Hydrophilic acrylic resins and waterborne coating composition containing same

Abstract: A hydrophilic acrylic copolymer contains as monomer constituents thereof (a) an acrylic monomer having a hydroxyalkylcarbonate group which is an addition reaction product of a hydroxyalkyl (meth)acrylate or its adduct with ε -caprolactone and a cyclic alkylenecarbonate, and (b) an acid group-containing monomer. The copolymer is dispersed in an aqueous medium containing a neutralizing base together with a crosslinker to prepare a thermosetting waterborne coating composition.

Description: BACKGROUND OF THE INVENTION This invention relates to a hydrophilic acrylic resin. It also relates to a coating composition containing the hydrophilic acrylic resin. Much interest has been placed today on waterborne paint free from the emission of VOC for energy saving and environmental reasons. For use in thermosetting waterborne paint formulations, the vehicle resin must have a functional group such as hydroxyl as a crosslinking site thereof and also an acid group such as carboxylic or sulfonic acid group to render the resin water-soluble. In case of acrylic resins, the hydroxyl group may be introduced to the resin by copolymerizing a hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate or methacrylate. The resins thus produced, however, are not fully satisfactory in their reactivity with a crosslinker such as melamine resins or blocked polyisocyanates because the cross-linking site thereof is not remotely spaced apart from the resin backbone chain formed of recurring carbon-to-carbon linkages and the curing with a crosslinker requires a relatively high temperature. JP-A-61/181877 discloses coating compositions containing an acrylic resin produced by copolymerizing an adduct of 2-hydroxyethyl (meth)acrylate with ε-caprolactone known as PLACCEL FA and FM series with conventional monomers. This acrylic resin exhibits improved reactivity with the crosslinker and improved flexibility or low temperature-impact strength of the cured films. This is because the crosslinking site is farther spaced apart from the resin backbone by an ester linkage formed by the ring-opening reaction of ε -caprolactone. However, the above lactone-modified monomers are not compatible with an acid group-containing monomer necessary for rendering the resin water-soluble because the ester linkage is liable to hydrolysis and the copolymers containing the lactone-modified monomer and the acid group-containing monomer are not stable upon storage in an aqueous medium. A need exists, therefore, for a hydrophilic acrylic resin which eliminates or ameliorates the above disadvantages when formulated in waterborne coating compositions as a vehicle resin thereof. SUMMARY OF THE INVENTION In the first aspect, the present invention provides a hydrophilic acrylic copolymer having a hydroxyl number of from 20 to 300, an acid number of from 10 to 100 and a number average molecular weight of from 1,000 to 50,000, said copoymer containing in the molecule (a) a plurality of pendant groups each terminated with a group of the formula: wherein R 7 is a C 2 -C 8 -alkylene bridge, and m is an integer of from 1 to 6; and (b) a plurality of acid group-terminated pendant groups. The above acrylic copolymer may be prepared by copolymerizing a monomer mixture of (a) 10 to 60 % by weight of the mixture of an acrylic monomer of the formula II: wherein R 1 is hydrogen or methyl, R 2 and R 3 are independently a C 2 -C 8 -alkylene bridge, n is zero or an integer of from 1 to 6, and R 4 and m are as defined; (b) 3 to 15 % by weight of the mixture of an ethylenically unsaturated monomer having an acid group; and (c) the balance of the mixture of an ethylenically unsaturate monomer other than monomers (a) and (b). In the second aspect, the present invention provides a hydrophilic acrylic copolymer having a hydroxyl number of from 20 to 300, an acid number of from 10 to 100 and a number average molecular weight of from 1,000 to 50,000, said copolymer containing in the molecule (a) a plurality of pendant groups each terminate with a group of the formula: wherein R 4 and m are as defined; (b) a a plurality of acid group-terminated pendant groups; and (c) a plurality of pendant groups each terminated with an amide group of the formula: wherein R 5 and R 6 are independently hydrogen, a C 1 -C 8 -alkyl, a C 6 -C 12 -cycloalkyl or a C 6 -C 12 -aryl. The acrylic copolymer just mentioned as above may be prepared by copolymerizing a monomer mixture of (a) 10 to 60 % by weight of the mixture of an acrylic monomer of the formula II: wherein all symbols are as defined; (b) 3 to 15 % by weight of the mixture of an ethylenically unsaturate monomer having an acid group; (c) 5 to 40 % by weight of the mixture of a monomer of the formula IV: wherein R 1 , R 5 and R 6 are as defined; and (d) the balance of the mixture of an ethylenically unsaturated monomer other than monomers (a), (b) and (c). In the third aspect, the present invention provides a waterborne, thermosetting coating composition comprising the hydrophilic acrylic copolymer of the present invention and crosslinker dispersed in an aqueous medium containing a neutralizing base. DETAILED DESCRIPTION OF THE INVENTION The characteristic feature of the hydrophilic acrylic copolymer of the present invention resides in that it contains a plurality of pendant groups each terminated with a hydroxyalkyl carbonate group of the formula I: wherein R 4 and m are as defined. This is particularly advantageous because each of the hydroxyl groups becoming a crosslinking site are spaced apart from the polymer backbone chain by a chemically stable alkylene carbonate linkage and, therefore, the copolymer is not liable to hydrolysis when formulated in a waterborne coating composition. The'hydrophilic acrylic copolymer of the present invention is prepared by copolymerizing a monomer mixture of (a) an acrylic monomer of the formula II: wherein all symbols are as defined; (b) an ethylenically unsaturated monomer having an acid group; and (c) an ethylenically unsaturated monomer other than monomers (a) and (b). The monomer mixture may optionally contain (d) an acrylamide or methacrylamide monomer of the formula: wherein R 1 , R 5 and R 6 are as defined, as a portion of monomer (c). The acrylic monomer having a hydroxyalkyl carbonate group of the formula II may be produced as disclosed in EP-A-0600417 by reacting a cyclic alkylenecarbonate with a hydroxylalkyl (meth)acrylate such as 2-hydroxyethyl methacrylate, 3-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, or an adduct of hydroxyalkyl (meth)acrylate with a lactone such as addcuts of 2-hydroxyethyl (meth)acrylate with ε-caprolactone sold by Daicel Chemical Industries, Ltd. under the name of PLACCEL FA and FM series. The reaction may be carried out at a temperature from room temperature to 180 °C, preferably from room temperature to 80°C in the presence of a catalyst. Preferably, said acrylic monomer (a) is an addition reaction product of a hydroxy-C 2 -C 8 -alkyl methacrylate with a cyclic C 2 -C 8 -alkylcarbonate or an addition reaction product of 2-hydroxyethyl (meth)acrylate-ε-caprolactone adduct with a cyclic C 2 -C 8 -alkylcarbonate. A preferred example of the cyclic carbonate is 5,5-dimethyl-1,3-dioxan-2-one otherwise called neopentyl glycol carbonate. Preferably, the acid group-containing monomer (b) is a polymerizable alkenenoic acid, or a half ester or amide of an ethylenically unsaturated dicarboxylic acid. Typical examples of carboxylic acid monomers are acrylic, methacrylic, crotonic or isocrotonic acid. Half esters of a dicarboxylic acid having an ethylenic unsaturation such as maleic, fumaric or itaconic acid with a low molecular weight aliphatic alcohol such as methanol, ethanol, n- or isopropanol, n-, iso- or t-butanol, methylcellosolve, ethylcellosolve, acetol, allyl alcohol or propargyl alcohol, and half amides of such unsaturated dicarboxylic acids such as itaconic acid monoanilide may also be used. Examples of sulfonic acid monomers include p-vinylbenzenesulfonic acid and 2-acryloylaminopropanesulfonic acid. Examples of acrylamides and methacrylamides include (meth)acrylamide, N-monoalkyl or N,N-dialkyl derivatives thereof, such as acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-dibutylacrylamide, N,N-dibutylmethacrylamide, N,N-dioctylacrylamide, N,N-dioctylmethacrylamide, N-butylacrylamide, N-butylmethacrylamide, N-octylacrylamide or N-octylmethacrylamide, Copolymerization of these amide monomers improves the workability and also facilitates the pH control of the hydrophilic acrylic resin of the present invention. The monomer mixture may optionally contain a small proportion of monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or an adduct thereof with ε-caprolactone to introduce hydroxyl groups into the resin. Examples of other comonomers include styrene, α-methylstyrene, acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-methacrylate or lauryl methacrylate. The proportion of hydroxyl group-containing monomers is from 10 to 60 %, preferably from 15 to 40 % by weight of the entire monomer mixture. With proportions less than this range the resin will not exhibit a curability sufficient to give a cured film having satisfactory water resistant and weatherability properties. Conversely, with proportions greater than the above range the resin will only give a cured film which is too rigid and brittle. The proprotion of acid group-containing monomers is from 3 to 15 %, preferably from 5 to 13 % by weight of the entire monomer mixture. With proportions less than this range the resin will be poorly soluble in water and conversely greater proportions will result in decreased water resistance properties. The proportion of amide monomers, if present, is from 5 to 40 %, preferably from 10 to 25 % by weight of the entire monomer mixture. Within this range various advantages as stated above may be expected. The balance of the monomer mixture is occupied with a comonomer or comonomers other than monomers having a functional group as identified above. The monomer mixture may be polymerized using conventional solution polymerization methods. For example, the polymerization is preferably carried out in a solvent such as ethoxypropanol or γ -butyrolactone at a temperature from 80 °C to 140 °C in the presence of a polymerization initiator such as benzoyl peroxide, t-butyl hydroperoxide, t-butylperoxy 2-ethylhexanoate, cumene hydroperoxide or azobisisobutyronitrile. The hydrophilic acrylic resin may also be produced by copolymerizing a hydroxyalkyl (meth)acrylate or its lactone adduct with other requisite monomers and then reacting the resulting copolymer with a cyclic carbonate such as 5,5-dimethyl-1,3-dioxan-2-one. For use as a vehicle resin of waterborne coating compositions, the hydrophilic acrylic resin of the present invention should have an acid number of from 10 to 100, preferably from 30 to 80, and a hydroxyl number of from 20 to 300, preferably from 50 to 200 to impart the resin with optimum levels of water-solubility and curability as discussed before in connection with the proportions of acid group-bearing monomers and hydroxyl group-bearing monomers. The resin should also have a number average molecular weight of from 1,000 to 50,000, preferably from 1,500 to 30,000. This is because resins of low molecular weights result in decrease in strength properties of cured films and because excessively high molecular weights decrease the spray workability of the coating composition of the present invention. The hydrophilic acrylic resin of the present invention is solubilized in water by neutralizing at least a portion of acid groups thereof with an amine such as mono-, di- or trimethylamine, mono-, di- or triethylamine, diisopropylamine, mono- or diethanolamine, or dimethylethanolamine. The hydrophilic acrylic resin of the present invention is dissolved or dispersed in an aqueous medium containing a neutralizing base together with a crosslinker to prepare a thermosetting, waterborne coating composition. The crosslinker may be an aminoplast resin or a blocked polyisocyanate. Examples of aminoplast resins include di-, tri-, tetra-, penta- or hexamethylolmelamine; ethers thereof with a lower alkanol such as methanol, ethanol, propanol, isopropanol, butanol or isobutyl alcohol; ureaformaldehyde condensation products; and co-condensation product of melamine and urea with formaldehyde. Blocked polyisocyanates are prepared by reacting an organic polyisocyanate with a blocking agent as is well-known in the art. Examples of polyisocyanates include aliphatic or cycloaliphatic polyisocyanates such as trimethylenediisocyanate, hexamethylenediisocyanate(HMDI), isophoronediisocyanate(IPDI), dimers, trimers or trimethylolpropane adducts of these diisocyanates; and aromatic polyisocyanates such as phenylenediisocyanate, tolylenediisocyanate (TDI), naphthylenediisocyanate, diphenylmethanediisocyanate (MDI), triphenylmethanetriisocyanate, dimer or trimer of TDI. Examples of blocking agents include alcohols such as methanol or ethanol; secondary amines such as diethanolamine, lactams such as caprolactam; and oximes such as methyl ethyl ketoxime. Melamine resins are preferable including commercially available hydrophilic or hydrophobic melamine resins sold under the name of CYMEL® 303, CYMEL® 325 and CYMEL® 1156 by American Cyanamid Company, YUBAN 20N, YUBAN 20SB and YUBAN 129 sold by Mitsui Toatsu Chemicals, Inc.; and SUMIMAL M-50W, SUMIMAL M-4ON and SUMIMAL M-30W sold by Sumitomo Chemical Company Limited. The ratio of the acrylic resin to the crosslinker in the coating composition is generally from 90:10 to 50:50, preferably from 80:20 to 60:40 by weight as solids. The waterborne coating composition of the present invention may contain, in addition to water, an organic solvent. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, ethoxyethanol, ethoxypropanol or methoxypropanol; esters such as methyl acetate, ethyl acetate or butyl acetate; lactones such as γ -butyrolactone; hydrocarbons such as toluene or xylene; ethers such as dibutyl ether or ethylene glycol diethyl ether; and amides such N-methylpyrrolidone. The coating composition may contain other conventional additives such as inorganic, organic or metallic pigments e.g. aluminum flakes, UV absorbers, antifoaming agents and surface smoothers. The following examples are given for illustrative purposes only. All parts and percents therein are by weight unless otherwise specified. Produciton Example 1 Macromonomer A A mixture of 2.88g (0.02 mol.) of 4-hydroxybutyl acrylate and 2.6g (0.02 mol.) of 5,5-dimethyl-1,3-dioxan-2-one was heated to make a solution. To this was added 0.038g (0.2 mmol.) of p-toluenesulfonic acid monohydrate. The mixture was heated at 40°C for 60 minutes with stirring. Thereafter the reaction mixture was cooled, filtered to remove solid matters and evaporated in vacuo to remove unreacted reactants. 1 H-NMR δ 0.8 (s, 6H, -C(C H 3 ) 2 , 3.1 (s, 2H, -C(CH 3 ) 2 -C H 2 -OH), 3.8 (OCOOC H 2 C(CH 3 ) 2 -) IR; ν 3450cm -1 (OH), 1745cm -1 (O-CO-O), 1720cm -1 (COO) Production Example 2 Macromonomer B A mixture of 2.6g (0.02 mol.) of 2-hydroxyethyl methacrylate and 2.6g (0.02 mol.) of 5,5-dimethyl-1,3-dioxan-2-one was heated to make a solution. To this was added 0.038g (0.02 mmol.) of p-toluenesulfonic acid monohydrate. The mixture was heated at 40°C for 60 minutes with stirring. Thereafter the reaction mixture was cooled, filtered to remove solid matters and evaporated in vacuo to remove unreacted reactants. 1 H-NMR δ 0.8 (s, 6H, -C(C H 3 ) 2 , 3.1 (s, 2H, -C(CH 3 ) 2 -C H 2 -OH), 3.8 (OCOOC H 2 C(CH 3 ) 2 -) IR; ν 3450cm -1 (OH), 1745cm -1 (O-CO-O), 1720cm -1 (COO) Production Example 3 Macromonomer C A mixture of 2.88g (0.02 mol.) of 4-hydroxybutyl acrylate and 5.2g (0.04 mol.) of 5,5-dimethyl-1,3-dioxan-2-one was heated to make a solution. To this was added 0.93g of AMBERLIST 15. The mixture was heated at 40 °C for 200 minutes with stirring. After the reaction, the mixture was cooled, filtered to remove solid matters and evaporated in vacuo to remove unreacted reactants. 1 H-NMR δ 0.8 (s, 6H, -C(C H 3 ) 2 , 3.1 (s, 2H, -C(CH 3 ) 2 C H 2 -OH), 3.8 (OCOOC H 2 C(CH 3 ) 2 -) IR; ν 3450cm -1 (OH), 1745cm -1 (O-CO-O), 1720cm -1 (COO) Example 1 A flask equipped with a stirrer, condenser, thermometer, nitrogen gas tube and drip funnel was charged with 500 parts of 2-ethoxypropanol and heated to 100°C. To this was added dropwise a mixture of 50 parts of styrene, 50 parts of methyl methacrylate, 200 parts of Macromonomer A, 120 parts of 2-ethylhexyl methacrylate, 380 parts of n-butyl acrylate, 40 parts of acrylic acid and 30 parts of azobisisobutyronitrile (AIBN) over 3 hours, followed by stirring at the same temperature for 30 minutes. Then a solution of 3 parts of t-butylperoxy 2-ethylhexanoate (TBPEH) in 50 parts of butyl acetate was added dropwise over 0.5 hours, followed by standing for 1.5 hours at 100 °C . Then the reaction mixture was evaporated in vacuo to remove 220 parts of solvent, and dissolved in a mixture of 99 parts of dimethylethanolamine and 570 parts of deionized water whereupon an aqueous varnish of acrylic resin having an acid number of 37 as solids, and a hydroxyl number of 49 as solids, and a number average molecular weight of 9500 (GPC method) was obtained. The aqueous varnish was diluted with deionized water to a Ford cup #4 viscosity of 20 seconds, and stored at 40°C for 10 days. The storage stability of the varnish was evaluated by measuring the viscosity before and after storage. The results are shown in Table 1 below. A waterborne coating composition was prepared by mixing 100 parts of the above varnish and 70 parts of YUBAN 20SB (melamine resin sold by Mitsui Toatsu Chemicals, Inc.) and diluting with deionized water to a Ford cup #4 viscosity of 20 seconds. This coating composition was applied on a tinplate, baked at 140 °C for 20 minutes and tested for curability. The coating composition was also tested for storage stability under the same conditions as before. The results are also shown in Table 1. In the following Examples, the procedure of Example 1 was followed to prepare an aqueous resin varnish and a waterborne coating composition using various materials shown therein. The results of storage stability and curability tests carried out under the same conditions as in Example 1 are shown in Table 1. Example 2 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer A 280 parts Monomethyl itaconate 80 parts Methyl methacrylate 200 parts Butyl acrylate 200 parts 2-Ethylhexyl methacrylate 200 parts Initiator AIBN (1st stage) 30 parts TBPEH (2nd stage) 3 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 100 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 30 OH number 55 Mn 11000 Example 3 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer B 280 parts Monomethyl itaconate 120 parts Styrene 100 parts Methyl methacrylate 100 parts Butyl acrylate 120 parts 2-Ethylhexyl methacrylate 240 parts Initiator AIBN (1st stage) 30 parts TBPEH (2nd stage) 3 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 100 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 30 OH number 63 Mn 11000 Example 4 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer C 280 parts Monobutyl maleate 35 parts Styrene 50 parts Methyl methacrylate 190 parts Butyl acrylate 100 parts 2-Ethylhexyl methacrylate 180 parts Initiator AIBN (1st stage) 30 parts TBPEH (2nd stage) 3 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 70 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 13 OH number 51 Mn 12000 Example 5 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer A 500 parts Methacrylic acid 30 parts Monobutyl maleate 60 parts Styrene 50 parts Methyl methacrylate 175 parts Butyl acrylate 125 parts 2-Ethylhexyl methacrylate 160 parts Initiator AIBN (1st stage) 20 parts TBPEH (2nd stage) 3 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 80 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 39 OH number 82 Mn 17000 Example 6 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer A 400 parts Methacrylic acid 30 parts Monobutyl maleate 100 parts Styrene 50 parts Methyl methacrylate 150 parts Butyl acrylate 150 parts 2-Ethylhexyl methacrylate 120 parts Initiator AIBN (1st stage) 20 parts TBPEH (2nd stage) 3 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 100 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 39 OH number 82 Mn 18000 Example 7 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer C 360 parts Methacrylic acid 20 parts Monomethyl itaconate 100 parts Styrene 160 parts Methyl methacrylate 50 parts Butyl acrylate 150 parts 2-Ethylhexyl methacrylate 160 parts Initiator AIBN (1st stage) 50 parts TBPEH (2nd stage) 3 parts Solvent removed 300 parts Neutralizer Triethylamine 80 parts Deionized water 650 parts Varnish properties Appearance clear Acid number 52 OH number 50 Mn 7000 Example 8 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer B 600 parts Methacrylic acid 20 parts Monobutyl itaconate 100 parts Styrene 70 parts Butyl acrylate 150 parts 2-Ethylhexyl methacrylate 60 parts Initiator TBPEH (1st stage) 50 parts TBPEH (2nd stage) 3 parts Solvent removed 300 parts Neutralizer Triethylamine 80 parts Deionized water 650 parts Varnish properties Appearance clear Acid number 45 OH number 129 Mn 8000 Comparative Example 1 Example 8 was repeated except that 600 parts of PLACCEL FM 1 (2-hydroxyethyl methacrylate-caprolactone adduct sold by Daicel Chemical Industries, Ltd.) were replaced for 600 parts of Macromonomer B. Acid number 45, OH number 138, and Mn 7,000. Comparative Example 2 Example 1 was repeated except that 280 parts of PLACCEL FM 1 were replaced for 280 parts of Macromonomer A. Acid number 30, OH number 62, and Mn 11,000. Example 9 A flask equipped with a stirrer, condenser, thermometer, nitrogen gas tube and drip funnel was charged with 500 parts of 2-ethoxypropanol and heated to 100°C. To this was added dropwise the following monomer and initiator mixture over 3 hours followed by stirring for 30 minutes. Styrene 25 parts Methyl methacrylate 25 parts Macromonomer A 400 parts 2-Ethylhexyl methacrylate 70 parts Butyl acrylate 280 parts Monobutyl maleate (in methanol) 100 parts Acrylamide (in methanol) 100 parts Methanol 300 parts AIBN 30 parts Then a solution of 3 parts of TBPEH in 50 parts of butyl acetate was added dropwise over 30 minutes, followed by maintaining the mixture at 100°C for 1.5 hours while distilling off 300 parts of methanol. Then the reaction mixture was evaporated in vacuo to remove 220 parts of solvent, and dissolved in a mixture of 100 parts of dimethylethanolamine and 570 parts of deionized water whereupon an aqueous varnish of acrylic resin having an acid number of 33 as solids, and a hydroxyl number of 82 as solids, and a number average molecular weight of 12,000 (GPC method) was obtained. The aqueous varnish was diluted with deionized water to a Ford cup #4 viscosity of 20 seconds, and stored at 40°C for 10 days. The storage stability of the varnish was evaluated by measuring the viscosity before and after storage. The results are shown in Table 2 below. A waterborne coating composition was prepared by mixing 100 parts of the above varnish and 70 parts of YUBAN 20SB (melamine resin sold by Mitsui Toatsu Chemicals, Inc.) and diluting with deionized water to a Ford cup #4 viscosity of 20 seconds. This coating composition was applied on a tinplate, baked at 140 °C for 20 minutes and tested for curability. The coating composition was also tested for storage stability under the same conditions as before. The results are also shown in Table 2. In the following Examples, the procedure of Example 9 was followed to prepare an aqueous resin varnish and a waterborne coating composition using various materials shown therein. The results of storage stability and curability tests carried out under the same conditions as in Example 9 are shown in Table 2. Example 10 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer A 280 parts Monomethyl itaconate 80 parts Acrylamide 100 parts Methyl methacrylate 200 parts Butyl acrylate 200 parts 2-Ethylhexyl methacrylate 200 parts Methanol 300 parts Initiator AIBN (1st stage) 30 parts TBPEH (2nd stage) 3 parts Methanol removed 300 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 100 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 31 OH number 57 % Amide monomer 10 Mn 12,000 Example 11 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer B 280 parts Monomethyl itaconate 120 parts Acrylamide 100 parts Styrene 100 parts Methyl methacrylate 100 parts Butyl acrylate 120 parts 2-Ethylhexyl methacrylate 240 parts Methanol 500 parts Initiator AIBN (1st stage) 30 parts TBPEH (2nd stage) 3 parts Methanol removed 500 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 100 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 49 OH number 63 % Amide monomer 10 Mn 12,000 Example 12 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer C 280 parts Monobutyl maleate 35 parts Acrylamide 120 parts Styrene 50 parts Methyl methacrylate 190 parts Butyl acrylate 100 parts 2-Ethylhexyl methacrylate 180 parts Methanol 300 parts Initiator AIBN (1st stage) 30 parts TBPEH (2nd stage) 3 parts Methanol removed 300 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 70 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 13 OH number 51 % Amide monomer 14 Mn 11,000 Example 13 Solvent 2-Ethoxypropanol 500 parts Monomer mixture Macromonomer A 500 parts Methacrylic acid 30 parts Monobutyl maleate 60 parts Acrylamide 125 parts Styrene 50 parts Methyl methacrylate 175 parts Butyl acrylate 125 parts 2-Ethylhexyl methacrylate 160 parts Methanol 300 parts Initiator AIBN (1st stage) 20 parts TBPEH (2nd stage) 3 parts Methanol removed 300 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 80 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 40 OH number 80 % Amide monomer 14 Mn 18,000 Example 14 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer A 400 parts Methacrylic acid 30 parts Monobutyl maleate 100 parts t-Butyl acrylamide 150 parts Styrene 50 parts Methyl methacrylate 150 parts Butyl acrylate 150 parts 2-Ethylhexyl methacrylate 120 parts Methanol 400 parts Initiator AIBN (1st stage) 20 parts TBPEH (2nd stage) 3 parts Methanol removed 400 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 100 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 52 OH number 82 % Amide monomer 15 Mn 17,000 Example 15 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer C 360 parts Methacrylic acid 20 parts Monomethyl itaconate 100 parts Methacrylamide 100 parts Styrene 160 parts Methyl methacrylate 50 parts Butyl acrylate 150 parts 2-Ethylhexyl methacrylate 160 parts Methanol 500 parts Initiator TBPEH (1st stage) 50 parts TBPEH (2nd stage) 3 parts Methanol removed 500 parts Solvent removed 300 parts Neutralizer Triethylamine 80 parts Deionized water 650 parts Varnish properties Appearance clear Acid number 52 OH number 50 % Amide monomer 10 Mn 8,000 Example 16 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer B 600 parts Methacrylic acid 20 parts Mononutyl itaconate 100 parts Acrylamide 200 parts Styrene 70 parts Butyl acrylate 150 parts 2-Ethylhexyl methacrylate 60 parts Methanol 500 parts Initiator TBPEH (1st stage) 50 parts TBPEH (2nd stage) 3 parts Methanol removed 500 parts Solvent removed 300 parts Neutralizer Triethylamine 80 parts Deionized water 650 parts Varnish properties Appearance clear Acid number 43 OH number 131 % Amide monomer 20 Mn 8,000 Example 17 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer A 510 parts Methacrylic acid 30 parts N,N-dimethylaminoethyl monoitaconate 100 parts Methacrylamide 150 parts Methyl methacrylate 100 parts Butyl acrylate 50 parts 2-Ethylhexyl methacrylate 60 parts Methanol 500 parts Initiator TBPEH (1st stage) 40 parts TBPEH (2nd stage) 3 parts Methanol removed 500 parts Solvent removed 300 parts Neutralizer Triethylamine 60 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 45 OH number 104 % Amide monomer 15 Mn 10,000 Example 18 Solvent Ethylene glycol monobutyl ether 500 parts Monomer mixture Macromonomer A 320 parts Methacrylic acid 20 parts Itaconic acid monoanilide 100 parts Acrylamide 200 parts Styrene 50 parts Methyl methacrylate 90 parts Butyl acrylate 100 parts 2-Ethylhexyl methacrylate 120 parts Methanol 500 parts Initiator TBPEH (1st stage) 20 parts TBPEH (2nd stage) 3 parts Methanol removed 500 parts Solvent removed 220 parts Neutralizer Triethylamine 80 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 38 OH number 66 % Amide monomer 30 Mn 19,000 Comparative Example 3 Example 11 was repeated except that 280 parts of PLACCEL FM1 were replaced for 280 parts of Macromonomer B. Acid number 49, OH number 67, % amide monomer 10 %, and Mn=12,000. Comparative Example 4 Solvent 2-Ethoxypropanol 500 parts Monomer mixture PLACCEL FM1 600 parts Methacrylic acid 20 parts Monomethyl itaconate 100 parts Acrylamide 200 parts Methyl methacrylate 100 parts Butyl acrylate 100 parts 2-Ethylhexyl methacrylate 160 parts Methanol 500 parts Initiator TBPEH (1st stage) 50 parts TBPEH (2nd stage) 3 parts Methanol removed 500 parts Solvent removed 220 parts Neutralizer Dimethylethanolamine 100 parts Deionized water 570 parts Varnish properties Appearance clear Acid number 41 OH number 108 % Amide monomer 16 Mn 8,000

Claims: A hydrophilic acrylic copolymer having a hydroxyl number of from 20 to 300, an acid number of from 10 to 100 and a number average molecular weight of from 1,000 to 50,000, said copolymer bearing in the molecule (a) a plurality of pendant groups each terminated with a unit of the formula: wherein R 4 is a C 2 -C 8 -alkylene bridge, and m is an integer of from 1 to 6; and (b) a plurality of acid group-terminated pendant groups. The hydrophilic acrylic copolymer according to claim 1, wherein said hydroxyl number, said acid number and said molecular weight are from 50 to 200, from 30 to 80 and from 1,500 to 30,000, respectively. The hydrophilic acrylic copolymer according to claim 1 produced by copolymerizing a mixture of: (a) 10 to 60 % by weight of the mixture of an acrylic monomer of the formula: wherein R 1 is hydrogen or methyl, R 2 and R 3 are independently a C 2 -C 8 -alkylene bridge, n is zero or an integer of from 1 to 6, and R 4 and m are as defined; (b) 3 to 15 % by weight of the mixture of an ethylenically unsaturated monomer having an acid group; and (c) the balance of the mixture of an ethylenically unsaturated monomer other than monomers (a) and (b). The hydrophilic acrylic copolymer according to claim 3, wherein said acrylic monomer (a) is an addition reaction product of a hydroxy-C 2 -C 8 -alkyl methacrylate with a cyclic C 2 -C 8 -alkylcarbonate. The hydrophilic acrylic copolymer according to claim 4, wherein said cyclic alkylcarbonate is 5,5-dimethyl-1,3-dioxan-2-one. The hydrophilic acrylic copolymer according to claim 3, wherein said acrylic monomer (a) is an addition reaction product of 2-hydroxyethyl (meth)acrylate-ε-caprolactone adduct with a cyclic C 2 -C 8 -alkylcarbonate. The hydrophilic acrylic copolymer according to claim 6, wherein said cyclic alkylcarbonate is 5,5-dimethyl-1,3-dioxan-2-one. The hydrophilic acrylic copolymer according to claim 3, wherein said acid group-containing monomer (b) is an polymerizable alkenenoic acid, or a half ester or amide of an ethylenically unsaturated dicarboxylic acid. A hydrophilic acrylic copolymer having a hydroxyl number of from 20 to 300, an acid number of from 10 to 100 and a number average molecular weight of from 1,000 to 50,000, said copolymer bearing in the molecule (a) a plurality of pendant groups each terminated with a unit of the formula: wherein R 4 is a C 2 -C 8 -alkylene bridge, and m is an integer of from 1 to 6; (b) a plurality of acid group-terminated pendant groups; and (c) a plurality of pendant groups each terminated with an amide group of the formula: wherein and R 5 and R 6 are independently hydrogen, a C 1 -C 8 -alkyl, a C 6 -C 12 -cycloalkyl or a C 6 -C 12 -aryl. The hydrophilic acrylic copolymer according to claim 9, wherein said hydroxyl number, said acid number and said molecular weight are from 50 to 200, from 30 to 80 and from 1,500 to 30,000, respectively. The hydrophilic acrylic copolymer according to claim 9 produced by copolymerizing a mixture of: (a) 10 to 60 % by weight of the mixture of an acrylic monomer of the formula: wherein R 1 is hydrogen or methyl, R 2 and R 3 are independently a C 2 -C 8 -alkylene bridge, n is zero or an integer of from 1 to 6, and R 4 and m are as defined; (b) 3 to 15 % by weight of the mixture of an ethylenically unsaturated monomer having an acid group; (c) 5 to 40 % by weight of the mixture of a monomer of the formula: wherein R 1 , R 5 and R 6 are as defined, and (d) the balance of the mixture of an ethylenically unsaturated monomer other than monomers (a), (b) and (c). The hydrophilic acrylic copolymer according to claim 11, wherein said acrylic monomer (a) is an addition reaction product of a hydroxy-C 2 -C 8 -alkyl methacrylate with a cyclic C 2 -C 8 -alkylcarbonate. The hydrophilic acrylic copolymer according to claim 12, wherein said cyclic alkylcarbonate is 5,5-dimethyl-1,3-dioxan-2-one. The hydrophilic acrylic copolymer according to claim 10, wherein said acrylic monomer (a) is an addition reaction product of 2-hydroxyethyl (meth)acrylate-ε-caprolactone adduct with a cyclic C 2 -C 8 -alkylcarbonate The hydrophilic acrylic copolymer according to claim 14, wherein said cyclic alkylcarbonate is 5,5-dimethyl-1,3-dioxan-2-one. The hydrophilic acrylic copolymer according to claim 10, wherein said acid group-containing monomer (b) is an polymerizable alkenenoic acid, or a half ester or amide of an ethylenically unsaturated dicarboxylic acid. The hydrophilic acrylic copolymer according to claim 10, wherein said monomer (c) is (meth)acrylamide, N-monoalkyl or N,N-dialkyl derivative thereof. A thermosetting waterborne coating composition comprising the hydrophilic acrylic copolymer of claim 1 and a crosslinker dispersed in an aqueous medium containing a neutralizing base. The coating composition according to claim 18, wherein said crosslinker is a melamine resin. The coating composition according to claim 18, wherein said crosslinker is a blocked polyisocyanate. A thermosetting waterborne coating composition comprising the hydrophilic acrylic copolymer of claim 9 and a crosslinker dispersed in an aqueous medium containing a neutralizing base. The coating composition according to claim 21 wherein said crosslinker is a melamine resin. The coating composition according to claim 21, wherein said crosslinker is a blocked polyisocyanate.

Inventors: NAKANO SHINJI, TAKAGI TAKESHI, YAMADA SHINYA, NAKANO, SHINJI, TAKAGI, TAKESHI, YAMADA, SHINYA
Applicants: NIPPON PAINT CO LTD, NIPPON PAINT CO., LTD.
Application year: 1995
Main classification: C08F220
IPC codes: C08F20, C08G18, C09D133, C08F220