JPS6239623B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a water-dispersed resin that has the property of gradually curing due to oxidation by oxygen in the air when water or a solvent is evaporated and the resin is left in the air (hereinafter referred to as air curable). In recent years, water-dispersed resins have come to be widely used in paints, adhesives, etc. because they are preferable to solvent-based resins in terms of environmental protection, work environment, resource saving, etc. However, they are still lacking in terms of performance. At present, it is difficult to say that they are comparable to solvent-based resins in various respects. 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. , there are problems with 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 to the dispersion system in the final water addition step, the viscosity of the dispersion system, in which the polymer was stably dispersed in the organic solvent, generally increases significantly and becomes viscous. In order to uniformly disperse such a dispersion system in water, it was necessary to take more steps and apply higher shearing force. 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. On the other hand, as a method for obtaining air-curable water-dispersible resins, for example, a method of modifying alkyd resin with semi-drying oil or drying oil is known, but the resulting oil-modified resin has poor weather resistance and drying speed. Further improvement was desired in this respect. The present invention has been made in view of the current state of the water-dispersed resins mentioned above, and provides an industrially advantageous water-dispersed resin that has excellent storage stability, a high drying rate, and a dry film that has excellent water resistance, weather resistance, etc. The purpose is to provide this service under the following conditions. That is, the gist of the present invention is that the general formula

[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 , m is an integer from 0 to 6, and n is an integer satisfying the following relationship. m=1
When n=2 to 5, when m=2 to 6, n=
2. ) 1 to 50% by weight of an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group;
A vinyl copolymer whose constituent units are 1 to 30% by weight of α/β-unsaturated carboxylic acid and 0 to 50% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group, and a higher unsaturated fatty acid or higher unsaturated fatty acid. Neutralizing the esterification reaction product with a saturated fatty acid ester, polymerizing a radically polymerizable monomer in an organic solvent in the presence of the thus obtained neutralized product, and adding water to the obtained polymer. A method for producing a water-dispersed resin is provided. 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 of [Formula], when m in the general formula is 0, 8(9)-
Acryloxytricyclo [5.2.1.0 ² , ⁶ ]
-4-decene (this is 8-acryloxytricyclo[5.2.1.0 ² , ⁶ )] -4-decene and 9-acryloxytricyclo[5.2.1.0 ² , ⁶ ] -
It means both 4-decene. same as below. ), 8(9)
-Methacryloxytricyclo[5.2.1.0
² , ⁶ ]-4-decene (universal name, dicyclopentenyl methacrylate), 8(9)-acryloxytricyclo[5.2.1.0 ² , ⁶ ]-2-methyl-4-
Decene, 8(9)-acryloxytricyclo[5.
2.1.0 ² , ⁶ ]-3-methyl-4-decene, 8
(9)-Methacryloxytricyclo[5.2.1.0
Examples thereof include ^{2,6 ]} -2-methyl-decene, 8(9)-methacryloxytricyclo[ ^{5.2.1.02,6 ]} -3-methyl-4-decene, and the like. Moreover, when m in the above general formula is 1, 2-
Dicyclopentenoxyethyl acrylate

[Formula] 2-dicyclopentenoxyethyl methacrylate, 2-
Dicyclopentenoxypropyl (meth)acrylate (this means 2-dicyclopentenoxypropyl acrylate and 2-dicyclopentenoxypropyl methacrylate. The same applies hereinafter), 3-
Examples include dicyclopentenoxyisobutyl (meth)acrylate, 3-dicyclopentenoxyneopentyl (meth)acrylate, and m is 2 to 6.
In the case of 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】

[Formula] etc., and as a specific example when m=0,
3(4)-acryloxy-1-cyclopentene, 3(4)
-Methacryloxy-1-cyclopentene, 4(5)-
Acryloxy-1-cyclohexene, 4(5)-methacryloxy-1-cyclohexene, 5(6)-acryloxybicyclo[2.2.1]-2-heptene,
5(6)-Methacryloxybicyclo[2.2.1]-
Examples include 2-heptene. Among these esters, 8(9)-acryloxytricyclo[5.2.1.0 ² , ⁶ ]-4- can be used to obtain a resin composition with excellent air curability.
Decene, 8(9)-methacryloxytricyclo[5.
2.0 ² , ⁶ ]-4-decene and 2-dicyclopentenoxyethyl (meth)acrylate are particularly used. The ester in which m is 1 to 6 in the general formula 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] Manufactured 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. be done. The vinyl copolymer used in the present invention contains the ester represented by the above general formula in a range of 1 to 50% by weight (hereinafter, % means % by weight). If it is less than 1%, the resulting water-dispersed resin will have poor air curability, 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. In addition, the vinyl copolymer in the present invention contains 1 to 30 α/β-unsaturated carboxylic acids so as to have hydrophilicity.
% and generally has an acid value 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.
%, the stability of the water-dispersed resin obtained after polymerizing the radically polymerizable monomer in the presence of such a vinyl copolymer deteriorates, and when it exceeds 30%, the water-dispersed resin becomes unstable. The film formed by this will have poor water resistance. Examples of such α/β-unsaturated carboxylic acids include acrylic acid, methacrylic acid,
itaconic acid, crotonic acid, cylindrical acid, maleic acid,
Fumaric acid and the like are preferably used. Furthermore, the vinyl copolymer has hydrophilic and nonionic moieties, and in order to enable an esterification reaction with higher unsaturated fatty acids, etc., which will be described later, a compound containing a polymeric unsaturated group and a hydroxyl group is added. It may be contained as a structural unit. Specific examples of this unsaturated compound include 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth)
Examples include acrylate and allyl alcohol. The amount of the unsaturated compound used in the vinyl copolymer is generally kept at 50% or less since if it exceeds 50%, the water resistance of the film formed by the water-dispersed resin will be poor. In the present invention, in addition to the ester represented by the above general formula, the α/β-unsaturated carboxylic acid, and the compound containing an unsaturated group and a hydroxyl group, 93% of other appropriate vinyl monomers are used as constituent units. It may be contained within the following range. 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. A vinyl copolymer whose constituent units are an ester of acrylic acid or methacrylic acid represented by the above general formula, an α/β-unsaturated carboxylic acid, an unsaturated compound having a hydroxyl group, and other monomers used as necessary. The combination can be obtained by copolymerizing each monomer according to a conventionally known method, but a solution polymerization method is particularly suitable. In the present invention, the vinyl copolymer is reacted with a higher unsaturated fatty acid or a higher unsaturated fatty acid ester to undergo an esterification reaction (this means both an esterification reaction and a transesterification reaction in the narrow sense of the reaction). The resulting product is called an esterification reaction product.However, if the vinyl copolymer has a hydroxyl group, it can be reacted with either higher unsaturated fatty acids or higher unsaturated fatty acid esters. good. When the vinyl copolymer does not contain a hydroxyl group, for example, an ester of an alcohol having an epoxy group and a higher unsaturated fatty acid is preferably used, or an ester in which the alcohol residue is a higher unsaturated alkyl is used. Is possible. Examples of higher unsaturated fatty acids used in the present invention include alkenoic acids such as oleic acid, alkadienoic acids such as linoleic acid, alkapolyenoic acids such as hylagonic acid, linolenic acid, gamma-linolenic acid, and eleostearic acid, and lycanic acid. Examples include keto acids, and linoleic acid and linolenic acid are preferably used. These can be used alone or as a mixture, but
Generally, glycerides exist in drying oils and semi-drying oils, so for example, soybean oil fatty acids obtained by hydrolyzing soybean oil, which is a semi-drying oil, or dehydrated castor oil, which is a drying oil, can be obtained by hydrolyzing soybean oil. Commercially available mixtures of various higher fatty acids, such as dehydrated castor oil fatty acids, can be used. In the present invention, higher unsaturated fatty acid ester refers to an ester having a carbon-carbon unsaturated bond and preferably having 9 or more carbon atoms in a monocarboxylic acid residue or 9 or more carbon atoms in an alcohol residue, but generally Esters of glycerin and higher unsaturated fatty acids and esters of alcohols having an epoxy group and higher unsaturated fatty acids are preferably used. Esterified products of polyhydric alcohols such as glycerides can be used not only completely esterified products but also partially esterified products, and in the case of triglycerides and diglycerides, unsaturated fatty acid residues may be present in certain ester bond parts. For example, other ester bonding moieties may contain saturated fatty acid residues such as lauric acid and stearic acid. Triesters of higher fatty acids among the above glycerides are present in fats and oils, but oils and fats containing unsaturated fatty acid esters include drying oils such as tung oil, oticica oil, and linseed oil, and synthetic drying oils such as dehydrated castor oil. , safflower oil, soybean oil, cottonseed oil, bran oil, and other semi-drying oils. Glycidyl alcohol is preferably used as the alcohol having an epoxy group, and examples of alcohols containing esters with unsaturated fatty acids include soybean oil fatty acid glycidyl ester, coconut oil fatty acid glycidyl ester, and the like. Conventionally known methods are used for the esterification reaction between the vinyl copolymer and the fatty acid or fatty acid ester. A method of appropriately heating in the presence of a compound, sodium alkoxide, acid, etc. is used. The amount of fatty acid or fatty acid ester used in the esterification reaction is such that the total amount of carboxyl groups and hydroxyl groups, if any, in the vinyl copolymer remains at least about 10% after the esterification reaction, and is usually It is used in an amount of 3 to 100 parts by weight per 100 parts by weight of the vinyl copolymer. If the amount is less than 3 parts by weight, it is difficult to achieve air curing properties, especially if the amount of ester is too small, the effect of imparting flexibility to the vinyl copolymer is poor, and if it exceeds 100 parts by weight, the resulting water The weather resistance of the dispersed resin will deteriorate. The esterification reaction product of the vinyl copolymer has a weight average molecular weight of 1,000 to 100,000, preferably 3,000 to 100,000.
A value in the range of 50000 is good. Weight average molecular weight
If it is less than 1,000, the water resistance of the film formed by the water-dispersed resin will not be sufficient, and if it is more than 100,000, the radically polymerizable monomer will be absorbed in the presence of the neutralized product obtained by adding a base to this esterification reaction product. After polymerizing the polymer, water is added to turn the dispersion system in which the polymer was stably dispersed in an organic solvent into a dispersion system in which the polymer is stably dispersed together with the solvent in water (hereinafter referred to as dispersion system). This change in state is called phase inversion.
Furthermore, an extra step is required to mechanically apply a high shearing force for forced dispersion. In the method of the present invention, such an esterification reaction product is neutralized with a base, and in the presence of the thus obtained neutralized product, a radically polymerizable monomer is polymerized in an organic solvent by a conventional method. Water is added to the 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 an appropriate mixture, and the amount is not particularly limited, but the final polymer
If the solvent required for producing the vinyl copolymer remains, the total amount is usually 10 parts by weight or more relative to 100 parts by weight. In addition, these solvents should be added in a range of 45% or less, preferably 3%.
When the monomers described below are polymerized in a system containing water in the range of ~30%, the viscosity increase in the phase inversion step described above is much more pronounced than when the monomers are polymerized in 100% organic solvent. eased. However, the amount of water is 45%
If the molecular weight exceeds 100%, it becomes difficult to control the molecular weight of the polymer. To neutralize the esterification reaction product of a vinyl copolymer with a base, the copolymer is usually dissolved in the above-mentioned solvent, and then ammonia, alkoxyamines such as trimethylamine and triethylamine, dimethylethanolamine, diethylethanolamine, triethylamine, etc. This is carried out by adding an alcohol amine such as ethanolamine or a base such as morpholine. The amount of base added is usually such that more than half of the carboxyl groups present in the vinyl copolymer esterification reaction product are neutralized. In the present invention, the radically polymerizable monomer polymerized in the presence of the above neutralized product is not particularly limited, but specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, -ethylhexyl (meth)
In addition to (meth)acrylic acid alkyl esters and glycidyl (meth)acrylates such as acrylates, alkenylbenzenes such as styrene, α-methylstyrene, and vinyltoluene, as well as vinyl acetate, vinylpyridine, butadiene, isoprene,
Examples include chloroprene, acrylonitrile, methacrylonitrile, etc., and these may be used alone or as a mixture of two or more. Furthermore, the (meth)acrylic acid ester represented by the above general formula used as a component of the vinyl copolymer can also be used, and the ester is generally used in an amount of 50% or less of the total polymerizable monomers. If necessary, small amounts of acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, acrylamide, methacrylamide, dimethylaminoethyl methacrylate, N-methylolacrylamide, N-butoxymethylacrylamide, 2- Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-acrylamide-
Hydrophilic monomers such as 2-methylpropanesulfonic acid and styrenesulfonic acid may be used in combination, and
Small amounts of polyacrylates such as ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and diallyl phthalate. A functional crosslinking agent may also be used. In addition, radical polymerization initiators include benzoyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide,
There are no particular restrictions, and any conventionally known compounds can be used, such as cumene hydroperoxide and azobisisobutyronitrile. The amount of the neutralized product used is about 5 to 95%, preferably about 5 to 80%, of the total amount of the neutralized product and the radically polymerizable monomer. If the amount of the neutralizer used is too small, the water-dispersed resin obtained by polymerizing the monomer in its presence will lack stability and will not have sufficient air curability; This is because 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 development of this good dispersion stability is mainly due to the esterification reaction between a vinyl copolymer containing a (meth)acrylic acid ester having a unique cyclic unsaturated group and a higher unsaturated fatty acid or ester. This is thought to be due to a graft copolymer in which a radically polymerizable monomer is graft-polymerized to a conjugate.
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 monomers are easily and smoothly grafted onto the cyclic unsaturated group, improving dispersion stability, and that the components in the higher fatty acids or higher fatty acid esters introduced into the vinyl copolymer have a surfactant effect. It is estimated that this contributes to the above-mentioned dispersibility. The method of the present invention is constructed as described above, and since the monomer is polymerized in an organic solvent in the presence of a neutralized product of the esterification reaction product of the vinyl copolymer, the monomer is not neutralized with a base. The degree of viscosity increase during phase inversion by gradually adding water to a resin dispersion system is significantly reduced compared to the case where a vinyl copolymer without a vinyl copolymer is used. 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.
In some cases, it is possible to omit a forced dispersion step using special means such as a resolver. In addition, the resin obtained by the method of the present invention has good storage stability and pigment miscibility due to excellent water dispersion stability, and furthermore, the resin has good storage stability and pigment miscibility due to excellent water dispersion stability, and furthermore, the resin has a cyclic incompatible group of the ester represented by the above general formula and the above fatty acid or fatty acid. Due to the air-curing property of the chain unsaturated bond portion of the ester, the air-curing rate is high, and the film 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 conventionally known metal desiccant may be used, or it may be modified by mixing with an amino resin, epoxy resin, etc. . Further, at this time, a pigment which is generally used for paints and which can be dispersed in water may be added. The present invention will be explained below with reference to Examples. In addition, in the following examples, evaluations of various physical properties, etc. were performed as follows. (1) Acid value: Determined by neutralization titration with 0.1N potassium hydroxide ethanol solution using phenolphthalein as an indicator. (2) Weight average molecular weight: Regarding the 5% tetrahydrofuran solution of the sample, 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: water-dispersed resin with solid content of 40%
Paint A was prepared by adding 40 g of titanium oxide and 1.2 g of 12% zirconium octylate to 100 g 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
The test was carried out using a weight of g, and expressed as the height of the fall of the weight. (c) Gloss 60°/60° specular gloss was measured. (d) Adhesion The results of a peel test using cellophane tape made with a razor to make 10 x 10 squares of 1 m/m are expressed as the remaining percentage. (6) Painting workability (A): Paint A was applied to a zinc-treated steel plate by airless spraying, left at room temperature for 20 minutes, and then dried at 80°C for 20 minutes. The condition of the coating film's underarms and pinholes was observed. The limit film thickness (μ) at which no defects occur in the coating film is indicated. Painting workability (B): After the above coating film was left at room temperature for 1 hour, water droplets were placed on it and the coating film was evaluated for blistering, peeling, and adhesion after 24 hours. This is an evaluation of the initial water resistance of the paint film, and is used to evaluate the drying properties of the paint. (7) Solid content: 1 g of water-dispersed resin was heated and dried, and the ratio of the remaining weight to the weight before drying 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. Reference Example 1 In 100g of butyl cellosolve, 8 (or 9)-acryloxytricyclo[5.2.1.0 ² , ⁶ ]-
4-decene 72g, acrylic acid 26g, 2-hydroxyethyl methacrylate 28g, styrene 25g, 2
-49 g of ethylhexyl acrylate, 4 g of lauryl mercaptan, and 4 g of azoisobutyronitrile were added dropwise over 3 hours, and the mixture was further stirred for 1 hour to carry out a copolymerization reaction to obtain a vinyl copolymer. The reaction temperature was 120°C for the initial 1.5 hours and 150°C thereafter.
Next, 32g of glycidyl ester of soybean oil fatty acid (higher unsaturated fatty acid ester content, approximately 80%) and 1g of triethylamine were added to this reaction system, and the mixture was heated at 150℃ for 30 minutes.
A time esterification reaction was carried out. The resulting copolymer esterification reaction product A had a solid content of 69.8%, an acid value of 66, a hydroxyl value of 73, and a weight average molecular weight of 16,300. Reference Examples 2 to 4 The physical properties shown in Table 1 were obtained in the same manner as in Reference Example 1, except that the types and amounts of each fatty acid or fatty acid ester and other monomers in Reference Example 1 were changed as shown in Table 1. A butyl cellosolve solution of vinyl copolymer D and esterification reaction products B and C was obtained.

【table】

[Table] Example 1 20 g of butyl cellosolve and 18 g of diethylethanolamine were added to 33.2 g of the solution of vinyl copolymer esterification reaction product A obtained in Reference Example 1, stirred at 100°C for about 30 minutes, and then methyl methacrylate
23.8g, 2-ethylhexyl acrylate 26.2
g, styrene 30g, azoisobutyronitrile 0.4
After adding 120 g of deionized water dropwise over a period of about 30 minutes, a water-dispersed resin was obtained. The phase inversion step at this time was easily carried out with little increase in viscosity. The properties of this water-dispersed resin and the physical properties of the resulting coating film are shown in Tables 2 and 3, respectively. Example 2 20 g of butyl cellosolve and 1.8 g of diethylethanolamine were added to 33.2 g of a solution of esterification reaction product A, stirred at 100°C for about 30 minutes, then 20 g of deionized water was added, and 23.8 g of methyl methacrylate was added.
g, 26.2 g of 2-ethylhexyl acrylate, 30 g of styrene, and 0.4 g of azoisobutyronitrile.
The mixture was added dropwise over time and allowed to react for an additional 2 hours. As the polymerization reaction progressed, the polymer solution gradually became translucent from a transparent state. Add 100g of deionized water to this solution.
was added dropwise over about 30 minutes to obtain a water-dispersed resin. The phase inversion step at this time was carried out extremely easily due to the low viscosity of the dispersion system. The properties of this water-dispersed resin and the physical properties of the resulting coating film are shown in Tables 2 and 3. Example 3 Solution of esterification reaction product B obtained in Reference Example 2 32.5
A water-dispersed resin was obtained in the same manner as in Example 1 except that g was used. The properties of this water-dispersed resin and the physical properties of the resulting coating film are shown in Tables 2 and 3. Example 4 Example 2 except that the solution of esterification reaction product C obtained in Reference Example 3 was used and the conditions shown in Table 2 were adopted.
A water-dispersed resin was obtained in the same manner as above. The properties of this water-dispersed resin and the physical properties of the resulting coating film are shown in Tables 2 and 3.

【table】

【table】

[Table] *Results of evaluation method (A) = Results of evaluation method (B) are shown.
Comparative example 60g of solution of esterification reaction product D obtained in Reference example 4
After adding 80 g of butyrocellosolve and raising the temperature to 120 DEG C., 140 g of butyl methacrylate, 20 g of butyl acrylate, and 0.8 g of t-butyl peroctoate were added dropwise over 3 hours, followed by further reaction for 2 hours to obtain a polymer solution. Next, add dimethylethanolamine to this polymer.
When 4.4g and 200g of deionized water were added, the viscosity of the dispersion increased significantly and the whole became a glutinous consistency, so the dispersion was taken out and placed in another container, which was extremely strong with a dissolver. The shearing force was forced to disperse over a long period of time. The degree of neutralization of this water-dispersed resin is 70%, the weight average molecular weight of the polymer is 72500, the acid value is 20, the hydroxyl value is 12,
The solid content was 39.7%. The pigment compatibility of the paint obtained by adding a specified pigment to this paint was somewhat good, but the storage stability was poor due to precipitation of aggregates. Paint workability (A) was 40, and blistering occurred in (B). In addition, the performance of the obtained coating film was as follows: Water resistance test results showed that blistering occurred, gloss was 50, and adhesion was 79/79.
100, impact resistance was 20 cm, and pencil hardness was HB.

Claims (1)

[Claims] 1 General formula [Formula] (wherein R ₁ is H or CH ₃ , R ₂ is [Formula] [Formula] [Formula] or [Formula] R ₃ is H or CH ₃ , m is An integer from 0 to 6, n is an integer that satisfies the following relationship: m=1
When n=2 to 5, when m=2 to 6, n=
2. ) 1 to 50% by weight of an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group;
A vinyl copolymer whose constituent units are 1 to 30% by weight of α/β-unsaturated carboxylic acid and 0 to 50% by weight of a compound containing a polymerizable unsaturated group and a hydroxyl group, and a higher unsaturated fatty acid or higher unsaturated fatty acid. Neutralizing the esterification reaction product with a saturated fatty acid ester, polymerizing a radically polymerizable monomer in an organic solvent in the presence of the thus obtained neutralized product, and adding water to the obtained polymer. A method for producing a water-dispersed resin characterized by: 2 The ester of acrylic acid is 8-acryloxytricyclo[5.2.1.0 ² , ⁶ ]-4decene or 9-acryloxytricyclo[5.2.1.0
² , ⁶ ]-4 Decene, the manufacturing method according to item 1.