JPS6258373B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a water-dispersed resin that is air-curable at room temperature. In recent years, water-dispersed resins have come to be widely used in paints, coatings, etc. because they are preferable to solvent-based resins in terms of environmental protection, work environment, resource saving, etc. However, there are still various performance issues. At present, it is difficult to say that they are comparable to solvent-based resins in this respect. In particular, in water-dispersed resins obtained by polymerizing monomers in the presence of emulsifiers, the molecular weight of the polymer is generally extremely large, which often causes coating defects such as pinholes. In addition to insufficient contact resistance, when a low molecular weight emulsifier is used, the emulsifier remains as it is in the film formed by the water-dispersed resin, causing problems in water resistance, weather resistance, etc. Alternatively, a radically polymerizable monomer is polymerized in an organic solvent in the presence of a polymer containing a hydrophilic compound such as carboxylic acid as a constituent unit, the resulting polymer is neutralized with a base, and water is added. A method for producing water-dispersed resin is known, but in this method,
When a large amount of water is added in the final step of adding water, the dispersion system, in which the polymer was stably dispersed in the organic solvent, generally increases in viscosity and becomes a glutinous viscous substance. In order to uniformly disperse the reaction system in water, it was necessary to apply high shearing force using a dissolver or the like. In order to prevent the above-mentioned increase in the viscosity of the polymer, it is known to reduce the amount of water added or to lower the molecular weight of the polymer, but in the former case, the original advantage as a water-dispersed resin is utilized. In the latter case as well, there was a drawback that the properties such as water resistance and weather resistance of the film formed from the resulting resin were impaired. The present invention was made in view of the current state of the water-dispersed resin described above, and has excellent storage stability and pigment miscibility.
The purpose of the present invention is to provide a water-dispersed resin having a high drying rate and a dry film having excellent water resistance, weather resistance, etc. under industrially advantageous conditions. That is, the gist of the present invention is the general formula (In the formula, R ₁ is H or CH ₃ , R ₂ is

【formula】 【formula】

【Formula】Also teeth

[Formula] R ₃ is H or CH ₃ , and m and n are integers that satisfy the following relationship. When m=1, n=2 to 5; when m=2 to 6, n=2. ) 0.5 to 50% by weight of an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group, and 1 to 30% by weight of an α/β-unsaturated carboxylic acid.
and 0 to 30% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group as a constituent unit. A method for producing a water-dispersed resin, characterized by polymerizing a polymer in an organic solvent and adding water to the obtained polymer, and the general formula (In the formula, R ₁ is H or CH ₃ , R ₂ is

【formula】 【formula】

【Formula】Also teeth

[Formula] R ₃ is H or CH ₃ , and m and n are integers that satisfy the following relationship. When m=1, n=2 to 5; when m=2 to 6, n=2. ) 0.5 to 50% by weight of an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group, and 1 to 30% by weight of an α/β-unsaturated carboxylic acid.
and 0 to 30% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group as a constituent unit. A method for producing a water-dispersed resin, which comprises polymerizing a polymer in a hydrophilic organic solvent containing 45% by weight or less of water, and adding water to the obtained polymer. Among the esters of acrylic acid or methacrylic acid having a cyclic unsaturated group used in the present invention, the cyclic unsaturated group is a dicyclopentenyl group.

As a specific example of the ester represented by the formula, when m in the above general formula is 1, 2-
Dicyclopentenoxyethyl acrylate 2-dicyclopentenoxyethyl methacrylate, 2-dicyclopentenoxypropyl (meth)
Acrylate (this means 2-dicyclopentenoxypropyl acrylate and 2-dicyclopentenoxypropyl methacrylate. The same applies hereinafter), 3-dicyclopentenoxyisobutyl (meth)acrylate, 3-dicyclopene Examples include tenoxyneopentyl (meth)acrylate, etc.
When m is 2 to 6, diethylene glycol mono-dicyclopentenyl ether acrylate Diethylene glycol = mono-dicyclopentenyl ether methacrylate, triethylene glycol = mono-dicyclopentenyl ether (meth)acrylate, tetraethylene glycol =
Examples include mono-dicyclopentenyl ether (meth)acrylate, pentaethylene glycol mono-dicyclopentenyl (meth)acrylate, and hexaethylene glycol mono-dicyclopentenyl ether (meth)acrylate. Further, as the cyclic unsaturated group possessed by the ester represented by the above general formula, in addition to the dicyclopentenyl group, for example,

【formula】

【formula】

Examples include [Formula]. Among these esters, 2-dicyclopentenoxyethyl (meth)acrylate is preferably used in that a water-dispersed resin with excellent water resistance can be obtained. The water solubility increases and the water dispersibility of the resin finally obtained increases. The ester is generally tricyclo[5.2.
1.0 ^2,6 ]-3-decenol (common name, dicyclopentenyl alcohol,

[Formula]), tricyclo[5.2.1.0 ^2,6 ]methyl-3-decen-ol

[Formula] cyclopenten-1-ol, 2-methyl-cyclopenten-1-ol, cyclohexen-1-ol, 2-methylcyclohexen-1-ol, bicyclo[2.2.
1]-2-heptenol, bicyclo[2.2.
1] It is produced by a method in which a product obtained by reacting an alcohol such as -3-methyl-2-heptenol with ethylene oxide, propylene oxide, etc. is further reacted with (meth)acrylic acid to esterify it. The vinyl copolymer used in the present invention contains the above-mentioned ester in an amount of 0.5 to 50% by weight (hereinafter, % refers to % by weight). If it is less than 0.5%, the water-dispersed resin obtained will have poor air curing properties, and therefore only a film with poor water resistance can be formed, and the storage stability of the water-dispersed resin will not be exhibited. On the other hand, if it is more than 50%, the film formed by the water-dispersed resin is likely to be colored, resulting in poor weather resistance. Further, the vinyl copolymer contains α/β-unsaturated carboxylic acid as a structural unit in an amount of 1 to 30% by weight so as to have hydrophilicity, and generally has an oxidation degree of 10 to 200. The amount of unsaturated carboxylic acid depends on the amount of the compound containing an unsaturated group and a hydroxyl group, which will be described later, but if it is less than 1% by weight, the radically polymerizable monomer is added in the presence of such a vinyl copolymer. The stability of the water-dispersed resin obtained after polymerizing the polymer becomes poor, and if the amount exceeds 30% by weight, the film formed by the water-dispersed resin will have poor water resistance. As such α/β-unsaturated carboxylic acids, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cylindrical acid, maleic acid, fumaric acid, etc. are preferably used. Furthermore, the vinyl copolymer may contain a compound containing a polymerizable unsaturated group and a hydroxyl group as a structural unit so as to have hydrophilicity and a nonionic moiety. Specific examples of this unsaturated compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, allyl alcohol, and the like. The amount of the unsaturated compound used in the vinyl copolymer depends on the amount of the carboxylic acid, but in general, if it is more than 30% by weight, the water resistance of the film formed by the water-dispersed resin will be poor.
% by weight or less. Vinyl copolymers have a weight average molecular weight of 500~
150,000, preferably in the range of 1,000 to 100,000. If the weight average molecular weight is less than 500, the film formed by the water-dispersed resin will not have sufficient water resistance.
If it is larger than 150,000, the radically polymerizable monomer is polymerized in the presence of a neutralized product obtained by adding a base to this copolymer, and then water is added to stabilize the polymer in an organic solvent. Even if an attempt is made to reverse the dispersion system, which was previously dispersed in water, into a dispersion system in which the polymer is stably dispersed together with the solvent in water (hereinafter, this change in the state of the dispersion system is referred to as phase inversion), the viscosity will change. This becomes extremely expensive, and requires an extra step to mechanically apply a high shearing force for forced dispersion. In the present invention, the vinyl copolymer contains, in addition to the above-mentioned ester, α/β-unsaturated carboxylic acid, and a compound containing an unsaturated group and a hydroxyl group, 98.5% by weight of other appropriate vinyl monomers as structural units. % or less. Specific examples of such vinyl monomers include (meth)acrylic acid alkyl esters such as butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, as well as glycidyl (meth)acrylate, styrene, α-methylstyrene, Alkenylbenzenes such as vinyltoluene, vinyl acetate, acrylonitrile, etc. can be mentioned. The constituent units are an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group as described above, an α/β-unsaturated carboxylic acid, an unsaturated compound containing a hydroxyl group, and other monomers as necessary. The vinyl copolymer can be obtained by copolymerizing each monomer according to a conventionally known method. In the method of the present invention, a radically polymerizable monomer is polymerized by a conventional method in an organic solvent in the presence of a neutralized product obtained by neutralizing such a vinyl copolymer with a base (i.e., by a solution polymerization method). A radically polymerizable monomer is polymerized by a method of polymerizing a radically polymerizable monomer), and water is generally added in an amount of 1 to 20 times the weight of the organic solvent to the thus obtained polymer. Specific examples of organic solvents used when polymerizing the radically polymerizable monomer described below in the presence of a neutralized vinyl copolymer include propanol, methyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, acetone,
Examples include methyl ethyl ketone, ethyl acetate, etc.
These may be used alone or in a suitable mixture, and the total amount, including the solvent required for producing the vinyl copolymer, is usually 20 parts by weight or more based on 100 parts by weight of the final polymer. To neutralize a vinyl copolymer with a base, the copolymer is usually dissolved in the above-mentioned solvent and then ammonia such as ammonia, trimethylamine, triethylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, etc.
This is carried out by adding a base such as an alkylamine, alcoholamine, or morpholin. The amount of base added is usually such that more than half of the carboxyl groups in the vinyl copolymer are neutralized. In the second invention of the method of the present invention, radicals are generated in a hydrophilic organic solvent containing 45% by weight or less of water in the presence of a neutralized product obtained by neutralizing such a vinyl copolymer with a base. A polymerizable monomer is polymerized by a conventional method (that is, a radically polymerizable monomer is polymerized by a so-called solution polymerization method), and the resulting polymer is generally added to the final water-dispersed resin. Water is added so that the weight of water is 1 to 20 times that of the organic solvent. As the hydrophilic organic solvent, the solvents listed above can be employed. In the above, the amount of water in these hydrophilic solvents containing water is set to 45% by weight or less because if it exceeds 45% by weight, it becomes difficult to control the molecular weight of the polymer, so it is more preferable. is 3-30% by weight
Used within the range of Water may be added in portions before and during polymerization of the radically polymerizable monomer. In addition, in order to neutralize the vinyl copolymer with a base in the second invention, the copolymer is usually dissolved in the above-mentioned solvent or a solvent containing water, and then, for example, ammonia,
trimethylamine, triethylamine, dimethylethanolamine, diethylethanolamine,
This is carried out by adding ammonia such as triethanolamine, a base such as an alkylamine, an alcoholamine, or a morpholine. The amount of base added is usually such that more than half of the carboxyl groups in the vinyl copolymer are neutralized. In the present invention, the radically polymerizable monomer polymerized in the presence of a neutralized vinyl copolymer is not particularly limited, but specific examples include methyl (meth)
Acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 8(9)-acryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene, 8
(9)-Methacryloxytricyclo[5.2.1.0
In addition to (meth)acrylic acid alkyl esters and glycidyl (meth)acrylates such as ^2,6 ]-4-decene, alkenylbenzenes such as styrene, α-methylstyrene, and vinyltoluene, as well as vinyl acetate, vinylpyridine, butadiene, Examples include isoprene, chloroprene, acrylonitrile, methacrylonitrile, etc., and a particularly preferred example is 8(9)-(meth)acryloxytricyclo[5.
2.1.0 ^2,6 ]-4-decene and the like.
These may be used alone or as a mixture of two or more. If necessary, these monomers may be supplemented with small amounts of acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, acrylamide, methacrylamide, dimethylaminoethyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide, 2-hydroxy Hydrophilic monomers such as ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid may be used in combination, and a small amount of ethylene glycol di Polyfunctional crosslinking agents such as polyacrylates such as methacrylate, tetraethylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and diallyl phthalate. May be used together. As the radically polymerizable monomer, a (meth)acrylic acid ester having a cyclic unsaturated group, which is used as a constituent component of the vinyl copolymer of the present invention, may also be used, and in this case, the amount used is particularly limited. Generally 50% by weight of total radical monomers
The following are preferred. As the type of monomer, 2-dicyclopentenoxyethyl (meth)acrylate and the like are particularly preferred since the film finally formed has excellent water resistance. The radical polymerization initiator used in the polymerization of these monomers is particularly limited, such as benzoyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide, cumene hydroperoxide, and azobisisobutyronitrile. Any conventionally known material may be used without any limitation. The amount of the neutralized vinyl copolymer used is approximately 5 to 95% of the total amount of the neutralized product and the radically polymerizable monomer.
% by weight, preferably about 5-80% by weight. If the amount of neutralized product used is too small, the water-dispersed resin obtained by polymerizing monomers in the presence of the neutralized product will lack stability.
Moreover, it does not have sufficient air curability, and if the amount is too high, the film formed by the water-dispersed resin will lack water resistance. The thus obtained neutralized vinyl copolymer contains a graft copolymer obtained by graft-polymerizing a portion of the radically polymerizable monomer to the neutralized product. However, the weight average molecular weight of such a graft copolymer is
It should be in the range of 5000 to 300000. If the weight average molecular weight is less than 5,000, the curing speed of the water-dispersed resin obtained will be slow and the final coating film will not have sufficient water resistance, while if it is greater than 300,000, the viscosity will be too high. This is because there are disadvantages such as poor painting workability and the need to reduce the resin concentration unnecessarily. The amount of water added to the polymer made of such a neutralized vinyl copolymer is appropriate, but in order to take advantage of the inherent advantages of water-dispersed resins such as environmental protection and resource saving, the amount of water should be increased. It is preferable to increase the amount of organic solvent and reduce the amount of organic solvent. In the method of the present invention, a water-dispersed resin with good dispersion stability can be obtained even if the ratio of water/organic solvent in the volatile component is 1 or more. Add and use.
The expression of this good dispersion stability is due to the graft polymerization in which a radically polymerizable monomer is graft-polymerized to a neutralized vinyl copolymer whose constituent component is a (meth)acrylic acid ester having a unique cyclic unsaturated group. This is thought to be caused by the copolymer. That is, it is thought that the dispersion stability of the water-dispersed resin obtained by the method of the present invention is developed by graft polymerization of the monomer to the above-mentioned vinyl copolymer to some extent. It is presumed that the cyclic unsaturated group allows monomers to be grafted easily and smoothly, resulting in improved dispersion stability. The solid content of the water-dispersed resin obtained by the present invention is usually 30 to 70% by weight. The method of the present invention is configured as described above, and the first
In the invention, the monomer is polymerized in an organic solvent in the presence of a neutralized product of the vinyl copolymer, so the dispersion of the resin is lower than when using a vinyl copolymer that has not been neutralized with a base. The degree of thickening during phase inversion by gradually adding water to the system is significantly reduced. Therefore, according to the present invention, phase inversion is easy even when the molecular weight of the neutralized product of the vinyl copolymer is large, and in some cases, it is possible to omit a forced dispersion step using a resolver or the like. In the second invention, the monomer is polymerized in a hydrophilic organic solvent containing 1 to 45% by weight of water in the presence of the neutralized product of the vinyl copolymer, so that the monomer is not neutralized with a base. Compared to when a vinyl copolymer is used, the degree of viscosity increase during phase inversion by gradually adding water to the resin dispersion system is significantly reduced, and when the monomer is mixed in an organic solvent that does not contain any water, Compared to the case of polymerization, the degree of viscosity increase during phase inversion is further reduced. Therefore, according to the present invention, phase inversion is easy even when the molecular weight of the neutralized product of the vinyl copolymer is large, and in some cases, it is possible to omit a forced dispersion step using a resolver or the like. The water-dispersed resin obtained by the first and second inventions of the method of the present invention has good storage stability, mechanical stability, and pigment miscibility due to excellent dispersion stability, and further has the above-mentioned cyclic saturated groups. Because it is air curable, it has high air curability, and the film that is finally formed has excellent water resistance and weather resistance. In addition, when the water-dispersed resin produced by the method of the present invention is used as a paint for room temperature or forced drying, a metal desiccant such as cobalt naphthenate, lead naphthenate or zirconium octylate may be used, and an amino acid curing agent may be used. Of course, it may be modified by mixing resins, epoxy resins, etc. In this case, there are cases in which the clear paint composition is used without adding any pigments, but in many cases, pigments that are generally used for paints and can be dispersed in water are added. Used as a water-based paint composition. Specific pigments include inorganic pigments such as titanium oxide, zinc oxide, barium metaborate, calcium carbonate, clay, Venkara, white carbon, and carbon black;
Examples include organic pigments such as azo pigments and phthalocyanine pigments. The present invention will be explained below with reference to Examples. In the Examples below, the acid value and molecular weight of the polymer, the storage stability of the coating material, and the various physical properties of the coating film obtained therefrom were evaluated as follows. (1) Acid value: phenolphthalein as an indicator
It was determined by neutralization titration with a 0.1N potassium hydroxide ethanol solution. (2) Weight average molecular weight: gel permeation
Determined by chromatographic method. (3) Hydroxyl value: The amount of acetic acid required to esterify the hydroxyl groups in 1 g of solid sample was determined, and expressed as the number of mg of potassium hydroxide required to neutralize this. (4) Storage stability of paint: Paint A was prepared by adding 40 g of titanium oxide and 1.2 g of 12% zirconium octylate to 100 g of a water-dispersible resin with a solid content of 40% and stirring at high speed. This paint was placed in a sealed container and allowed to stand at 50°C for 7 days, and then the presence or absence of coagulation, lumps, and viscosity were observed. If there were no abnormalities, it was evaluated as good. If this result is good, it is considered that the storage stability of the water-dispersed resin itself is also good. (5) Physical properties of the paint film: Paint A was applied to a zinc-treated steel plate by air spray to a film thickness of 40 μm, left at room temperature for 20 minutes, then dried at 80°C for 20 minutes and then at room temperature for 5 days. A coating film was obtained, and the physical properties of the coating film were measured in accordance with JISK5400. (a) Water resistance A coated steel plate was immersed at 20°C for 10 days, and the coated steel plate was rated as good if it showed no blistering, peeling, or rust. (b) Impact resistance: 500 on Dupont impact tester
A weight of g was used. (c) Gloss 60°/60° specular gloss was measured. (d) Adhesion 10 x 10 squares of 1 m/m were made with a razor, and the results of a peel test using Sellotape were expressed as the remaining percentage. (6) Paint workability (A) After applying the above paint A to a zinc-treated steel plate using an airless sprayer and leaving it at room temperature for 20 minutes.
After drying at 80°C for 20 minutes, the condition of the underarms and holes in the paint film was observed. The critical film thickness (μ) at which these coating film defects do not occur is indicated. (7) Solid content: The ratio of the residual weight to the weight before drying when 1 g of water-dispersed resin was heated and dried was expressed as a percentage. (8) Phase inversion property: Evaluation was made based on the degree of viscosity increase when the phase inversion step was performed using a high-speed stirrer. A case where an aqueous dispersion was easily obtained without significant thickening was evaluated as good. (9) Pigment miscibility: 40 g of titanium oxide was added to 50 g of a water-dispersed resin with a solid content of 40%, and after stirring at high speed, a pigment paste was prepared, and the dispersion miscibility of the pigment was evaluated using a grind gauge. A dispersibility of 5μ or less was considered good. (10) Painting workability (B): Paint A was applied to a zinc-treated steel plate using airless spray, left at room temperature for 20 minutes, dried at 80°C for 20 minutes, left at room temperature for 1 hour, and the paint film After 24 hours, water droplets were placed on the paint, and the paint film was evaluated for blistering, peeling, and adhesion. This is an evaluation of the initial water resistance of the paint film, and is used to evaluate the drying properties of the paint. Reference Example 1 100g of butyl cellosolve was placed in a separable flask equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen introduction tube, and the mixture was heated at 135°C in a nitrogen stream.
72 g of 2-dicyclopentenoxyethyl acrylate in which 8 g of azoisobutyronitrile was dissolved, 31 g of methacrylic acid, 50 g of butyl methacrylate,
47 g of 2-ethylhexyl acrylate and 4 g of lauryl mercaptan were added dropwise over 3 hours, and the mixture was further stirred for 2 hours to carry out a copolymerization reaction.
100, and a butyl cellosolve solution of a vinyl copolymer having a weight average molecular weight of 9,350 was obtained. The composition ratio of the vinyl copolymer was almost the same as the charge ratio of various polymerizable monomers. Reference Examples 2 to 5 Type and amount of each monomer, base,
A butyl cellosolve solution of a vinyl copolymer having the acid value, hydroxyl value, and weight average molecular weight shown in Table 1 was prepared in the same manner as in Reference Example 1, except that the amounts of the polymerization initiator, solvent, etc. and the reaction temperature were changed as shown in Table 1. I got it. The composition ratio of the vinyl copolymer was almost the same as the charge ratio of each polymerizable monomer.

[Table] Example 1 60 g of the copolymer solution obtained in Reference Example 1 was charged with 80 g of butyl cellosolve and 4.4 g of dimethylethanolamine into a Sebarapuru flask similar to Reference Example 1, and the temperature was raised to 100°C after purging with nitrogen. After that, 120 g of butyl methacrylate in which 1 g of azoisobutyronitrile was dissolved, 20 g of butyl acrylate, 8 (or 9)-acryloxy-tricyclo [5.2.
A mixed solution of 20 g of 1.0 ^2,6 ]-4-decene was added dropwise into the flask over a period of 3 hours, followed by stirring for 5 hours to carry out homogeneous polymerization to obtain a polymer solution. Next, 200 g of pure water was added to this polymer and stirred to obtain a milky white water-dispersed resin. The degree of neutralization of this water-dispersed resin with dimethylethanolamine is 70%, and the weight average molecular weight of the polymer is
72,000, the acid value of the polymer was 20, the solid content was 39.8%, and the water/organic solvent ratio in the volatile components was 2.0.
Further, the step of adding pure water and inverting the phase was easily carried out without any significant increase in viscosity. Table 3 shows the physical properties of the coating film etc. obtained from this water-dispersed resin. Examples 2 to 4 The procedure was the same as in Example 1, except that the types and amounts of each monomer, vinyl copolymer solution, catalyst, butyl cellosolve, water, etc., and the reaction temperature were changed as shown in Table 2. A water-dispersed resin having the physical properties shown in Table 2 was obtained. However, in Examples 3 and 4, the monomers were polymerized in an organic solvent containing water in the presence of the vinyl copolymer. Table 3 shows the physical properties of the coating film etc. obtained from this water-dispersed resin.

【table】

【table】

[Table] Comparative Example 1 As shown in Table 2, 80 g of butyl cellosolve was added to 60 g of the vinyl copolymer obtained in Reference Example 5, the atmosphere was replaced with nitrogen, the temperature was raised to 120°C, and then azoisobutyronitrile was added.
120g of butyl methacrylate dissolved in 1.0g,
A mixed solution of 20 g of butyl acrylate and 20 g of styrene was added dropwise over a period of 3 hours, followed by stirring for 5 hours to carry out homogeneous polymerization to obtain a polymer solution. Next, add 4.4 g of dimethylethanolamine and 200 g of pure water to this polymer.
When adding g, the viscosity of the dispersion system increased significantly and the whole became a sticky substance, so the dispersion system was taken out and placed in another container, and an extremely strong shearing force was applied for a long time using a resolver. forced to disperse. The degree of neutralization of this water-dispersed resin is 70%, the weight average molecular weight of the polymer is 72000, the acid value is 20, and the solid content is 39.80%.
The water/organic solvent ratio in the volatile components was 2.0.
Table 3 shows the physical properties of the paint etc. obtained by adding a predetermined pigment to this. The pigment miscibility was insufficient, the storage stability of the paint was poor, and the water resistance of the paint was poor. Comparative Example 2 Using the vinyl copolymer solution of Reference Example 6 and the monomer composition shown in Table 2, a water-dispersed resin was obtained in the same manner as in Comparative Example 1. The properties and physical properties of the paint etc. are shown in Tables 2 and 3.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ is H or CH ₃ , R ₂ is [Formula] [Formula] [Formula] or [Formula] R ₃ is H or CH ₃ , and m and n are integers that satisfy the following relationship. When m = 1, n = 2 to 5; when m = 2 to 6, n = 2.) 0.5 to 50% by weight of an acrylic acid or methacrylic acid ester having a cyclic unsaturated group; α/β-unsaturated carboxylic acid 1-30% by weight
and 0 to 30% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group as a constituent unit. 1. A method for producing a water-dispersed resin, which comprises polymerizing a polymer in an organic solvent and adding water to the obtained polymer. 2. The manufacturing method according to claim 1, wherein the ester of acrylic acid is 2-dicyclopentenoxyethyl acrylate or 2-dicyclopentenoxyethyl methacrylate. 3. The manufacturing method according to claim 1 or 2, wherein the vinyl copolymer further contains an α/β-unsaturated carboxylic acid alkyl ester or alkenylbenzene as a constituent unit. 4 The radically polymerizable monomer is 2-dicyclopentenoxyethyl acrylate, 2-dicyclopentenoxyethyl methacrylate, 8-acryloxytricyclo[5.2.1.0 ^2,6 ]-4- Decene, 9-acryloxytricyclo[5.2.1.
0 ^2,6 ]-4-decene, 8-methacryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene and 9-methacryloxytricyclo[5.2.1.0
Claims 1 to 3 contain at most 50% by weight of one or more ester-based radically polymerizable monomers selected from the group consisting of ^2,6 ]-4-decene. The manufacturing method described in any of the above. 5 General formula (In the formula, R ₁ is H or CH ₃ , R ₂ is [Formula] [Formula] [Formula] or [Formula] R ₃ is H or CH ₃ , and m and n are integers that satisfy the following relationship. When m = 1, n = 2 to 5; when m = 2 to 6, n = 2.) 0.5 to 50% by weight of an acrylic acid or methacrylic acid ester having a cyclic unsaturated group; α/β-unsaturated carboxylic acid 1-30% by weight
and 0 to 30% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group as a constituent unit. 1. A method for producing a water-dispersed resin, which comprises polymerizing a polymer in a hydrophilic organic solvent containing 45% by weight or less of water, and adding water to the obtained polymer. 6. The manufacturing method according to claim 5, wherein the ester of acrylic acid is 2-dicyclopentenoxyethyl acrylate or 2-dicyclopentenoxyethyl methacrylate. 7. The manufacturing method according to claim 5 or 6, wherein the vinyl copolymer further contains an α/β-unsaturated carboxylic acid alkyl ester or alkenylbenzene as a constituent unit. 8 The radically polymerizable monomer is 2-dicyclopentenoxyethyl acrylate, 2-dicyclopentenoxyethyl methacrylate, 8-acryloxytricyclo[5.2.1.0 ^2,6 ]-4- Decene, 9-acryloxytricyclo[5.2.1.
0 ^2,6 ]-4-decene, 8-methacryloxytricyclo[5.2.1.0 ^2,6 ]-4-decene and 9-methacryloxytricyclo[5.2.1.0
Claims 5 to 7 contain 50% by weight or less of one or more ester-based radically polymerizable monomers selected from the group consisting of ^2,6 ]-4-decene. The manufacturing method described in any of the above.