JPH0211607B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention consists of a polymerizable monomer having an amphoteric group, a monomer having two or more radically polymerizable unsaturated groups in the molecule, and other polymerizable monomers. The present invention relates to a novel amphoteric group-containing copolymer, a method for producing the same, and a coating composition containing the amphoteric group-containing copolymer as a component. The present inventors have previously synthesized a new polymerizable amphoteric compound, and are currently applying for a patent (Patent application filed in 1983-
No. 123899, patent application No. 125996 (1973). The compound has the formula [In the formula, R ₁ , R ₂ , R ₃ , R ₄ are H, CH ₃ ,
is either C ₂ H ₅ and R ₅ is H, or a C ₁ to C ₂₀ group that may contain a -SO- group, -COO- group, or -O- group in the chain. It is an alkyl group, and R ₆ ′ is -OH group, -SH group, -SR ₇ group (R ₇ is
C ₁ -C ₄ alkyl groups) and one or more C ₁
~May be substituted with a _C4 alkyl group
It is a _C1 - _C12 alkylene group, and A is a COOH group or a _SO3H group. ] or expression, [In the formula, R ₈ , R ₉ , R ₁₀ are each H or C ₁ to
It is a C ₆ alkyl group, and R ₁₁ is H or -SO in the chain.
a C ₁ to C ₂₀ alkyl group, which may contain either a - group, a -COO- group, an -O- group, or

and R ₁₂ ' is a C ₂ -C ₁₂ alkylene group which may be substituted with one or more C ₁ -C ₆ alkyl groups. ] It is a polymerizable amino acid compound shown by. The amino and acid moieties of these compounds are, for example, of the formula [In the formula, -B- represents -COO- or -SO ₃ -. ] Exists in a mixed state of tautomers shown as Furthermore, the ionic part of the above formula depends on the environment in which the system is placed, It changes like this. Therefore, by controlling the system environment such as hydrophilicity and pH, the ionic moiety of this compound can be made to take any desired form, and characteristics can be developed accordingly. And this type of compound has good reactivity,
It has surface activity, electrochemical properties, biochemical properties, etc. The purpose of the present invention is to focus on the excellent properties of such compounds and to develop the use of these compounds in various fields. On the other hand, in the field of polymer industry, water-based resins have recently been emphasized in place of the conventionally widely used solvent-based resin varnishes from the viewpoint of resource conservation and pollution prevention, and research and development related to this has been increasing. Emulsion resins are characterized by being able to utilize polymers with particularly high molecular weights among water-based resins, and usually contain a low molecular weight surfactant as an essential component, which stabilizes the dispersion of resin particles in water. However, since this surfactant remains in the molded product, it has a major drawback in that it impairs the functions of the molded product, such as water resistance and strength. The present inventors have already discovered a surfactant-free product by copolymerizing the above-mentioned type of amphoteric monomer compound and a normal polymerizable monomer in an aqueous medium by a two-component dropping method. Succeeded in producing soap-free emulsion resin (patent application 1973-
No. 46510). The object of the present invention is to be a soap-free type, which does not cause lumps even when the volatile content is set high, has resin particles of a single particle size, has excellent chemical and mechanical stability, and has high reactivity. An object of the present invention is to provide a copolymer that produces an emulsion resin having good properties. Still another object of the present invention is to provide a compound having two or more radically polymerizable ethylenically unsaturated groups in its molecule, in addition to the amphoteric monomer compounds of the type mentioned above and ordinary polymerizable monomers. By copolymerizing a monomer as a third component, the coating performance of an emulsion resin coating composition is further improved compared to a copolymer that does not contain the third component. According to the present invention, (a) Eq. (In the formula, R is H or CH ₃ , R ₂ is H or a C ₁ to C ₂₀ alkyl group which may contain an -SO- group, -COO- group, -O- group in the chain, _R3
is a C ₁ to C ₁₂ alkylene group or phenylene group,
A is -COOH or -SO ₃ H group. ); and (b) at least one monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule.
There is provided an emulsion resin of an amphoteric group-containing copolymer comprising a seed and (c) at least one polymerizable monomer other than the above (a) and (b). According to another aspect of the present invention, the amphoteric group-containing copolymer is obtained by copolymerizing the monomers (a), (b), and (c) in an aqueous medium by a two-part dropping method. Manufactured by Furthermore, according to the present invention, there is provided a coating composition containing the above-mentioned amphoteric group-containing copolymer as a resin emulsion, and the coating composition does not lose the excellent characteristics of the above-mentioned component monomer (a). without any trouble,
Due to the properties of component (b), the properties of the baked coating obtained from the coating composition, such as water resistance, solvent resistance, and gloss, can be further improved compared to the case where it is not contained. In the present invention, the polymerizable amino acid compound represented by the above formula [] as component (a) can also be produced by reacting a benzyl halide compound with an aminosulfonic acid compound having a primary or secondary amino group. can. Specific examples of such polymerizable amino acid compounds of the formula [] include N-(vinylbenzyl)taurine, N-(isopropenylbenzyl)taurine, 2-{N-(vinylbenzyl)}aminopropanesulfonic acid-( 1), 2-{N-(isopropenylbenzyl)}aminopropanesulfonic acid-(1), 1-{N-(vinylbenzyl)}aminopropanesulfonic acid-(2), 1-{N-(isopropenylbenzyl)} benzyl)}aminopropanesulfonic acid-(2), 3-{N-(vinylbenzyl)}aminobutanesulfonic acid-(2), 3-{N-(isopropenylbenzyl)}aminobutanesulfonic acid-(2) , 2-{N-(vinylbenzyl)}aminobutanesulfonic acid-(1), 2-{N-(isopropenylbenzyl)}aminobutanesulfonic acid-(1), 1-{N-(vinylbenzyl)}amino -2-
Methylpropanesulfonic acid-(2), 1-{N-(isopropenylbenzyl)}amino-2-methylpropanesulfonic acid-(2), 3-{N-(vinylbenzyl)}aminopentanesulfonic acid-(2) ), 3-{N-(isopropenylbenzyl)}aminopentanesulfonic acid-(2), 4-{N-(vinylbenzyl)}amino-2-
Methylpentanesulfonic acid-(3), 4-{N-(isopropenylbenzyl)}amino-2-methylpentanesulfonic acid-(3), 3-{N-(vinylbenzyl)}aminopropanesulfonic acid-(1) ), 3-{N-(isopropenylbenzyl)}aminopropanesulfonic acid-(1), 4-{N-(vinylbenzyl)}aminobutanesulfonic acid-(2), 4-{N-(isopropenylbenzyl) )}aminobutanesulfonic acid-(2), 4-{N-(vinylbenzyl)}aminobutanesulfonic acid-(1), 4-{N-(isopropenylbenzyl)}aminobutanesulfonic acid-(1), 5-{N-(vinylbenzyl)}aminopentanesulfonic acid-(1), 5-{N-(isopropenylbenzyl)}aminopentanesulfonic acid-(1), 10-{N-(vinylbenzyl)}amino Decanesulfonic acid-(1), 10-{N-(isopropenylbenzyl)}aminodecanesulfonic acid-(1), N-methyl-N-(vinylbenzyl)taurine, N-methyl-N-(isopropenylbenzyl) )
Taurine, N-ethyl-N-(vinylbenzyl) taurine, N-ethyl-N-(isopropenylbenzyl)
Taurine, N-propyl-N-(vinylbenzyl) taurine, N-propyl-N-(isopropenylbenzyl) taurine, N-butyl-N-(vinylbenzyl) taurine, N-butyl-N-(isopropenylbenzyl)
Taurine, N-heptyl-N-(vinylbenzyl) taurine, N-heptyl-N-(isopropylbenzyl) taurine, N-dodecyl-N-(vinylbenzyl) taurine, N-dodel-N-(isopropenylbenzyl)
Taurine, N-heptadecyl-N-(vinylbenzyl)taurine, N-heptadecyl-N-(isopropenylbenzyl)taurine, N-(2-octadecylsulfinethyl)-
N-(vinylbenzyl)taurine, N-(2-octadecylsulfinethyl)-
N-(isopropenylbenzyl)taurine, N-(2-stearoyloxyethyl)-N-
(vinylbenzyl)taurine, N-(2-stearoyloxyethyl)-N-
(isopropenylbenzyl) taurine, 2-{N-(vinylbenzyl)-N-methyl}
Aminopropanesulfonic acid-(1), 2-{N-(isopropenylbenzyl)-N-
methyl}aminopropanesulfonic acid-(1), 2-{N-dodecyl-N-(vinylbenzyl)}
Aminopropanesulfonic acid-(1), 2-{N-dodecyl-N-(isopropenylbenzyl)}aminopropanesulfonic acid-(1), 2-{N-octadecyl-N-(vinylbenzyl)}aminopropanesulfone Acid-(1), 2-{N-(isopropenylbenzyl)-N-
octadecyl}aminopropanesulfonic acid-(1), 1-{N-methyl-N-(vinylbenzyl)}
Amino-2-methylpropanesulfonic acid-(2), 1-{N-(isopropenylbenzyl)-N-
methyl}amino-2-methylpropanesulfonic acid-(2), 3-{N-methyl-N-(vinylbenzyl)}
Aminopropanesulfonic acid-(1), 3-{N-(isopropenylbenzyl)-N-
These include methyl}aminopropanesulfonic acid (1), N-(vinylbenzyl)orthanyl acid, N-(vinylbenzyl)methanilic acid, and N-(vinylbenzyl)sulfanilic acid. In the present invention, the monomer (hereinafter abbreviated as polyfunctional monomer) having two or more radically polymerizable ethylenically unsaturated groups in the molecule of component (b) is a polyhydric alcohol. Examples include polymerizable unsaturated monocarboxylic acid esters, polymerizable unsaturated alcohol esters of polybasic acids, and aromatic compounds substituted with two or more vinyl groups. Examples of these polyfunctional monomers include the following compounds. Ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate,
Glycerol diacrylate, glycerol acroxy dimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,
1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylethane dimethacrylate, 1,1,1-trishydroxymethylethane trimethacrylate, 1,1,
1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane triacrylate, 1,1,1-trishydroxymethylpropane dimethacrylate, 1,
1,1-trishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene. In the present invention, the polymerizable monomer (c) other than the above (a) and (b) refers to a monofunctional monomer having one polymerizable group in the molecule, and is divided into the following groups. . Carboxyl group-containing monomers, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
maleic acid, fumaric acid, etc. Hydroxyl group-containing monomers, such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol,
Metaallylic alcohol etc. Nitrogen-containing alkyl acrylates or methacrylates, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like. Polymerizable amides such as acrylic amide, methacrylic amide, etc. Polymerizable nitriles, such as acrylonitrile,
such as methacrylonitrile. Alkyl acrylates or methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-
such as ethylhexyl acrylate. Polymerizable aromatic compounds, such as styrene, α-
Methylstyrene, vinyltoluene, t-butylstyrene, etc. α-olefins, such as ethylene, propylene, etc. Vinyl compounds, such as vinyl acetate, vinyl propionate, etc. diene compounds such as butadiene, isoprene, etc. These monomers (c) may be used alone or in combination. By using the above-mentioned water-soluble monomers, the concentration gradient of the Twitter monomer (i.e., the polymerizable amino acid compound of a) and the water-soluble monomer from the outer shell to the inside of the emulsion particles is created. As a result, the physical properties of the emulsion and the molded product (coating film) are improved. The copolymer according to the present invention has the above-mentioned (a) polymerizable amino acid compound, (b) polyfunctional monomer, and (c) monomer as constituent monomers. The proportion of such monomers used may be changed as appropriate depending on the stability of the emulsion resin of the copolymer and the coating film performance, and usually the polymerizable amino acid (a) is compound
It may be selected within the range of 0.2 to 30%, preferably 0.5 to 15%. If it is less than 0.2%, the dispersion stability of the emulsion particles in an aqueous medium will be impaired, and 30%
%, the water resistance of the coating film tends to be poor. In addition, the polyfunctional monomer (b) is usually contained in the total monomers,
It may be selected within the range of 0.01 to 20%, preferably 0.1 to 10%. If it is less than 0.01%, the desired physical properties of the coating film cannot be obtained. Moreover, if it exceeds 20%, the dispersion stability of the emulsion particles in the aqueous dispersion medium will be impaired. In addition, when using the above-mentioned water-soluble monomers ~ as the monomer (c), it is preferable to select these in the range of 40% or less of the total monomers.
If it exceeds 40%, the water resistance of the film tends to be poor. An emulsion resin of the copolymer is produced by polymerizing the constituent monomers in a predetermined proportion as described above in an aqueous medium in the presence of a polymerization initiator by a two-component dropping method. In addition, such polymerization is performed by dropping two liquids of the polymerizable amino acid compound (a), the polyfunctional monomer (b), and the other monomer (c) separately. However, in the case of the other water-soluble monomers (c), some or all of these may be mixed with the polymerizable amino acid compound and added dropwise. As the polymerization initiator, usual ones can be used, such as organic peroxides such as benzoyl peroxide, t-butyl peroxide, and cumene hydroperoxide, azobiscyanovaleric acid, azobisisobutyronitrile, azobis-(2 , 4-dimethyl)valeronitrile, azobis-(2-amidinopropane) hydrochloride, and other organic azo compounds, potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, and other inorganic water-soluble radical initiators; Examples include redox initiators obtained by combining an inorganic water-soluble radical initiator with sodium pyrosulfite, sodium bisulfite, divalent iron ions, etc., and these initiators can be used alone or in a mixture of two or more. . Such a polymerization initiator may be added to the reaction medium in advance, or may be added dropwise at the same time as the constituent monomers. The amount of these polymerization initiators used is usually 0.05 to 5%, preferably 0.1 to 5% based on the total monomers.
It may be selected within a range of 3%. Further, if necessary, an appropriate amount of a conventional chain transfer agent (for example, mercaptans such as lauryl mercaptan and hexyl mercaptan) may be used in combination (usually mixed with the other monomer (c)). In addition, in such polymerization, there is no problem in using a low molecular weight emulsifier or dispersant together, but since the polymerizable amino acid compound has the function of an emulsifier or dispersant (suspension stability), The use of these agents used in ordinary emulsion polymerization can be omitted. A specific example of this polymerization operation will be shown below. First, water, which is a reaction medium containing a polymerization initiator (a hydrophilic organic solvent may be added if necessary), is heated at a polymerization temperature (usually 4 to 100°C) under normal or elevated pressure in an inert gas atmosphere. ), and add the above-mentioned polymerizable amino acid compound (if necessary, a mixture with other water-soluble monomers of (c)) or its aqueous solution (a basic substance may be present if necessary). All or part of the polyfunctional monomer (b) and the other monomer (c) are added dropwise at the same time over a period of 10 to 300 minutes, and at the same temperature after the dropwise addition. It should be aged for 5 minutes to 10 hours. Viscosity of stable water dispersion (25℃)
A milky to creamy emulsion resin with a nonvolatile content of 2 to 65% is obtained at 10 to 50,000 cps. The coating composition according to the present invention has an emulsion resin of the copolymer as a main component, and specifically, the main component may be used alone or in addition to a conventional resin vehicle, such as melamine, if necessary. resin,
Aminoplast resins such as urea resins and guanamine resins, phenoplast resins, epoxy resins, etc.
Organic and inorganic coloring pigments, extender pigments, anti-rust pigments, and other additives (fillers, extenders, thickeners,
fusing agents, etc.), surfactants, PH adjusters, water,
It is prepared by mixing an appropriate amount of solvent, etc., and dispersing and mixing at room temperature. Furthermore, by introducing hydroxyl groups into the emulsion resin (specifically, using the monomer as the component (c) above) and combining it with the above aminoplast resin, better low-temperature curing properties are achieved. Furthermore, a cured coating film with good water resistance can be formed. The coating composition prepared as described above is applied to a suitable object to be coated (metal plate, wood, paper base material, plastic base material, etc.) using a conventional method to a film thickness of 5 to 500 μm. A good cured coating is formed by drying at a temperature of ~240°C for 20 seconds to 60 minutes. Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. Note that "parts" in the example sentences mean "parts by weight." Reference example 1 Add deionized water to two flasks equipped with a stirrer.
Prepare 400g of N-methyltaurine sodium salt and 300g of ethylene glycol monomethyl ether. The temperature was raised to 70°C, and a mixed solution of 153 g of (vinylbenzyl) chloride, 100 g of ethylene glycol monomethyl ether, and 0.15 g of p-nitrosophenol was added dropwise over 1 hour while stirring. At this time, add 8g of caustic soda every 10 minutes six times,
Add so that the total is 48g. Stirring was continued for a further 5 hours to complete the reaction. After adding 120 g of concentrated hydrochloric acid to the resulting reaction mixture solution, it was concentrated using a rotary evaporator to 1/3 of the initial volume. Pour the concentrated solution into 4 times the volume of acetone to precipitate the salt, and filter. Concentrate using a rotary evaporator until the amount of solvent in the filtrate is less than 30%, and pour into 5 times the volume of acetone to precipitate a pale yellow solid substance. This was recrystallized with deionized water to give the formula: N-methyl-N-(vinylbenzyl) represented by
180 g of taurine (hereinafter referred to as compound A) is obtained. Reference example 2 Add taurine to two flasks equipped with a stirrer.
Prepare 125g, 40g of caustic soda, 200g of deionized water, and 600g of ethylene glycol monoethyl ether.
While maintaining the temperature at 60℃ and stirring, add 114 g of allyl glycidyl ether and p-nitrosophenol.
Add 0.1 g of the mixture dropwise over 20 minutes, then continue stirring for 2 hours. The resulting reaction mixture solution with a pH of 9 is treated with an ion exchange resin (Amberlite IR-120) to remove Na ⁺ ions and obtain a solution with a pH of 4. When this solution is concentrated using a rotary evaporator until the solvent becomes 70% of the total solution, needle-shaped crystals are precipitated. Analysis by NMR and IR reveals that this is unreacted taurine. When the filtrate of the mixture is poured into three volumes of acetone, a brown oily substance precipitates.
After separation, vacuum drying and formula N-(2-hydroxy-3-allyloxypropyl)taurine (hereinafter referred to as compound B) represented by
Gain 96g. Example 1 216 parts of deionized water was charged into a reaction vessel equipped with a stirrer, and while stirring and maintaining the temperature at 80°C, a mixture of 4.5 parts of azobiscyanovaleric acid, 4.9 parts of triethylamine, and 45 parts of deionized water was added. solution was added. Next, at the same temperature, a first mixed solution consisting of 6 parts of Compound A, 2.4 parts of triethylamine, and 90 parts of deionized water, 156 parts of methyl methacrylate, and n-
A second mixed solution consisting of 135 parts of butyl acrylate and 3 parts of ethylene glycol dimethacrylate was simultaneously added dropwise over a period of 60 minutes. After the dropwise addition, a mixed solution of 1.5 parts of azobiscyanovaleric acid, 1.6 parts of triethylamine, and 15 parts of deionized water was added at the same temperature, and stirring was continued for 60 minutes to obtain a solution with a non-volatile content of 45%, pH of 7.8, and viscosity (at 25°C). )108cps,
An emulsion with a particle size of 0.224μ was obtained. This emulsion is free of lumps, has good mechanical stability, and when observed under an electron microscope shows a uniform particle size distribution. Furthermore, the polymer constituting this emulsion had such a high molecular weight that it could not be measured by gel permeation chromatography because it was insoluble in tetrahydrofuran. In addition,
The viscosity (25° C.) was measured using a B-type viscometer, and the particle size was measured using a light scattering method and an electron microscope. Mechanical stability was evaluated as good if no fusion occurred when one drop of the emulsion was rubbed between the thumb and forefinger five times. The same applies to the following examples. Example 2 (Reference Example) 180 parts of deionized water was charged in the same reaction vessel as in Example 1, and while stirring and maintaining the temperature at 80°C under a nitrogen gas atmosphere, 0.675 parts of potassium persulfate and 0.225 parts of sodium bisulfite were added. part was added. Then,
At the same temperature, a first mixed solution consisting of 6 parts of compound B, 30 parts of 2-hydroxyethyl acrylate, and 90 parts of deionized water, 77.4 parts of methyl methacrylate, n
-A second mixed solution consisting of 103.2 parts of butyl acrylate, 77.4 parts of styrene, and 6 parts of divinylbenzene was simultaneously added dropwise over a period of 12 minutes. After dropping, add 0.255 parts of potassium persulfate at the same temperature.
0.075 parts sodium bisulfite and deionized water
Add a mixed solution consisting of 30 parts and continue stirring for 60 minutes to obtain a solution with a non-volatile content of 45%, pH 3.0, viscosity (25℃)
An emulsion with a single particle size distribution was obtained at 88 cps and a particle size of 0.188μ. This emulsion was completely free of lumps and had good mechanical stability. Furthermore, the polymer constituting this emulsion had such a high molecular weight that it could not be measured by gel permeation chromatography because it was insoluble in tetrahydrofuran. Example 3 Into the same reaction vessel as in Example 1, 216 parts of deionized water was charged, and while stirring and maintaining the temperature at 80°C, 4.5 parts of azobiscyanovaleric acid, 4.28 parts of dimethylethanolamine, and 45 parts of deionized water were added. A mixed solution of: Then compound A6 at the same temperature
1 part, 2.1 parts of dimethylethanolamine, 6 parts of 2-hydroxyethyl acrylate, and deionized water.
A first mixed solution consisting of 90 parts, 77.4 parts of methyl methacrylate, 103.2 parts of n-butyl acrylate,
A second mixed solution consisting of 77.4 parts of styrene, 24 parts of 2-hydroxyethyl acrylate, and 6 parts of tetraethylene glycol dimethacrylate was simultaneously added dropwise over a period of 60 minutes. After the dropwise addition, a mixed solution consisting of 1.5 parts of azobiscyanovaleric acid, 1.42 parts of dimethylethanolamine, and 1.5 parts of deionized water was added at the same temperature, and stirring was continued for 60 minutes to obtain a solution with a nonvolatile content of 45%, pH 7.8, and viscosity. (25℃) 68cps,
An emulsion with a particle size of 0.148μ and a single particle size distribution was obtained. This emulsion was free of lumps and had good mechanical stability. Since the polymer constituting this emulsion was insoluble in tetrahydrofuran, its molecular weight was so high that it could not be measured by gel permeation chromatography. Examples 4 to 23 In the manufacturing method of Example 3, except that the first mixed solution and the second mixed solution having the compositions shown in Table 1 are simultaneously dropped in the respective predetermined times required for dropping,
Various emulsions (Nos. 4 to 23) were obtained according to the same method and conditions. The properties of such emulsion are shown in Table 1.

【table】

【table】

【table】

[Table] Example 24 The same method and conditions were followed as in Example 3, except that the amount of deionized water initially charged into the reaction vessel was changed to 110 parts. An emulsion with a single particle size distribution of 0.123μ was obtained. This emulsion exhibits dilatancy and B
The viscosity could not be measured using a type viscometer. Example 25 (Reference Example) A non-volatile content of 45% and a pH of 7.0 were prepared using the same method and conditions as in Example 3 except that Compound B was used in place of 6 parts of Compound A and 2.1 parts of dimethylethanolamine. 6, viscosity 36cps, particle size
An emulsion with a single particle size distribution of 0.124μ was obtained. Example 26 (Reference Example) Into the same reaction vessel as in Example 1, 216 parts of deionized water and 1.5 parts of sodium dodecylbenzenesulfonate were charged, and while stirring and maintaining the temperature at 80°C, 4.5 parts of azobiscyanovaleric acid, A mixed solution consisting of 4.28 parts dimethylethanolamine and 45 parts deionized water was added. Then, at the same temperature, 6 parts of compound B,
A first mixed solution consisting of 2.1 parts of dimethylethanolamine, 6 parts of 2-hydroxyethyl acrylate, and 90 parts of deionized water and methyl methacrylate.
744 parts, n-butyl acrylate 103.2 parts, styrene 74.4 parts, 2-hydroxyethyl acrylate 24 parts
and a second mixed solution consisting of 6 parts of ethylene glycol dimethacrylate were simultaneously added dropwise over a period of 20 minutes. After dropping, add 1.5 parts of azobiscyanovaleric acid and dimethylethanolamine at the same temperature.
After adding a mixed solution consisting of 1.42 parts and 15 parts of deionized water, stirring was continued for 60 minutes until the non-volatile content was 45%,
An emulsion with a pH of 7.7, a viscosity (25°C) of 88 cps, and a particle size of 0.180 μ was obtained. The emulsion was uniform and stable, with no lumps at all. Example 27 (Reference Example) In the production method of Example 26, instead of 1.5 parts of sodium dodecylbenzenesulfonate, the formula 1.5 parts of the compound and 0.42 parts of dimethylethanolamine
45% non-volatile content, PH7.5, viscosity (25℃)
An emulsion of 48 cps and a particle size of 0.148 μ was obtained. Example 28 (Reference example) 216 parts of deionized water was charged into the same reaction vessel as in Example 1, and while stirring and maintaining the temperature at 80°C, 4.5 parts of azobiscyanovaleric acid, 4.28 parts of dimethylethanolamine, and deionized water were added. A mixed solution consisting of 45 parts of water, 3 parts of Compound B, 3 parts of 2-hydroxyethyl acrylate and 45 parts of deionized water were added. Then, at the same temperature, the compound
A first mixed solution consisting of 3 parts of B, 3 parts of 2-hydroxyethyl acrylate, and 45 parts of deionized water;
A second mixed solution consisting of 78.3 parts of methyl methacrylate, 104.4 parts of n-butyl acrylate, 78.3 parts of styrene and 24 parts of 2-hydroxyethyl acrylate was simultaneously added dropwise over a period of 60 minutes.
After dropping, add azobiscyanovaleric acid at the same temperature.
After adding a mixed solution consisting of 1.5 parts of dimethylethanolamine, 1.42 parts of dimethylethanolamine, and 15 parts of deionized water, stirring was continued for 60 minutes to obtain a solution with non-volatile content of 45%, pH of 7.2, viscosity (at 25°C) of 42 cps, and particle size of 0.188 μ. An emulsion was obtained. Example 29 In 70 parts of the emulsion obtained in Example 3, 5.6 parts of hexamethoxymethylolmelamine (trade name "Cymel 303" manufactured by American Cyanamid) was dissolved in 9.2 parts of ethylene glycol monobutyl ether and 3.7 parts of deionized water. A thermosetting coating composition was prepared by gradually adding an aminoplast resin solution of 100% by weight using a lab mixer while stirring. When the above composition was applied to a steel plate to a dry film thickness of approximately 20 μm and heat-cured for 20 minutes at 100°C, 120°C, 140°C or 160°C, a transparent coating film was obtained. . As a result of extracting such a coating film with acetone for 4 hours using a Soxhlet extractor, it was found that the coating film cured at 100℃ was 86% cured at 120℃.
93% for cured coating, 96% for 140℃ cured coating and 160
99% remained in the film cured at °C. In addition, the coating film exhibited good water resistance (no abnormalities were observed after immersion in boiling water for 1 hour). Examples 30-42 In Example 29, a coating composition was prepared using the same technique and method, except that 70 parts of the emulsion of each example shown in Table 2 was used instead of the emulsion obtained in Example 3. did. The above composition was applied to a steel plate to a dry film thickness of approximately 20 μm, and heat-cured at 100°C, 120°C, 140°C or 160°C for 20 minutes each. Table 2 summarizes the percentage of the paint film remaining after time-long acetone extraction (insoluble fraction) and the appearance of the paint film when immersed in boiling water for 1 hour (only for paint films cured at 140°C). Note that Examples 41 and 42 are reference examples.

【table】

Claims (1)

[Claims] 1 (a) Formula (In the formula, R is H or CH ₃ , R ₂ is H or a C ₁ to C ₂₀ alkyl group which may contain an -SO- group, -COO- group, -O- group in the chain, _R3
is a C ₁ to C ₁₂ alkylene group or phenylene group,
A is -COOH or -SO ₃ H group. ); and (b) at least one monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule.
An emulsion resin composition obtained by copolymerizing a seed and (c) at least one polymerizable monomer other than (a) and (b) above in an aqueous medium. 2 The monomer (b) above is an ester of a polymerizable unsaturated monocarboxylic acid of a polyhydric alcohol, a polymerizable unsaturated alcohol ester of a polybasic acid, or an aromatic substituted with two or more vinyl groups. The emulsion resin composition according to claim 1, which is selected from the group of compounds of the above-mentioned group. 3 The monomer (c) above is a carboxy group-containing monomer, a hydroxy group-containing monomer, a nitrogen-containing alkyl acrylate or methacrylate, a polymerizable amide, a polymerizable nitrile, an alkyl acrylate or methacrylate, a polymerizable aromatic compound , α-
The emulsion resin composition according to claim 1 or 2, which is selected from olefin compounds, vinyl compounds, and diene compounds. 4. The emulsion resin composition according to claim 1 or 2, which contains a hydroxyl group-containing monomer as the monomer (c). 5 (a) Formula (In the formula, R is H or CH ₃ , R ₂ is H or a C ₁ to C ₂₀ alkyl group which may contain an -SO- group, -COO- group, -O- group in the chain, _R3
is a C ₁ to C ₁₂ alkylene group or phenylene group,
A is -COOH or -SO ₃ H group. ); and (b) at least one monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule.
A paint whose main component is an emulsion resin obtained by copolymerizing a seed and (c) at least one polymerizable monomer other than the above (a) and (b) in an aqueous medium. 6 The monomer in (b) above is an ester of a polymerizable unsaturated monocarboxylic acid of a polyhydric alcohol, a polymerizable unsaturated alcohol ester of a polybasic acid, or an aromatic substituted with two or more vinyl groups. The paint according to claim 5, which is selected from the group compounds. 7 The monomer in (c) above is a carboxy group-containing monomer, a hydroxy group-containing monomer, a nitrogen-containing alkyl acrylate or methacrylate, a polymerizable amide, a polymerizable nitrile, an alkyl acrylate or methacrylate, a polymerizable aromatic compound , α-
The paint according to claim 5 or 6, which is selected from olefin compounds, vinyl compounds, and diene compounds. 8. The paint according to claim 5 or 6, which contains a hydroxyl group-containing monomer as the monomer (c). 9. The paint according to claim 8, which contains an aminoplast resin.