conveniently using methods similar to those used in making secondary amines. In a typical manufacturing method, an epoxide compound is added to an aqueous solution of a secondary amine, and the temperature is adjusted to 50-60°C.
and hold for about 3 hours. Usually, initially, 2
Although two layers are present, the product is either a clear homogeneous solution or a micellar dispersion, depending on the combination of epoxide compounds. Epoxides are usually insoluble in water, so unreacted epoxide in the reaction product can be easily detected by diluting a portion of the product with excess water. Although other solvents or solvent mixtures may be used, aqueous mixtures or water are the preferred solvents because the reaction proceeds easily and the reaction can be easily monitored. Optionally the epoxide may be selected to contain ethylenically unsaturated groups or certain other functional groups or combinations of functional groups, but if the secondary amine does not contain ethylenically unsaturated groups, , this group must be contained in the epoxide compound. For example, the epoxide compound can be allyl glycidyl ether or other epoxyalkyl allyl ether, glycidyl, glycidyl acrylate or glycidyl methacrylate, or other epoxyalkyl acrylate or methacrylate. Epoxide compounds can also be used, for example, ethylene oxide or higher alkyl oxides, benzyl oxide, epichlorohydrin, epoxy resins, glycidol, "versacic acid"("Ve-
rstic acid") or other glycidyl ethers. Although the range of structures of the monomers of the invention that can be prepared using the simple method described above is very wide,
The range of monomers () is not limited by these manufacturing methods. The desired and useful properties of the monomeric compounds of this invention derive from the structure of the monomers themselves rather than from their method of preparation. The monomers of the invention may contain groups capable of modifying certain physical properties of the polymers derived therefrom, such as halogen or cyano groups; It may be a group which can subsequently take part in further chemical reactions, for example a hydroxyl group or an allyl group. Also, depending on its end use, the monomeric compounds can readily be made to be fully water-soluble, exhibit surface activity in aqueous media, or be water-insoluble. formula: A water-dilutable dispersion containing particles of the addition polymer is prepared from an addition polymer having a residue of a polymerizable monomer represented by the formula (wherein A' and B' have the above-mentioned meanings). It is possible. Alternatively, the addition polymer is one prepared by polymerization of monomers containing at least 0.1% by weight of a monomer of formula (), based on the total weight of the monomers. Furthermore, the formula: Water-dilutable dispersions of polymer particles as described above may be prepared by polymerizing ethylenically unsaturated monomers containing at least one of the monomers in water and/or water-miscible liquids. . Furthermore, it is a group reactive with a secondary amine, and
During or after polymerization of the monomer, the formula: An ethylenically unsaturated monomer containing at least one monomer having a reactive group to be reacted with a substance having the above-mentioned meaning (wherein A has the above meaning) is added to water and/or a water-miscible liquid. A dispersion of the polymer particles can be produced by polymerization in a polymer. A water-dilutable coating composition can be prepared from a water-dilutable dispersion of polymer particles as described above,
Also, water-based paints can be prepared from dispersions of polymer particles as described above. Furthermore, water-based paints can be prepared which additionally contain polymer particles that do not contain residues of monomers (). Water-dilutable dispersions of the polymer particles described above may be as low as 5% by weight based on the total weight of the dispersion.
% by weight. However, dispersions with low solids content create difficulties in preparing coating compositions such as paints with suitable viscosities for brush or roller application, whereas dispersions with very high solids content The body is difficult to handle and can undergo changes in viscosity during storage.
Polymer content is 45-60 based on the total weight of the dispersion
Preferably, it is % by weight. Although the polymer particles are typically substantially spherical, the polymer particles in the dispersions of the present invention are not limited to this shape. For example, the polymer particles may be similar clusters of small particles or may be ellipsoidal. Particle size can be varied within a wide range. The particle size distribution can be broad or narrow. Usually, the average particle size, expressed in diameter, is 0.05 microns or more and 10 microns or less, but preferably 1 micron or less in diameter. The dispersion of the invention is water dispersible; i.e.
The liquid or liquid mixture that constitutes the continuous phase is fully miscible with water. Suitable liquids that may constitute the continuous phase include water, methanol, ethanol, isopropanol, acetone and ethylene glycol. Mixtures of these liquids may also be used. The liquid may contain dissolved salts. Tap water may also be used. The composition of the polymer can vary within wide limits. Suitable ethylenically unsaturated monomers that can be used to prepare the polymer dispersion include: allyl alcohol, allyl glycidyl ether, allyl acrylate, allyl methacrylate, acrylonitrile, acrylamide, methyl or higher alkyl acrylates or methacrylate,
Maleic anhydride or maleic acid ester, styrene or substituted styrene, vinyl alcohol, vinyl acetate, vinyl chloroacetate, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl methyl ether, vinyl propyl ether, vinyl butyl ether, vinyl benzoate, lauric acid Vinyl, vinyl methoxyethyl ether, vinyl benzyl ether, vinyl sulfonic acid, vinyl pyrrolidone, vinyl pyridine, methacrylonitrile, methacrylamide, ethylene and higher olefins. Difunctional or higher functionality monomers include, for example, ethylene glycol dimethacrylate, poly(ethylene oxide) dimethacrylate or divinylbenzene. The monomer residues () according to the invention are usually present in relatively low proportions in the polymer, preferably from 0.1 to 5% by weight, based on the total weight of the polymer. The polymer can have any suitable average molecular weight so long as it is large enough to enable it to form a distinct particulate phase without remaining in solution. The molecular weight of the polymer in the dispersed particles is
Preferably it is larger than 10,000, but it can be very large, eg up to several million in size. In extreme cases, the polymer can be crosslinked, in which case each particle consists of a single crosslinked polymer molecular chain and is therefore a gel particle. Water-dilutable dispersions can contain any ingredients commonly used in emulsion polymerization processes, such as emulsifiers and surfactants, and these can be nonionic or ionic. Water-soluble polymers include, for example, what are commonly referred to as "protective colloids," such as hydroxyethylcellulose, poly(vinyl acetate/vinyl alcohol), poly(vinylpyrrolidone), poly(acrylamide), and sodium carboxymethylcellulose. It is possible. Surfactant-type polymeric species may also be included, such as those that can be formed "in situ" during the manufacture of block or graft copolymers or water-dilutable dispersions. To reduce and control the molecular weight of polymers,
Chain transfer agents such as thioglycolic acid, primary octyl mercaptan and other mercaptans may also be included. The dispersion may also contain materials that modify its properties or the properties of the coating composition subsequently derived from the dispersion, such as plasticizers or coalescing agents.
Other additives include defoamers and biocides.
and pH regulators. Water-dilutable dispersions of polymer particles can be used in conjunction with polymers. These other polymers may be soluble or insoluble in the water-dilutable continuous phase of the dispersion and may contain monomeric residues as described above;
It does not need to be contained. When polymers are used together in this manner, the proportion of said monomer residues present is not more than 0.1% by weight, based on the total weight of the polymer;
Preferably it should not be less than 1% by weight. The water-dilutable dispersions of this invention are particularly useful because they produce coatings with good adhesion to substrates. This is demonstrated by suitable comparative experiments with coatings prepared from dispersions that do not contain the polymer residues but are otherwise very similar. If the polymers of the dispersions being compared have compositions such that the particles coalesce at room temperature, a small amount of each dispersion may be poured onto the substrate to form a thin fluidized bed and the dilute phase evaporated. A thinner polymer coating can be formed. The water sensitivity and adhesion performance of the coating can then be evaluated by simple laboratory tests after the coating is immersed in water. For example, the speed at which blisters appear and the ease with which the coating is peeled from the substrate by contacting the coating surface with an adhesive tape and peeling from the substrate may be compared. Even when said monomer residues are present at only 1 or 2% by weight, based on the total weight of the polymer, the dispersions of the present invention have a higher , showing significantly improved performance in these tests. Similarly, if the composition of the polymer is such that elevated temperatures are required to promote particle coalescence, a comparison of the water sensitivity of the coatings indicates that the dispersions of the present invention exhibit this property. It turns out that it is excellent. The improved performance is particularly pronounced when the substrate has a coating derived from an alkyd-based coating; in contrast, coatings derived from conventional dispersions typically have "wet adhesive" properties.
(wet adhesion) is extremely poor in adhesion performance. Water-dilutable dispersions of polymer particles containing monomer residues as described above can be prepared using various known "emulsion polymerization" methods.
can be manufactured using any of the following methods. These methods include simple "one-shot" methods in which monomers, including the monomer(s), an emulsifier or surfactant, water and/or a water-dilutable liquid, and The temperature of the mixture of free radical polymerization initiators is increased to cause controlled decomposition of the polymerization initiators. As the polymerization progresses, polymer particles and a monomer phase corresponding to a third phase different from the aqueous phase are generated. Polymer particles are stabilized against aggregation and coagulation by adsorbed emulsifier or surfactant molecules and usually ionic residues that remain after decomposition of the polymerization initiator. The monomer phase is ultimately consumed, yielding a water-dilutable dispersion of polymer particles as the product. When producing high polymer content dispersions, i.e. containing more than 25% by weight of polymer based on the total weight of the dispersion,
A “seed and feed” method will be adopted. In this method, a small portion of the total monomers is polymerized in the presence of an emulsifier or surfactant to produce a dilute dispersion of seed polymer. Polymerization is then carried out for several hours with the remaining monomer added as "feed", during which time the existing particles increase in size and some new particles are formed. During this stage additional polymerization initiators and/or surfactants may be added. The product obtained is a water-dilutable dispersion with a high solids content.
Alternatively, the monomers can be emulsified in water and the emulsion used as the "feed". In other known variations of this method, "protective colloids"
A water-soluble polymer called 100% is dissolved in the aqueous phase before polymerization starts. "Protective colloids" have many complex roles, such as contributing to the stability and rheology of the resulting dispersion of polymer particles. According to one method of the invention, a monomer of formula () is dissolved in a water-miscible solvent. Suitable solvents include water, methanol, ethanol, ascent and ethylene glycol. A monomer solution is fed to the polymerization system of the method. Another method uses a solution of a monomer of formula () in a solvent that is miscible with a mixture of other monomers. Suitable solvents are, for example, isopropanol and higher alcohols, esters such as ethyl acetate and butyl acetate, ketones, toluene and higher aromatic hydrocarbons. In this alternative method,
The monomer solution and all or part of the remaining monomer mixture are mixed before being added to the latter polymerization zone. The inventors have found that it is usually easier to store and handle monomers of formula () as solutions. For aqueous solutions of monomers, it is preferred that the concentration of monomers is between 20 and 50% by weight, based on the total weight of the solution. For monomer solutions in organic solvents, the monomer concentration is preferably 30-70% by weight, based on the total weight of the solution. Direct contact of the monomer solution with the polymerization initiator prior to addition to the polymerization zone should be avoided. Adding the monomer of formula () according to one of the two methods above using only the last 50%, preferably no more than 25% based on the weight of monomer supplied. is the preferred method. It is believed that by using this method, more of the monomer containing the monomer residues is placed on the surface of the polymer particle. However, when the monomer of formula () does not have favorable copolymerization properties with other monomers, an alternative method is to add the monomer of formula () to the diluent phase of the zone prior to initiation of polymerization. is preferred. For example, if the monomer of formula () has an allyl functionality as the only ethylenically unsaturated group and the other monomer is a methacrylate ester, it is preferred to carry out the above alternative method. . If desired, the composition of the total monomers supplied may be varied if monomers of formula () are incorporated, e.g. as the polymeric component of the particles to be more plastic or more hydrophilic. obtain. That is, the amount of plasticizing monomer or hydrophilic monomer, respectively, can be increased during the addition of the monomer of formula () to the polymerization zone. As mentioned above, the water-dilutable dispersions of polymer particles of the present invention can be prepared by methods in which the monomer residues are generated in situ during the polymerization process or during a subsequent step. Alternatively, in the monomer mixture,
At least one reactive monomer capable of reacting simultaneously or subsequently with the secondary amine may be included. Preferably, the reactive monomer contains an epoxy group, although other suitable reactive groups may also be present. During the polymerization process or after polymerization and particle formation, a compound of formula () is added and conditions are adjusted so that the compound reacts with the monomer residues of the reactive monomer to form the group A. A monomer residue of formula () in which at least one of ' and B' has a carbon-carbon bond that is part of a polymer molecular chain is obtained. When water-dilutable dispersions are prepared by this method, conditions should be chosen such that the amount of the compound of formula () remaining unreacted is minimized. This means that the reaction mixture can be heated at a temperature other than room temperature, e.g.
Helped by holding time. The water-based paint of the present invention is a mixture of a water-dilutable dispersion of polymer particles as described above and a water-dilutable dispersion of pigment, often referred to as "milu base."
Millubase is an inorganic pigment such as titanium dioxide;
Other inorganic particulate materials such as calcium carbonate, silica and clay; substituted celluloses, water-soluble polymers such as methacrylic acid or acrylic acid copolymers, and may further contain wetting and dispersing agents. Milubase can be prepared by any of a variety of methods known to those skilled in the art. These methods include a dispersion or milling step in which particles of particulate material are separated in the presence of a dispersant to prepare a fluid, stable dispersion. Many other ingredients may be added to contribute to desired coating properties.
For example, water-soluble polymers and chelating agents may be added to adjust rheology and improve coating properties. Compounds that promote film formation, increase plasticization, freeze resistance, resistance to biological action and deterioration or reduce foaming during application may also be added. The coating composition may be selected to provide a primer, flat, semi-gloss or gloss coating and may be formulated to be suitable for both indoor and outdoor use. By selecting harder compositions for the polymer in the water-dilutable dispersion of polymer particles, coatings can be prepared that yield hard, durable films after drying at elevated temperatures. The paint of the present invention has several important properties:
Due to the presence of said monomeric residues, it has significantly improved performance. This can be readily demonstrated by preparing other water-dilutable dispersions similar to the dispersions of the invention tested, except that they do not contain the monomer residues described above. Separately, the two types of dispersions
Two paints are prepared by mixing with Millubase in the same proportions. The water resistance of the paints can be tested and compared using a variety of commonly used test methods. For example, the "wet adhesion" of a paint film can be measured using a Gardner rub tester according to standard test methods; the film's resistance to blistering, softening back and exposure to heat, high humidity conditions. The time required for recovery can be evaluated; blistering and adhesion to various substrates can be determined by aging the coating for a given period of time and immersing the coated substrate in water. It has been observed that even when low proportions of said monomer residues are present in the water-dilutable dispersion, the coatings exhibit a surprisingly significantly improved performance in these tests. Examples of the present invention are shown below. In the examples, parts and percentages are by weight. Example 1 Formula () where A=hydroxybutyl group, B=methacryloxyhydroxypropyl group
(a) A secondary amine was first prepared by reaction of 1,2-epoxybutane with aminoethylimidazolidinone. The latter starting compound is known and can be prepared by reacting diethylenetriamine with urea. Processing part Temperature control was accomplished by immersing the lower half of the round-bottomed flask in a water bath that could be heated electrically or cooled if necessary by the addition of ice. Mixture X was stirred until homogeneous and then Y was added. Two phases were clearly recognized. The temperature was raised and then maintained at 40°C for 3 hours with stirring. The product was a clear, homogeneous solution.
When a sample of this product is diluted with excess water,
It was found that there was no separation into two layers, and therefore the conversion of epoxybutane was high. Characterization by nuclear magnetic resonance spectroscopy (NMR) showed that the product is a secondary amine of formula () in which group A is a hydroxybutyl group. (b) The secondary amine obtained in (a) was reacted with glycidyl methacrylate. Treatment section Secondary amine solution [prepared in (a)] 1550 Distilled water 300 Glycidyl methacrylate 774 The same equipment as used in (a) was used. The reactants were charged to the flask and stirred. Two layers were clearly visible. The temperature was increased and held at 55-60°C for 3 hours with stirring. The product was a clear, homogeneous solution. A sample of the product did not separate into two layers when diluted with excess water.
Characterization by NMR showed that the product was a tertiary amine of formula () in which group A was a hydroxybutyl group and group B was a methacryloxyhydroxypropyl group and was substantially free of impurities. . Example 2 Formula () where A=cyanoethyl group, B=methacryloxyhydroxypropyl group
Preparation of Monomers (a) A secondary amine was first prepared by reaction of acrylonitrile and aminoethylimidazolidinone. Processing part This was done by immersing the sample in water and adding ice as necessary. Mixture X was stirred until homogeneous.
Y was added for an hour or so, during which time the temperature was not allowed to exceed 25°C. Then increase the temperature,
It was held at 30°C for an additional 4 hours. Finally, the temperature was raised and maintained at 80° C. for 1 hour while blowing inert gas. The effluent gas was passed into dilute sodium hydroxide solution. (b) The product of (a) was reacted with glycidyl methacrylate. Solution obtained in process part (a) 138 Glycidyl methacrylate 55 The same solution as in step (a) was used. The reactants were charged into the flask and the temperature was raised to 50°C with stirring and held at 50°C for 4 hours. The product was a clear, homogeneous solution. The sample did not undergo phase separation when overly diluted with water. NMR characterization showed that the product was a substantially pure tertiary amine of formula () in which group A was a cyanoethyl group and group B was a methacryloxyhydroxypropyl group. Example 3 This example is the same as Example 1 except that isopropanol was used instead of distilled water as the diluent in steps (a) and (b). The product was a clear, homogeneous isopropanol solution. Example 4-6 The same method as Example 1 was repeated except that various reactants were used instead of epoxybutane (Reactant Y) in step (a). Example No. Reactant Part Y 4 Propylene oxide 402 5 Allyl glycidyl ether 790 6 Glycidol 513 In each example the product was a substantially pure, clear, homogeneous solution. Example 7 Preparation of a monomer of formula () in which A is a group derived from the "versatine" acid ester of glycidol and B is a methacryloxyhydroxypropyl group (a) "Versatine" of glycidol ”)
The acid ester (molecular weight approximately 242) was reacted with aminoethylimidazolidinone ("Versatic" is a registered trademark of Siel Corporation). Processing part
Mixture X was made homogeneous by raising the temperature to 40°C and stirring. Add Y and mix
It was held at 40-50°C for 3 hours. The product at this stage was insoluble in water, but when diluted with a dilute aqueous acid solution, it gave a clear homogeneous solution, thus indicating complete consumption of the epoxy compound. "Versatin" acid is a C _5-10 α-tertiary carbon carboxylic acid. (b) Solution obtained in process part (a) 246 Glycidyl methacrylate 88 Using the same equipment as in (a), the reactants were heated at 50°C for 2.5
Holds time. A sample of the product yielded a clear, homogeneous solution when diluted with dilute aqueous hydrochloric acid. Neutralization of this solution yielded an emulsion with some self-stabilization. Example 8 In this example, an amine mixture containing monomers of formula () was constructed by reaction of aminoethylimidazolidinone and glycidyl methacrylate. Processing part X: Aminoethyl imidazolidinone 905 Distilled water 589 Y: Glycidyl methacrylate 1145 The same equipment as in Example 1 was used. Mixture X was stirred until homogeneous. Y was added and the temperature was held at 30°C for 3 hours. The temperature was increased and held at 50-60°C for an additional 3 hours. The product was a clear, homogeneous solution. Samples diluted with excess water did not result in phase separation, indicating that the epoxy compound was completely reacted. Characterization by NMR showed that the product was a mixture of amines, some containing methacrylate groups, some methacrylamide groups, and some containing no ethylenically unsaturated groups. The latter would remain as an unpolymerized water-soluble impurity if the product of this example was copolymerized with other monomers in an aqueous medium to produce a dispersion of polymer particles. Example 9 Allyl glycidyl ether (790 parts) was added to step (a)
except that allyl glycidyl ether (621 parts) was used in place of glycidyl methacrylate in step (b).
The same method as in Example 1 was carried out. Example 10 The same procedure as Example 1 was carried out except that in step (b) allyl glycidyl ether (621 parts) was used in place of glycidyl methacrylate. Example 11 In this example, the monomer obtained in Example 3 was used to produce a polymer. Processing part P: Methyl ethyl ketone 300 Azo diisobutyronitrile 0.5 Q: Product of Example 3 10 Methyl methacrylate 180 Butyl acrylate 20 R: Azo diisobutyronitrile 0.5 Ethyl acetate 5 A stirrer, condenser and thermometer were attached. A round bottom flask was used. The flask was heated with an electric mantle. Mixture P was heated to reflux. After 20 minutes, the addition of Mixture Q and half of Mixture R was started and completed in about 2 hours. The remainder of Mixture R was added and refluxed for an additional 30 minutes. A viscous polymer solution was obtained as the product, from which the polymer could be separated, if desired, by adding excess methanol and washing the polymer precipitate and drying. Example 12 This example demonstrates the preparation of an aqueous dispersion of particles consisting of a copolymer of methyl methacrylate, 2-ethylhexyl acrylate, and a monomer of formula () above. The following raw materials were used: Raw material part A: Water 614 Polyethylene glycol monooleate, molecular weight 400 2.3 “Ceosize” 1.4 WPO9L* B: Methyl methacrylate 342 2-ethylhexyl acrylate 261 Polyethylene glycol monooleate molecular weight 400 34.4 Disonyl sodium sulfosuccinate 4 C: Monomer of formula ()※※ 6.4 Water 15.1 D: Water 62 Ammonium persulfate 2 Boax 1.5 *“Ceosize” is a registered trademark for commercially available hydroxyethyl cellulose. * *The monomer of formula () is, according to Example 1,
It was prepared by reacting an aqueous solution of aminoethyl imidazolidinone with an equimolar amount of butylene oxide, followed by an equimolar amount of glycidyl methacrylate. In this monomer, A _{= CH3CH2CH} (OH) _CH2- or

[expression] or or

[Formula] R ₁ =R ₂ =-CH ₂ -CH ₂ - Aqueous raw solution A was prepared at 85°C in a glass reactor equipped with a capped flange top, stirrer, condenser and thermometer. The monomer mixture was fed to the reactor at a controlled rate using a small pump, and the initiator solution was added at regular intervals using a biuret. 32 parts B and 13 parts D were added and after a further 45 minutes, 514 parts B was added at a constant rate over 2 hours. 30 for the same time as above
Part D was added at a rate of 3 parts per 10 minutes. During this step, the temperature was increased and maintained at 90°C. The remainder of B, all of C and an additional 9 parts of D were added over an additional 30 minutes. After these additions are complete
After 10 minutes, the remainder of D was added. After an additional 10 minutes, the latex was cooled. A stable and high solids content aqueous dispersion of polymer particles containing 1% of monomer residues of formula () was obtained as product. Example 13 In this example, the monomer of the formula () was used as an isopropanol solution, that is, the raw material C was composed of 128 parts of the monomer of the formula () described in Example 12 and 8.7 parts of isopropanol. It is the same as Example 1 except that it was used. The same procedure as Example 12 was repeated, except that Feedstock C was mixed with the remainder of Feedstock B before adding once 30 minutes. A stable and high solids content aqueous dispersion of polymer particles containing 2% of monomer residues of formula () was obtained as product. Example 14 This example compares the polymer dispersions of Examples 12 and 13 with a polymer dispersion containing no residues of the monomer of formula ("dispersion of Example 14"). This is a comparative example showing the following. Except that the monomer of formula () was not used.
A stable, high solids content aqueous dispersion of polymer particles was prepared by a method similar to Example 12.
This dispersion is easily distinguished from the dispersions of Examples 12 and 13 by the following simple test: Spray a hardboard panel with a conventional alkyd primer and allow to dry for one week: Then spray with a conventional alkyd. and dry for a week: then 70
Cure was placed in a heating oven for 7 hours to complete curing.
A coating of the dispersions of Examples 12-14 is applied to the alkyd surface using an 8 mil deep applicator bar and dried in a 30°C oven for 30 minutes. The coating is aged at 25°C for an hour. Using a sharp knife, make a cross-shaped scratch on each coating about 1 inch long. This panel is immersed in water at 25°C for 1 hour. Note any changes in the appearance of the coating. Immediately after immersion in water, excess water is removed and adhesive tape is applied over the cross-shaped scratches on the coating and the tape is peeled off laterally. Record the difficulty of removing the coating.

[Table] Examples 15-19 Dispersions were prepared in the same manner as in Example 12, except that in these Examples, raw material C containing monomers of various formulas () was used. Various monomers were prepared by reaction of various compounds as shown below with aminoethylimidazolidinone (AEUr): Example 15: (AEUr/allyl glycidyl ether)/glycidyl methacrylate Example 16: (AEUr/ (glycidol)/glycidyl methacrylate Example 17: (AEUr/glycidyl methacrylate)/glycidyl methacrylate Example 18: (AEUr/glycidyl “versatate”)/glycidyl methacrylate Example 19: (AEUr/acrylonitrile)/glycidyl methacrylate As a product, the formula A stable high solids content dispersion of polymer particles containing 1% of monomer residues was obtained. Example 20 In this example, an aqueous dispersion of polymer particles was prepared by the following method. : parts Raw material A: Water 192 Sodium carboxymethylcellulose 2 Raw material B: Methyl methacrylate 17 Butyl acrylate 17 Poly(ethylene oxide)/nonylphenol (average 25 units per molecule) 1 Di-octyl sodium sulfosuccinate
0.5 Raw material C: Monomer of formula () used in Example 12
1.9 Water 0.5 Raw material D: Water 4.7 Potassium persulfate 2.3 Raw material A was charged to a round bottom flask (500 ml) equipped with a magnetic stirrer and a condenser. Immerse the flask in a hot water bath, increase the temperature, and while stirring
The temperature was maintained at 85°C to obtain a homogeneous mixture without lumps. Other raw materials were added as shown below:

Table: After a further 15 minutes, the latex obtained was cooled. Approximately 5% of monomer residues of formula () are used as a product.
An aqueous dispersion of polymer particles was obtained. Example 21 This example demonstrates the preparation of a dispersion of particles consisting of a copolymer of styrene, 2-ethylhexyl acrylate, and a monomer of formula (). Raw material part A: Water 611 Polyethylene glycol monooleate molecular weight 400 2.3 “Cerocise” WPO9L 1.4 B: Styrene 318 2-ethylhexyl acrylate 286 Polyethylene glycol monooleate molecular weight
400 34.4 Di-nonyl sodium sulfosuccinate 4.0 C: Monomer of the formula () as described below 13.1 Isopropanol 11.3 D: Water 62 Ammonium persulfate 2 Borax 1.5 The monomer of the formula () is an aminoethylimidazolidinone. Same as that used in Example 12, except that it was prepared by reacting a solution of isopropanol (used in place of water in Example 12) with an equimolar amount of butylene oxide followed by an equimolar amount of glycidyl methacrylate. It is similar. A method similar to Example 12 was used except that Feed C was mixed with Feed B before being added to the polymerization zone. Approximately 2% of the monomer residue of formula () is used as a product.
A stable, high solids content dispersion of particles of polymer was obtained. Example 22 This example illustrates the preparation of a copolymer dispersion of vinyl acetate, vinyl "versatate" and a monomer of formula () as described below in a manner similar to Example 12. Raw material part A: Water 533 Poly(ethylene glycol)/nonylphenol used in Example 20 15.1 Hydroxyethyl cellulose 10.8 Di-octyl sodium sulfosuccinate
3.2 Sodium carbonate 2.2 B: Vinyl acetate 551 ※“VeOVa10” 138 C: Water 60 Ammonium persulfate 2.2 D: ※※ Monomer of formula () as described below
14.5 Water 11.2 *“VeOVa” is a registered trademark for commercially available vinyl ester. It was then prepared by reacting with equimolar amounts of glycidyl methacrylate; thus, in formula (),

[Formula] or CH ₂ (OH) CH (OH) CH ₂ − or R ₁ =R ₂ =-CH ₂ -CH ₂ -. Raw material A aqueous solution was prepared by raising the temperature of raw material A to 60°C. 72 parts B and 15.5 parts C were added and the temperature was raised to 85°C. After 40 minutes, the remainder of B and 34 parts of C were added to the reactor for 4.5 hours; D was added during the last 1.5 hours of this step. After another 10 minutes, the remainder of C was added. After 10 minutes, the dispersion was cooled. The product was a stable high solids content dispersion of particles of vinyl acetate copolymer containing about 2% monomer residues of formula (). Example 23 This example describes the preparation of a dispersion of methyl metal acrylate/butyl acrylate/methoxy ether of poly(ethylene glycol) monomethacrylate/monomer of formula () as described in Example 13 in water/methanol. shows. a stirrer, a thermometer, and a flanged lid;
Nitrogen supply line and up-and-over
A round bottom flask with a condenser was used.
The condenser collects the distillate from the reactor and
It was set up so that it could be used to dilute the monomer mixture before returning it to the reactor and dropping it. Ingredients part A: Water 315 Methanol 466 Methoxy ether of poly(ethylene glycol) monomethacrylate 18.7 B: Methyl methacrylate 26 Butyl acrylate 24 Azodiisobutyronitrile 1 C: Methyl methacrylate 214 Butyl acrylate 198 Poly(ethylene glycol) Methoxy ether of monomethacrylate 16 Methanol 48 Azodiisobutyronitrile 6.7 D: Methyl methacrylate 46.6 Butyl acrylate 421 Monomer of formula () mentioned in Example 13 11.2 Isopropanol 7.1 Asodiisobutyronitrile 1.3 E: Asodiisobutyronitrile 1.6 Feedstock A was charged to the reactor and the temperature was raised to 65°C. After adding raw material B, the temperature was raised to reflux and held for 30 minutes, after which raw material C was added. After addition for 30 minutes, D was added for 1 hour. Reflux was continued and after 0.5 hours 0.8 parts of E was added. After another 0.5 hour, the remainder of E was added.
After 0.5 hours, the dispersion was cooled. The product was a stable dispersion of polymer particles in a water/methanol medium containing about 2% of monomer residues of formula (). Example 24 This example demonstrates the preparation of a first dispersion of polymer particles consisting of a copolymer of methyl methacrylate/2-ethylhexyl acrylate/glycidyl methacrylate. The copolymer of the initial dispersion was subsequently reacted with a secondary amine to introduce monomer residues of formula (). The same equipment as in Example 12 was used. Ingredients part A: Water 550 Poly(ethylene glycol) monooleate molecular weight 400 2.3 “Cellocise” WPO9L 1.3 B: Methyl methacrylate 315 2-ethylhexyl acrylate 283 Poly(ethylene glycol) monooleate molecular weight 400 34.4 Di-nonyl sodium sulfosuccinate 4.0 Glycidyl methacrylate 18.5 D: Water 62 Ammonium persulfate 2 Borax 1.5 E: Secondary amine obtained by reaction of an aqueous solution of aminoethylimidazolidinone with an equimolar amount of butylene oxide 13 Water 31 Raw materials A, B and D was used to prepare an aqueous dispersion of polymer particles according to the method of Example 12.
The temperature of this dispersion was adjusted to 60°C. After addition of E, this temperature was maintained for 3 hours with stirring. A stable, high solids content dispersion of polymer particles containing monomer residues of formula () as product was obtained. Example 25 This example demonstrates the preparation of an aqueous dispersion of polymer particles consisting of a copolymer of methyl methacrylate/2-ethylhexyl acrylate/monomer of formula () described below. Except that the composition of the monomers was different, resulting in a polymer with a lower Tg during the addition of the monomer of formula ().
A method similar to Examples 12 and 13 was carried out. Ingredients Part A: Water 614 Poly(ethylene glycol) monooleate, molecular weight 400 2.3 “Cellosize” 1.4 B: Methyl methacrylate 287 2-ethylhexyl acrylate 196 Poly(ethylene glycol) monooleate, molecular weight 400 27.5 Di-nonyl sodium sulfosuccinate nate 3.2 C: Methyl methacrylate 49 2-ethylhexyl acrylate 72 Monooleate of poly(ethylene glycol) Molecular weight 400 6.9 Di-nonyl sodium sulfosuccinate 0.8 Monomer of formula ()* 12 Isopropanol 8 D: Water 62 Ammonium persulfate 2 Borax 1.5 (*This monomer was prepared by reacting aminoethyl imidazolidinone with an equimolar amount of allyl glycidyl ether in isopropanol, and then reacting with an equimolar amount of glycidyl methacrylate) Prepare an aqueous solution of raw material A at 81°C did. 32 parts B and 13 parts D were added. All of B and 36 copies of D are 2
It was added at a constant rate over time. During this step, the temperature was increased and maintained at 90°C. All of C and 9 parts of D were added at a constant rate over a period of 30 minutes. The remainder of D was added 10 minutes after the addition of these ingredients was complete. After an additional 10 minutes, the latex was cooled. The product was a stable, high solids content dispersion of polymer particles consisting of a copolymer containing about 2% of monomer residues of formula (). Example 26 This example shows the preparation of two water-based paints using the dispersions of polymer particles prepared in Examples 13 and 14, respectively, as binders. Ingredients part A: Water 10.23 Hydroxyethylcellulose 0.24 Aminomethylpropanol 0.08 “Tamol” 731* 0.24 “Gasco”* 3.21 “Viscalex” VG2* 1.61 Ammonia 0.16 B : Propylene glycol 7.00 “Tamol” 731 0.24 Aminomethylpropanol 0.08 Titanium dioxide 21.66 C: Propylene glycol 2.23 D: “Texano”※※2.01 *Commercially available paint additives, “Teamo”, “G”
"asco" and "Viscaex" are registered trademarks. ※※Commercially available coalescing agent "Texano" is a registered trademark. The thickener (A) solution was prepared by simple stirring. The mill base (B) was prepared using a high-speed dispersion machine. The pigment was dispersed into fine particles with stable dispersion, and then (C) was added to this.The following components were used in the following order for the paint, and the following components were added at each stage. Prepared by thorough mixing before addition: Dispersion of polymer particles (prepared in Example 13 or 14) 49.0 Water 2.02 Milbase (B/C) 31.21 Thickener solution (A) 15.76 Coalescing Agent (D) 2.01 Paints 1 and 2 were prepared in Example 13 and
It was prepared using the dispersion of polymer particles prepared in 14. The polymer used to prepare Coating 1 contained a monomer residue of formula (), and in one method this residue was not present in Coating 2. This is the only difference between the two types of paint. The substantial difference in water sensitivity and wet adhesion of the two coatings can be determined by the simple test described below: A hardboard panel was coated with an alkyd basecoat and an alkyd gloss coating as in Example 14. Samples of two paints 1 and 2 were coated onto the alkyd paint surface using a coating plate to give 8 mil (thou)
A wet film was formed. The paint was dried for 4 hours at 25°C and 25% relative humidity. The panel was immersed in water for 1 hour at 25°C and then measured. Paint 2 blistered and recovery to original paint hardness was slow (20 minutes). Paint 1 did not blister and the recovery rate was faster. (10 minutes). In another test, the paint was applied onto an alkyd coated substrate. After curing for 7 days, the coating was scored with four scratches approximately 1 inch long with a sharp knife to form a cross line with eight tips. The panels were placed in a "Gardner" cleanability tester and subjected to the back and forth action of a nylon bristle brush. The panels were wetted with a standard cleaning solution during the test. The test was stopped when the gloss of the coating disappeared from the cross line zone. In paint 2, the gloss disappeared after 220 reciprocations, and after 420 reciprocations, the gloss completely disappeared, whereas in paint 1, the gloss did not disappear even after 600 reciprocations. Example 27 This example demonstrates the significant difference in the adhesion performance of an aqueous dispersion that does not contain the monomer residue of formula () and an aqueous dispersion that contains this residue. The board was coated with a conventional alkyd solution base coat and allowed to dry for one week. One half of the board was then coated with the dispersion of Example 14 using a paint brush, and the other half was coated with the dispersion of Example 13. After drying, a second coat of each dispersion was applied to each half of the board in a similar manner. After drying for one day, the entire surface of the board was coated with a conventional solution-based gloss paint. After another day, the adhesive tape was pressed onto the surface of the painted board. When using the dispersion of Example 14, 3
The entire layer coating system could be easily peeled off from the base coat, indicating poor adhesion to the substrate. When using the dispersion of Example 13, no lifting or peeling of the coating was possible, indicating that the presence of the monomer residue of formula () significantly improves the adhesion performance. . The structures and proton NMR spectra of the polymerizable monomers of the present invention prepared in Examples 1, 2, 5, and 10 are shown in FIGS. 1 to 4, respectively. The NMR measurement of the monomer of Example 1 shown in FIG.
This was done by dissolving the sample in deuterated chloroform (CDC ₂ ) and tetramethylsilane (TMS) and applying a 200 MHz electric field. TMS produces a reference peak for the peak produced by the monomer. The peaks a to f shown on the spectrum in FIG. 1 are:
They correspond to the various brotones indicated by arrows on the structural formula shown in FIG. For example, peak f corresponds to two protons of _-CH2- adjacent to the methacrylate moiety. The absence of fine structure around peak f indicates that aminoethylimidazolidone (AEI) and glycidyl methacrylate (GMA) have reacted. The absence of a peak corresponding to epoxybutane (EB) indicates that EB
Indicates that it has reacted with AEI. The NMR spectrum shown in FIG. 2 was measured under the same conditions as the NMR spectrum shown in FIG. 1, except that isopropanol was added to CDC ₃ instead of TMS. The absence of multiple structures in the 4.2-5.3 ppm shift region is associated with acrylonitrile (ACN) and glycidyl methacrylate (GMA).
indicates that it reacted with AEI. The NMR spectrum shown in Figure 3 uses deuterium oxide (D ₂ 0) as the solvent and deuterated water
water) (HDO) as standard and 60M
This was measured in the same manner as the NMR spectrum shown in Figure 1, except that Hz was applied. Peaks a to i shown in FIG. 3 similarly correspond to protons in the structural formula. The strong peak for -CHOH is due to allyl glycidyl ether (AGE) and
It shows the reaction between GMA and AEI. The NMR spectrum shown in FIG. 4 was measured under the same conditions as in FIG. The characteristic peaks a to c shown in FIG. 4 indicate the corresponding protons in the structural formula.

[Brief explanation of drawings]

Figures 1 to 4 show Examples 1 and 2, respectively.
Protons of polymerizable monomers prepared in 5 and 10
The NMR spectrum is shown.

Claims (1)

[Claims] 1 Formula: [In the formula, A represents a group: [Formula], B represents a group: [Formula], R ₃ is Y-(CH ₂ ) _o - (n is 0 to 16),
[Formula] or [Formula], R ₄ is a C ₁ to _{C 9} alkyl group, and V is -OH
or -CN, T is [Formula] or _CH2 =CH- _CH2 , W is -H or _-CH3 , and Y is -H or -OH]. body. 2 formulas (In the formula, A has the meaning given below) is reacted with a substance containing an epoxide group and having a structure to provide the group B given below when reacted with an amino group. The formula: [In the formula, A represents a group: [Formula], B represents a group: [Formula], R ₃ is Y-(CH ₂ ) _o - (n is 0 to 16),
[Formula] or [Formula], R ₄ is a C ₁ - C ₉ alkyl group, V is -OH or -CN, T is [Formula] or CH ₂ =CH-CH ₂ -, W is -H or _-CH3 , Y is -H or -OH]. 3 The substance containing an epoxide group and having a structure for providing group B is glycidyl (meth)
3. The method of claim 2, wherein the method is selected from acrylates or allyl glycidyl ethers.