Functionalization of polymer through enamine of acetoacetate

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

(Field of Invention) The present invention relates to a method for producing a polymer having a reactive functional group. In particular, the present invention relates to a method for producing a polymer containing an acetoacetate functional group, and a polymerization method for reacting an acetoacetate group with a functional amine to produce enamine.

【0002】

The polymers of the present invention have many uses, including coatings, sealants, adhesives and impregnants, and are very useful as solutions or dispersions of water or water-cosolvent mixtures. ..

【0003】

The coatings produced from the polymers of the present invention improve tensile properties such as solvent resistance, dust absorption resistance, printing resistance and block resistance, surface abrasion resistance, adhesion and impact resistance and tensile strength. ..

【0004】

(Background of the Invention) It is generally known that introducing one or other desired functional groups into a polymer molecule is useful for improving the properties of the polymer. The desired functional group is such that the compound already having such a functional group is used as a monomer during the production of the polymer, or the polymer having precursor groups is post-reacted with a suitable reagent. It can be introduced by converting to the desired functional group.

【0005】

We have found new, unexpected and useful methods for post-reacting polymers with precursor groups to introduce the desired functional groups into the polymers.

【0006】

An advantage of the present invention is to provide a method for producing a functionalized polymer by a post-polymerization reaction.

【0007】

Another advantage of the present invention is to provide a novel monomer having a functional group.

【0008】

Yet another advantage of the present invention is to provide a polymer having functional groups that are incompatible with the polymerization method.

【0009】

(Related Techniques) It is generally known that the properties of a polymer are improved by introducing a desired functional group. Nothing is disclosed about the post-polymerization method that reacts with a sex amine to produce enamine.

【0010】

The European patent application EP0442653A2 is a method for producing a polymer having a desired group represented by Y, that is, NH bound to carbon or nitrogen.₂ And / or -NH₂ -Disclosures a method of reacting a polymer with a precursor group (which is reactive with an enol carboxyl group) with a single enol carboxyl group and at least one compound having at least one Y []. Here, the enol-based carboxyl group means a carboxyl group having an enol property by binding to an alphamethylene or methane group that is bonded to an electron-withdrawing group].

【0011】

European patent application EP0483583A2 states that polyacetacetate or polyacetacetamide can be reacted with an amino group-containing alkoxy-silane to obtain a polyenamine that has a long processing time and is crosslinked without the action of atmospheric humidity. It is disclosed. It states that this is an advantage for coatings thicker than 50μ.

【0012】

(Overview of the Invention) One aspect of the present invention is to react an acetoacetate functionalized polymer with a compound having an amine group and at least one additional functional group, and further functional groups bonded via the enamine of the acetoacetate group. It produces a polymer having.

【0013】

Another aspect of the present invention is to react an acetoacetate functionalized monomer with a compound having an amine group and at least one additional functional group to produce a new functionalized monomer. This monomer can subsequently be polymerized to produce a functionalized polymer.

【0014】

(Detailed Description) One aspect of the present invention is a further functional group in which an acetoacetate functionalized polymer is reacted with a compound having an amine group and at least one additional functional group and bonded via the enamine of the acetoacetate group. It produces a polymer having.

【0015】

Another aspect of the present invention is to react an acetoacetate functionalized monomer with a compound having an amine group and at least one additional functional group to produce a new functionalized monomer. This monomer can subsequently be polymerized to produce a functionalized polymer.

【0016】

In yet another aspect of the invention, a polymer obtained by polymerizing an acetoacetate functionalized monomer, an amine functional group and at least one incompatible functional group (groups that do not maintain functionalizing activity under the conditions of the polymerization step). Is reacted with a compound having. The novel polymer is produced as having an incompatible functional group attached to the polymer via the acetoacetate group enamine.

【0017】

Yet another aspect of the invention provides a polymer functionalization package and a functionalization method. The main chain of the acetoacetate functionalized polymer can be produced, and the ratio of the compound having an amine group and at least one additional functional group is substantially 1 from an excess of about 1 mol of amine based on acetoacetate. It can be varied over a range of less than a molar and can be tailored to the properties individually required for the end application. This is one of the means to maintain an inventory of relatively low types of polymerization products and by custom-functionalizing the polymer with an appropriate amount of amine functionalized reactants, the final in various forms. Applications Polymers can be obtained.

【0018】

Yet another aspect of the invention provides a method of allowing the introduction of desired functional groups in the desired area, eg, concentrated on the surface of the polymer particles.

【0019】

Polymers with functional groups attached via enamine, which is an acetoacetate group, are useful in coatings, adhesives, polymer blends, plastic additives, dispersants, flocculants and separation techniques.

【0020】

(Polymer) The preferred polymer used in the present invention is a vinyl polymer having a pendant acetoacetate group, also known as beta-ketoester. As used herein, "pendant" means attached to a polymer backbone and available for further reaction. The pendant should not be construed in the strict sense of excluding the attachment of such groups at the ends of the polymer chains. Therefore, polymers with acetoacetate functionality introduced at the end of the chain by acetoacetate-functionalized mercapton, as shown in US Pat. No. 4,960,924, are also useful in the present invention. In general, the pendant acetoacetate group is an organic divalent radical R attached to the acetoacetate moiety.¹ Trivalent organic radical R with two acetoacetate groups² It binds to the polymer main chain via.

【0021】

[Chemical 1]

<img file="JPH07138317A_D0001.tif" />【0022】

The acetoacetate functionalized polymer can be produced by means known in the art. A preferred method is to polymerize with an acetoacetate functionalized monomer. The preferred monomer is acetoacetoxyethyl methacrylate, which is hereinafter referred to herein as "AAEM" for convenience.

【0023】

[Chemical 2]

<img file="JPH07138317A_D0002.tif" />【0024】

Examples of other monomers useful for introducing acetoacetate functionality include acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, allyl acetoacetate, acetoacetoxybutyl methacrylate, 2,3-di (acetoacetoxy) propyl methacrylate and the like. Be done. In general, any polymerizable hydroxyfunctionalized monomer is diketene or other suitable acetoacetylating agent (eg, "Comparison of Methods for the Preparation of Acetoacetylated Coating Resins", Witzeman, JS; Dell Nottingham, It can be converted to the corresponding acetoacetate by reaction with W .; Del Rector, FJ Coating Technology; Vol. 62, 1990, 101. (and references contained therein).

【0025】

The vinyl polymers of the present invention are mostly copolymers of acetoacetate functionalized monomers and other monomers. Useful examples of comonomer include, for example, simple olefins such as ethylene, alkyl acrylates and methacrylates in which the alkyl group has 1 to 20 carbon atoms (more preferably 1 to 8 carbon atoms), and vinyl acetate. Acrylic acid, methacrylic acid, acrylonitrile, styrene, isobornyl methacrylate, acrylamide, hydroxyethyl acrylate and methacrylate, hydroxypropyl methacrylate and acrylate, N-vinylpyrrolidinone, ptadiene, isoprene, vinyl halides such as vinyl chloride and vinylidene chloride, alkyl Maleate, alkyl fumarate, fumaric acid, maleic acid, itaconic acid and the like can be mentioned. It may also contain low levels of divinyl or polyvinyl monomers, such as glycol polyacrylates, allyl methacrylates, divinylbenzene, etc., in order to introduce a controlled amount of gel into the latex particles, which is sometimes desirable. However, what is important is that doing so does not significantly impair the quality of film formation. It may also contain a chain transfer agent to adjust the molecular weight of the polymer.

【0026】

The acetoacetate functionalized polymer may contain from about 0.5% to 100% by weight acetoacetate functionalized monomers. In either application, the amount of acetoacetate functionalized monomer required will vary on a case-by-case basis depending on the desired degree of post-functionalization required for the individual end application. However, in general, the concentration of acetoacetate monomer will be between 1-40%. A typical coating will typically contain about 0.5-20% by weight of acetoacetate monomer. A polymer having a molecular weight of 1,000 to 1,000,000 or more can be used. Low molecular weight polymers should contain sufficiently high levels of acetoacetate to maximize the degree of postfunctionalization. For example, copolymers of AAEM with a molecular weight of less than 10,000 typically contain more than 30% AAEM.

【0027】

Generally, vinyl polymers are prepared as dispersions or emulsion polymers in water by suitable free radical polymerization means using free radical initiators and suitable heating means. When a film-forming polymer is desired, an emulsion polymer having a glass transition temperature of 60 ° C. or lower is generally useful. This is because these polymers, together with the coalescent, form a high quality film at ambient temperature. If dissolved polymers are used in the film-forming process, they are film-forming, so polymers with higher glass transition temperatures can be readily used.

【0028】

In one aspect of the invention, polymerization in an aqueous medium, especially aqueous emulsion polymerization, is used for the preparation of the polymer. Known dispersants (eg, anionic and / or nonionic emulsifiers such as alkylsulfate alkali salts or ammonium salts, alkylsulphonic acids, fatty acids, oxyethylated alkylphenols, etc.) can also be used. The amount of dispersant used is usually 0.1-6% by weight based on the total weight of the monomers. Heat or redox starting means can also be used. Known free radical initiators (organic hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-amyl hydroperoxide, ammonium and / or alkali peroxide, t-butylperpivalate, t- Butylperbenzoate, benzoyl peroxide, di (n-propyl) peroxydicarbonate, organic peroxides such as acetylcyclo-hexylsulfonyl peroxide, etc.) are typically used in an amount of 0.05-3.0% by weight based on the total weight of the monomers. be able to. In redox systems where the initiator is used with a suitable initiator (eg, reduced sugar, isoascorbic acid, sodium bisulfite, sodium thiosulfate, hydroxylamine, hydrazine, sodium hydrosulfite), sometimes, for example, iron sulphate, It can be used at similar levels with metal catalysts such as salts of transition metals such as copper sulphate, vanadium sulphate. Also, non-oxidizing heat initiators such as 2,2'-azo-bis-isobutyronitrile, 4,4'-azo-bis (4-cyanopentanoic acid), 2,2'-azo-bis. (2-Amidinopropane) Dihydrochloride or the like can be used. Often, chain transfer agents such as low levels of mercaptans (eg, 0.05-6% by weight n-octyl mercaptan, n-dodecyl mercaptan, butyl or methyl mercaptopropionate, mercaptopropic acid based on total monomer weight). To adjust the molecular weight using.

【0029】

The present invention can also be carried out using a solvent-soluble or water-soluble polymer. When doing this, if the monomer mixture is water soluble, the polymer can be prepared directly in water, or in most cases this is the polymerization solvent such as isopropanol, butyl cellosolve, propylene glycol, etc. Use a water-miscible solvent such as. In this case, water may be contained in the polymerization mixture or may be added after the completion of the polymerization. In these cases, the polymer is prepared in a known organic solvent such as xylene, butyl acetate, methyl ethyl ketone, methyl tertiary butyl ether and the like. When used with or without water, the organic solvent may use an organic soluble free radical initiator, such as azo-bis-isobutyronitrile, t-butyl peroctate or benzoyl peroxide, which It is useful for ensuring smooth copolymerization even under such heating conditions. Another method of making the water-soluble polymer of the present invention is vinyl with acrylic or methacrylic acid or other polymerizable acid monomer (usually 10% or more) so that the emulsion polymer can be stabilized by the addition of ammonia or other bases. Examples include a method of preparing a dispersion polymer. It is advantageous to use this type of water-soluble polymer in a blend with a known dispersion polymer, and those having a pendant acetoacetate functional group are preferable. Blends of alkali-soluble resins and latex polymers have a particularly favorable combination of properties for luster and rheology and are useful in coating and print ink applications.

【0030】

In another aspect of the invention, the aqueous dispersion comprises copolymer particles composed of at least two mutually incompatible copolymers. These mutually incompatible copolymers have the following morphological shapes, such as core / shell, core / shell particles in which the shell phase incompletely encapsulates the core, core / shell with a polyphase core. It can be present as particles, interpenetrating network particles, and so on. In all of these, most of the surface area of the particle will be occupied by at least one outer phase, and the interior of the particle will be occupied by at least one inner phase. The mutual incompatibility of the two polymer compositions can be investigated by various means known in the art. Such means include the use of a scanning electron microscope using staining means to highlight the differences between the appearances of the phases.

【0031】

Emulsion polymerization means used to prepare such dispersions are well known in the art. Some cross-linking or gel structure by sequential polymerization via low-level cross-linked monomers such as allyl methacrylate, diallyl phthalate, diallyl maleate, butylene glycol dimethacrylate, divinylbenzene, triallyl isocyanurate, ethylene glycol diacrylate, etc. May be advantageous to generate in the core. The slightly cross-linked core does not adversely affect film formation and in some cases provides a better coating, especially if the pendant acetoacetate is concentrated in the shell.

【0032】

As mentioned above, this technique is primarily used for functionalized vinyl polymers dissolved or dispersed in aqueous solvents. Unfortunately, vinyl polymers containing pendant acetoacetates tend to be hydrolyzed in water, especially by heat aging. This hydrolysis occurs at most pHs, producing acetoacetic acid, which in turn decomposes into acetone and carbon dioxide.

【0033】

[Chemical 3]

<img file="JPH07138317A_D0003.tif" />【0034】

In the prior application, U.S. Patent Application No. 632,302, a solution to this problem is to treat the aqueous acetoacetate polymer after preparation with 1 molar equivalent of ammonia or a primary amine such as ethanolamine, methylamine or isopropylamine. Disclosed the law. As described in this application, the polymer is typically neutralized to a basic pH, preferably pH 9 or higher, with one of the amines described above. Under these conditions, enamine is produced. The reaction to produce enamine generally increases in rate as the temperature rises. Generally, the production of enamine is completed within 8 hours. Another option is to raise the pH to about 9, equilibrate the system, readjust the pH to about 9, and replace the amine consumed by the production of enamine. Enamines are typically above pH 7 and are stable to hydrolysis.

【0035】

The present inventors have newly found that a method for introducing a further functional group or a functionalized side chain into an acetic acid acetate polymer can be obtained by an enamine reaction means. R shown in the following equation² Means a functional group or a linking group having a functional group.

【0036】

[Chemical 4]

<img file="JPH07138317A_D0004.tif" />【0037】

Steric hindrance primary amines such as t-butylamine and aromatic amines such as aniline are generally less suitable as they impair the production of enamines. Since the production of enamine is a reversible reaction, the amine compound should be non-volatile if the composition is exposed to the atmosphere prior to the use of functional groups. However, as long as the volatile amine is stored under conditions where it cannot evaporate (eg, in a closed container), the wet composition has considerable storage stability.

【0038】

Other methods of making vinyl polymers containing equivalent pendant enamine functional groups include the use of pre-produced enamine monomers derived from suitable amine and acetoacetate monomers. In this case, it is necessary to maintain the pH on the alkaline side during the polymerization in order to prevent the enamine from returning to acetacetate by hydrolysis.

【0039】

(Functional group) Equation: -R² NH₂ In R² Can be a functional group or a linking group having a functional group. An example of a linking group is C₂ ~ C₁₈Divalent groups such as alkyl, alkoxyl and polyalkoxyl groups such as polyoxyethylene chains and polyoxypropylene chains having a molecular weight of about 72 to about 400,000 can be mentioned.

【0040】

Examples of types of property-imparting functionl groups that can be introduced by the methods of the present invention include cross-linking groups, adhesion promoters, ultraviolet blocking groups, surface active compounds, latex stability. Examples include a latex stabilizing group and a separating binding group. Functional groups of these types are well known in the art and are, for example, mercaptoethylamine, taurine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, polyoxypropyleneamine, polyoxyethyleneamine. , 2-Aminoethylethyleneurea, 2-dimethylaminoethylamine, amino acids, allylamines, and 4-amino-2,2,6,6-tetramethylpiperidinyloxy-free radicals.

【0041】

In one aspect, compounds having an amine functional group and additional functional groups include those containing either a first amine functional group and a second or third amine functional group for enamine production. In the case of the tertiary amine, a cationic latex is obtained. That is, treatment of the tertiary amine functionalized polymer with a proton source or alkylating agent can produce ammonium cations.

【0042】

The sterically stabilized latex can be produced, for example, by reacting an acetoacetate polymer with a polyethoxylated amine. The technique also provides a means of adjusting the polarity of the polymer by choosing from hydrophilic or hydrophobic amines. Similarly, the index of refraction of the polymer can be adjusted with the appropriate functional group on the amine to increase or decrease the index of refraction. The compatibility of the various combinations of polymers can also be improved for blending by introducing the desired functional groups into either or both polymers.

【0043】

Monomers with specific functional groups are generally made into polymers because of the potential for chemical changes in functional value under polymerization conditions or because of the properties of the functional groups that produce undesired effects in the polymerization process. Not suitable for introduction. For example, a mercaptan functional group causes a chain transfer action during free radical polymerization, causing the product profile to be a lower molecular weight product than if a functional group without the chain transfer action were to be used. Olefin functional groups tend to be consumed during the free radical polymerization process, but can be post-added according to the present invention. The second amine may cause inhibition and chain transfer during free radical polymerization.

【0044】

(Additives) The polymers and additives of the present invention can be formulated according to the final application selected. Additives include, for example, thickeners, dispersants, pigments, extenders, fillers, antifreezes, plasticizers, adhesion promoters, film-forming aids, wetting agents, defoaming agents, colorants, non-aldehydes. Base biocides, soaps and slip agents can be added.

【0045】

Hereinafter, some embodiments of the present invention will be described with reference to Examples. These should not be construed as limiting the scope of the invention, which is more fully described in the specification and claims. Unless otherwise stated, percent is weight% based on total solids.

【0046】

Example 1 501.7 g of water, 18.1 g of Rhodapex CO-436 (ammonium salt of sulfated nonylphenoxypoly (ethyleneoxy) ethanol; Rhone Poulenc), 7.5 g of methacrylate, 597.6 g of acetoacetoxyethyl methacrylate, 888.9 g of methyl methacrylate , And 44.9 g of a monomer mixture containing n-dodecyl mercaptan, a polymer was prepared. 47.2 g was removed from this monomeric emulsion mixture and added to a kettle heated to 85 ° C containing 1317.9 g water and 8.74 g Rhodapex CO-436. An initiator filler consisting of 2.26 g sodium persulfate dissolved in 50.0 g water was added. After 10 minutes of initiation, the remaining monomeric emulsion was added slowly over 2 hours with another feed stream, 1.13 g of sodium persulfate dissolved in 50 g of water. After 2 hours, the emulsion was cooled to ambient temperature.

【0047】

Polymer solubilization To 500 g of the emulsion diluted with water to a solid content of 41.8%, 370 g of primary amine-terminated polyethoxylate (Jeffamine M-1000, Texaco) having a molecular weight of 1000 (0.95 equivalent based on the acetic acid functional group) was added. .. The resulting mixture was a clear solution of a highly viscous material (7160 cps on a B-type viscometer) and was a rheological solution.

【0048】

This example illustrates that an emulsion polymer can be solubilized with a suitable amine to produce a uniform soluble resin by the formation of enamine.

【0049】

Example 2 501.7 g of water, 45.7 g of 23% solution of sodium dodecylbenzene sulfonate, 19.42 g of methacrylic acid, 298.8 g of acetoacetoxyethyl methacrylate, 578.2 g of methyl methacrylate, 597.6 g of butyl acrylate, and 3.0 g of n- Polymers were prepared from a monomer mixture containing dodecyl mercaptan. 47.2 g of this monomeric emulsion mixture was removed, containing 1317.9 g of water and 22.0 g of sodium dodecylbenzene sulfonate solution and added to a kettle heated to 85 ° C. An initiator filler consisting of 2.26 g sodium persulfate dissolved in 50.0 g water was added. After 10 minutes of initiation, the remaining monomeric emulsion was added slowly over 2 hours with 1.13 g of sodium persulfate dissolved in 50 g of water in another feed stream. After 2 hours, the emulsion was cooled to ambient temperature. To the aliquot of the emulsion was added 1 equivalent of the amines shown in Table 1. The latex polymer was equilibrated for 2 days, then lyophilized and the Tg of the polymer was measured by a differential scanning calorimeter.

【0050】

[table 1]

Effect of Enamine Production on Polymer Tg Amine Tg (° C) Control (none) 23 Ammonia 26 Ethanolamine 30 4-Amine-2,2,6,6-Tetramethylpiperidin 39 [0051]

This example illustrates that the Tg of a polymer can be adjusted after the polymer has been formed by the post-addition of the primary amine of choice and the formation of the corresponding enamine.

【0052】

Example 3 Functionalized Monomer 1 (Ethylethyleneurea Enamine of Allylacetacetate) Functionalized monomers were prepared by treating allyl acetoacetate (77 g, 0.543 mol) with aminoethylethylene urea (70 g, 0.543 mol) in 149 g of ethyl acetate containing 0.4 g of fetishazine. The reaction mixture was connected to a Dean-Stark trap (used to remove water by azeotrope) and heated under reflux for a total of 13 hours. The reaction solvent was then removed under reduced pressure using a rotary evaporator to give a total of 122 g of product.

【0053】

Example 4 Functionalized Monomer 2 (AAEM Hydroxyethyl Enamine) Functionalized monomers were prepared by treating acetoacetoxyethyl methacrylate (AAEM) (200 g) with ethanolamine (62.7 g) in 500 g methylene chloride. The reaction mixture was stirred at room temperature for 20 minutes, then heated to reflux for 1 hour and cooled to room temperature. The cooled reaction mixture was poured into a separatory funnel and washed twice with saturated sodium chloride solution. The organic solution was dried over anhydrous potassium carbonate. The dry organic solution was then filtered to remove potassium carbonate. The resulting organic solution was concentrated under reduced pressure using a rotary evaporator to give 239 g of the desired product: 1H NMR (270MHz, CDCL3) d 1.85 (br s, 6H), 3.3 (br q, 2H). , 3.62 (br t, 2H), 3.8 (m, 1H), 4.2 (m, 4H), 4.38 (s, 1H), 6.02 (s, 1H), 8.5 (m, 1H).

【0054】

Example 5 Preparation of solution polymers with enamine-functionalized monomers A reaction flask containing 286 g of xylene was heated to 105 ° C under a nitrogen atmosphere. A mixture of 120 g of butyl methacrylate, 67 g of butyl acrylate, 10 g of enamine produced from AAEM and ethanolamine of Example 4, and 3 g of methacrylic acid in 14 g of xylene was dissolved in 6 g of t-butyl peroct. It was fed over 2 hours with a mixture of ate. The reaction was held at 105 ° C for an additional 30 minutes, when 0.5 g of t-butyl peroctate was added to the reaction mixture. The reaction was maintained at 105 ° C. for 10 minutes and cooled to room temperature. The final solution was shown to contain 38% by weight of solid polymer material by drying the sample in the oven at high temperature (150 ° C for 30 minutes). The polymer was shown to have an enamine structure by examining the UV spectrum of a thin film of polymer cast on a quartz disc. According to the UV spectrum, the wavelength of 283 nm contained a large characteristic absorption of beta-aminoclotonate.

【0055】

Example 6 Vinyl acetate emulsion polymer 490 g water, 1.8 g nonylphenoxy polyethylene oxide sulfonate (Rhodapex) 58% solution of ammonium salt of CO-436), 3 g acetic acid, 3.6 g sodium acetate, 2083.4 g vinyl acetate, 21.6 g sodium vinyl sulfonate and 71.3 g allylacet acetate, 1026 g water (60 ° C). A 45% solution containing 100 nm particles of 60 g BA / MMA / MAA latex polymer, 24 g sodium persulfate 2.75% aqueous solution, 24 g sodium hydrogen sulfite 1.25% aqueous solution, 12.0 g sodium bisulfite An emulsion polymer having an overall composition of vinyl acetate 96.45 / allyl acetoacetate 3.3 / vinyl sulfonate sodium 0.25 was prepared by addition to a reaction kettle containing a 0.2% aqueous solution of monoiron, 3 g acetic acid and 3 g sodium acetate. The above monomer emulsion was placed in a reaction kettle with 120 g of a solution of 2.25% sodium bisulfite and 2.4 g of a solution of t-butyl hydroperoxide, 1.8 g of sodium persulfate, and 120 g of water under a nitrogen atmosphere. Supplied over 3.5 hours. After the addition of the monomers, the reaction was maintained at 60 ° C. for 15 minutes, then a solution of 30 g of an aqueous solution of 8% t-butyl hydroperoxide was added to the kettle with 120 g of an aqueous solution of 5% isoascorbic acid. .. The reaction mixture was then cooled to room temperature to give a latex containing 51.6% solid polymer.

【0056】

Example 7 Functionalization of vinyl acetate emulsion A sample of 100 g of the emulsion polymer of Example 6 was treated with 1.55 g of aminoethylethylene urea. The reaction system was maintained at room temperature. The next morning, a thin film of polymer on a quartz disc showed that it had a UV characteristic absorption peak of beta-aminocrotonate structure at a wavelength of 280 nm.

【0057】

Example 8 (Meta) Acrylate Emulsion Polymer Polymer from a monomer mixture containing 629.99 g of water, 9.89 g of a 23% aqueous solution of sodium dodecylbenzene sulfonate, 790.02 g of butyl acrylate, 686.57 g of methyl methacrylate, 376.20 g of acetoacetoxyethyl methacrylate, and 28.22 g of methacrylic acid. Was prepared. 58.72 g was removed from this monomeric emulsion and added to a reaction kettle heated to 85 ° C containing 1757.93 g of water, 8.22 g of a 23% aqueous solution of sodium dodecylbenzenesulfonate and 3.02 g of sodium persulfate. The monomer emulsion was added to the kettle at the same time as 50 g of a 1.7% aqueous solution of sodium persulfate for 180 minutes. After the addition, the reaction system was maintained at 85 ° C for 30 minutes and then cooled to 65 ° C. After the reaction mixture reaches 65 ° C, a 0.48 aqueous solution of ferrous sulfate Add 1.0 g, 0.54 g of 70% active t-butyl hydroperoxide dissolved in 19 g of water, and 0.38 g of isoascorbic acid dissolved in 19 g of water to the reaction kettle. The reaction is maintained at 65 ° C for 15 minutes and cooled to room temperature. As a result, an emulsion polymer having a solid content of 43.3% was produced.

【0058】

Example 9 Preparation of cationic latex A 10 g sample of the experimental latex prepared in Example 8 was diluted with 33.3 g of 0.1 mol potassium chloride aqueous solution and 0.18 g of Triton X-405 (70% aqueous solution, manufactured by Union Carbide). The latex sample was then treated with 0.356 g of dimethylaminoethylamine and allowed to equilibrate overnight. Acoustic mobility was measured using a Penkem 7000 instrument while varying the pH of the system. Random Acoustic Foretic Mobility (RAM) is approximately -1.8 x 10 at pH 10-8.5^-10 , + 1.2 × 10 at pH 8 ~ 2^-10 Met. This means that the latex is anionic (negative charge) at high pH and cationic (positive charge) at low pH, and whether or not the tertiary amine group is protonated, respectively. It is clearly shown. Therefore, the tertiary amine group needs to be introduced into the latex particles.

【0059】

Example 10 Latex polymer A has a solid content of 39.7% and a composition of 50 (2-ethylhexyl acrylate 54 / styrene 2.0 / acrylonitrile 25 / methacrylic acid 4 / acetoacetoxyethyl acrylate 15) // 50 (isobutyl methacrylate 40 / methyl methacrylate 58 / methacrylic acid). It is a two-stage emulsion polymer of 2). Latex B is a two-stage emulsion with a solid content of 41.6% and a composition of 50 (butyl acrylate 3 / styrene 91.6 / divinylbenzene 4.4 / methacrylic acid 1) // 50 (butyl acrylate 83 / acetoacetoxyethyl acrylate 10 / methacrylic acid 7). It is a polymer. All of these are prepared by conventional means well known in the art. In the examples listed below, a latex sample (100 g) is treated with butyl cellosolve (8.93 g) and butyl carbitol (2.98 g), followed by the addition of the appropriate amount of the indicated functional amine. Prepared.

【0060】

Amine Amount Late MEK Acetone Print Resistance Kusu swelling ratio spot test None (control) 0 A 7.3 1 3 2- (2-Aminoethyl) 1.45 A 4.5 5 7 -Aminoethanol 4-Amino-2,2,6,6 2.17 A 5.1 N / A 9 -Tetramethylpiperidin None (control) 0 B 4.5 0 4 2- (2-Aminoethyl) 1.01 B 3.8 4 7 -Aminoethanol N-Methylethylenediamine 1.13 B 3.3 9 5 2-((3-Aminopropyl 0.86 B 3.4 6 7) Amino) -Propanol N-Ethylethylenediamine 0.72 B 3.3 6 4 [0061]

In the above example, the use of diamines (one amine is the first amine and the other amine is the second amine) improves the solvent and print resistance of transparent coatings used on wood and other solid substrates. It shows that it can be done.

【0062】

Test method Print resistance test The coating is cast on aluminum to a DFT 1 mil and air dried for 4 hours. Place a piece of cheesecloth on the coating, then place a weight on the cheesecloth and apply a pressure of 4 psi. After 4 hours, the weights and cheesecloth are removed and the indentations formed by the cheesecloth are inspected. Samples are evaluated on a scale of 0 to 10, where 0 indicates a completely defective product with cheese cloth irreversibly attached to the coating, and 10 indicates no visual damage to the coating when the cheese cloth is removed. ..

【0063】

Acetone spot test The coating is cast on aluminum to a DFT 1 mil and air dried for 1 week. A fiberglass filter disc (Gelman 66075 or similar) is dipped in acetone, then placed on the coating and covered with a watch glass. After 2 minutes, the filter is removed and the excess acetone is sucked up with a tissue and inspected for film damage. Samples are evaluated on a scale of 0 to 10, where 0 indicates a completely defective product with the coating dissolved in the solvent and 10 indicates no visual damage to the coating.

【0064】

MEK swelling ratio test A latex polymer coating with a thickness of about 10-12 mils in the wet state and a dry coating thickness of about 2 mils is cast onto a sheet of polypropylene. The dry film is removed from polypropylene and cut into 1 cm x 1 cm square samples. Immerse the sample in methyl ethyl ketone for 2 hours. The swollen sample is removed from the solvent and the length of one edge is measured. The volume is determined from the obtained length to obtain the reported swelling value. The lower the value, the better the solvent resistance of the coating by nature.

【0065】

Glossary The meanings of the abbreviations used in this application are shown in the following list. Polymer Tg is a measure of polymer hardness and melt flow. The higher the Tg, the lower the melt flow and the harder the coating. Tg is described in the "Principles of Polymer Chemistry (1953)" Cornell University Press. Tg can be measured in practice and can also be calculated as explained by FOX on Bull. Amer. Physics Soc., P. 1,3, 123 (1956). The Tg used in the present specification is an actually measured value. A differential scanning calorimetry (DSC) can be used to measure the Tg of the polymer (heating rate of 10 ° C / min, Tg obtained from the first inflection point). DFT is the thickness of the dry film.