JP3015015B1 - One-part curable resin emulsion composition - Google Patents

Abstract

The present invention provides a one-part curable resin emulsion composition capable of forming a film having excellent polymerization stability, film forming property, water (whitening) resistance, solvent resistance and corrosion resistance. In an aqueous medium containing an emulsifier comprising at least one of a reactive surfactant and a water-soluble polymer compound, a structural unit derived from the following component (A) and a structural unit derived from the following component (B) A copolymer having a structural unit derived and a structural unit derived from the following component (C) is dispersed, and the structural unit derived from the component (A) is 0.5 to 40% by weight in the copolymer. , The structural unit derived from the component (B) is set to 0.01 to 5% by weight in the copolymer, and the structural unit derived from the component (C) is set to 55 to 99.49% by weight in the copolymer. One-part curable resin emulsion composition. (A) a dicyclopentadiene derivative. (B) an alkoxylyl group-containing monomer. (C) A polymerizable monomer copolymerizable with the above components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a one-part curable resin emulsion composition, and more particularly to a one-part curable resin emulsion composition which can be cured by baking at room temperature or low temperature.

[0002]

2. Description of the Related Art In recent years, as the trend toward environmental conservation has increased, the shift from solvent-based resins to water-based resins has become active in various industries, and resin emulsions have become widespread in terms of safety and the like. However, since the resin emulsion contains an emulsifier such as a surfactant, it has the following difficulties. That is, the emulsifier plays a very important role in the process of emulsion polymerization, but when used in various applications as an emulsion, the emulsifier becomes an obstacle, causing foaming of the emulsion, lowering the drying rate of the emulsion, Side-effects such as a decrease in adhesion to the film, a decrease in the water resistance of the film, and a decrease in the gloss of the film, and the physical properties are inferior to those of the solvent-based resin.

[0003]

In order to solve such a problem, a so-called soap-free technology for eliminating an emulsifier in an emulsion has recently attracted attention. Among them, a method using a reactive surfactant has been widely used. At present, a method using a water-soluble polymer compound has become effective. However, a film obtained by a soap-free emulsion using the above-mentioned reactive surfactant or water-soluble polymer compound has a certain level of water (whitening) resistance and corrosion resistance, but has a three-dimensional network structure due to crosslinking. , It is inferior in solvent resistance.

[0004] Therefore, as means for improving the solvent resistance of the soap-free emulsion, introduction of divinylbenzene, polymerizable silane or the like has been attempted. However, the above-mentioned divinylbenzene and polymerizable silane have a property that the polymerization stability and the film-forming property are deteriorated, so that there is a problem that the number of used parts cannot be increased. On the other hand, when the number of parts of divinylbenzene or polymerizable silane used is reduced, there is almost no problem in terms of polymerization stability and film forming property, but on the other hand, there is a problem that sufficient solvent resistance cannot be obtained.

The present invention has been made in view of such circumstances, and a one-part curing method capable of forming a film having excellent polymerization stability, film forming property, water (whitening) resistance, solvent resistance and corrosion resistance. It is an object of the present invention to provide a mold resin emulsion composition.

[0006]

In order to achieve the above object, the one-part curable resin emulsion composition of the present invention comprises:
In an aqueous medium containing an emulsifier comprising at least one of a reactive surfactant and a water-soluble polymer compound, a structural unit derived from the following component (A) and a structural unit derived from the following component (B) A copolymer having units and a structural unit derived from the following component (C) is dispersed, and (A)
The structural unit derived from the component is 0.5 to 40 in the copolymer.
% By weight, the structural unit derived from the component (B) is set to 0.01 to 5% by weight in the copolymer, and the structural unit derived from the component (C) is set to 55 to 99.49% by weight in the copolymer. It has a configuration that has been done. (A) A dicyclopentadiene derivative represented by the general formula (1) . (B) an alkoxylyl group-containing monomer represented by the general formula (2) . (C) A polymerizable monomer copolymerizable with the above components (A) and (B).

The inventor has conducted a series of studies in order to obtain a one-part curable resin emulsion composition having excellent physical properties. As a result, in an aqueous medium containing an emulsifier comprising at least one of a reactive surfactant and a water-soluble polymer compound, a structural unit derived from a dicyclopentadiene derivative (A component) and an alkoxyl group-containing monomer A copolymer having a specific ratio of a structural unit derived from a polymer (component B) and a structural unit derived from a polymerizable monomer (component C) copolymerizable with component A and component B described above is dispersed. The present inventors have found that the obtained one-part curable resin emulsion composition can achieve the intended purpose, and have reached the present invention.
That is, the one-part curable resin emulsion composition,
Without impairing the stability of the resin, it is possible to significantly improve the solvent resistance, and without lowering the film forming property,
Since the crosslink density can be increased, water (whitening) resistance and corrosion resistance can be further improved.

[0008]

Next, an embodiment of the present invention will be described.

[0009] The one-part curable resin emulsion composition of the present invention comprises an aqueous medium containing an emulsifier comprising at least one of a reactive surfactant and a water-soluble polymer compound.
A copolymer obtained by copolymerizing a dicyclopentadiene derivative (A component), an alkoxylyl group-containing monomer (B component), and a specific polymerizable monomer (C component) is dispersed. It is. Water is most suitable as the aqueous medium.

As the specific dicyclopentadiene derivative (component A), dicyclopentadiene represented by the following general formula (1) derived from dicyclopentadiene represented by the following structural formula (3): derivatives is needed use.

[0011]

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[0012]

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Specific examples of the dicyclopentadiene derivative (component A) represented by the general formula (1) include dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl acrylate, and dicyclopentenyloxyethyl methacrylate. And the like. These may be used alone or in combination of two or more. Of these, dicyclopentenyloxyethyl acrylate is preferred in terms of reactivity, curability, and the like.

The dicyclopentadiene derivative (component A) represented by the above general formula (1) can be obtained by adding a number to the carbon atom in the compound as shown in the following general formula. And a group represented by the following general formula (1 ′).

[0015]

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[0016]

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The dicyclopentadiene derivative (component A) represented by the general formula (1) is, for example, a dicyclopentadiene represented by the structural formula (3) and a dicyclopentadiene represented by the following general formula (4). It can be obtained by performing an addition reaction with the represented carboxylic acid.

[0018]

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The dicyclopentadiene derivative (component A) represented by the above general formula (1) is composed of a compound represented by the following structural formula (5) and a carboxylic acid represented by the above general formula (4). It can also be obtained by an esterification reaction with an acid.

[0020]

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The amount of the dicyclopentadiene derivative (component A) used is in the range of 0.5 to 40% by weight (hereinafter abbreviated as "%") in the monomer mixture to be the copolymer-forming material. It is necessary to set, and it is preferably 1 to 20%. That is, if the use amount of the component A is less than 0.5%, the solvent resistance is inferior, and if it exceeds 40%, the cost becomes too high and practicality is imposed.

[0022] As the specific alkoxysilyl group-containing monomer (B component), alkoxysilyl group-containing monomer represented by the Symbol of the general formula (2) is used.

[0023]

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Specific examples of the alkoxylyl group-containing monomer (component B) represented by the above general formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, and vinylmethyldiethoxysilane. , Vinylmethyldipropoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltripropoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldipropoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, etc. It is below. These may be used alone or in combination of two or more. Above all, γ-methacryloxypropyltrimethoxysilane is preferable in terms of characteristics, price, and the like.

The amount of the alkoxyl group-containing monomer (component (B)) to be used must be set so as to be in the range of 0.01 to 5% in the monomer mixture serving as the copolymer-forming material. Preferably it is 0.05-3%. That is, if the amount of the component B is less than 0.01%, the solvent resistance is poor, and if it exceeds 5%, the polymerization stability and the film forming property are poor.

The specific polymerizable monomer (component C) is not particularly limited as long as it can be copolymerized with the dicyclopentadiene derivative (component A) and the alkoxylyl group-containing monomer (component B). It does not do. Examples of such a polymerizable monomer (component C) include acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
Unsaturated carboxylic acids such as maleic anhydride and fumaric acid; sulfonic acid group-containing monomers such as vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl acrylate and sulfoethyl methacrylate; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate; Hydroxy-containing monomers such as hydroxypropyl methacrylate, allyl alcohol, caprolactone-modified hydroxy acrylate, caprolactone-modified hydroxy methacrylate, bishydroxyethyl phthalate monoacrylate, and bishydroxyethyl phthalate monomethacrylate; 2-acryloxyethyl acid phosphate; 2, -Methacryloxyethyl acid phosphate, 2-acryloxypropyl acid phosphate, 2- Tacryloxypropyl acid phosphate, 2-acryloxy-3-chloropropyl acid phosphate, 2-methacryloxy-3-chloropropyl acid phosphate, 2-acryloxyphenylethyl phenyl phosphate, 2-methacryloxyphenylethyl phenyl phosphate Acidic phosphate ester monomers such as methyl acrylate, ethyl acrylate, n
-Propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-
Acrylic esters such as ethylhexyl acrylate, cyclohexyl acrylate and isobornyl acrylate, methyl methacrylate, ethyl methacrylate,
Methacrylates such as n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, styrene, vinyl toluene,
aromatic monomers such as α-methylstyrene; vinyl esters such as vinyl acetate; halogen-containing monomers such as vinyl chloride and vinylidene chloride; cyano group-containing monomers such as vinyl ethers, acrylonitrile and methacrylonitrile; N,
N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N-methylolacrylamide, 4-vinylpyridine, vinylimidazole, acrylamide, methacrylamide, and other nitrogen-containing monomers, glycidyl acrylate, glycidyl methacrylate, and the like. And glycidyl group-containing monomers. These may be used alone or in combination of two or more.

The amount of the polymerizable monomer (component (C)) used is:
55-99. In the monomer mixture to be the copolymer-forming material.
It is necessary to set so as to be in the range of 49%, preferably 77 to 98.95%. That is, when the use amount of the component C is less than 55%, the dicyclopentadiene derivative (component A) and the alkoxylyl group-containing monomer (B
In contrast, when the content of component (A) and component (B) is too high, the price is high, and practicality is exceeded. Because it is inferior.

The special emulsifier used to make the one-part curable resin emulsion composition of the present invention soap-free includes a reactive surfactant and a water-soluble polymer compound. Used in conjunction with seeds.

The reactive surfactant is a surfactant having a double bond capable of radical polymerization in one molecule.
This reactive surfactant has a monomer emulsifying power like a normal emulsifier, forms micelles in the process of emulsion polymerization to provide a polymerization site for the monomer, and has a radical polymerizable double bond to form another monomer. It is copolymerized with a monomer and immobilized on the surface of polymer particles to improve the dispersion stability of the particles. Therefore,
After the emulsion polymerization, it hardly remains in the emulsion as an emulsifier, and has a feature of a soap-free emulsion different from a conventional emulsion. Examples of the reactive surfactant include anionic or nonionic reactive surfactants. Specifically, a sulfate salt of polyoxyethylene allyl glycidyl nonyl phenyl ether (Adecaria soap SE series, Asahi Denka Kogyo Co., Ltd.), alkyl allyl sulfosuccinic acid sodium salt (Eleminol JS-2, Sanyo Chemical Co., Ltd.),
Bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfate (Antox MS60,
Nippon Emulsifier Co., Ltd.), polyoxyethylene allyl glycidyl nonyl phenyl ether (Adecaria Soap NE series, manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene nonyl propenyl phenyl ether (Aqualon RN series,
Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene nonylpropenyl phenyl ether sulfate ammonium salt (Aqualon HS series, Daiichi Kogyo Seiyaku Co., Ltd.) and the like. These may be used alone or in combination of two or more.

Further, the water-soluble polymer compound includes:
Examples thereof include carboxylic acid-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and the like, and these may be used alone or in combination of two or more.

The content of the special emulsifier is in the range of 0.1 to 20 parts by weight per 100 parts by weight of the copolymer (resin solids) dispersed in the aqueous medium (hereinafter abbreviated as "parts"). Is preferably set, and particularly preferably 0.5 to 3
Department. That is, when the content of the emulsifier is less than 0.1 part, the synthesis of the emulsion becomes difficult, and
If the amount exceeds the above-mentioned parts, the water (whitening) resistance, corrosion resistance and the like tend to be inferior.

In the production of the one-part curable resin emulsion composition of the present invention, a polymerization initiator is used to copolymerize the components A to C. Preferred examples of the polymerization initiator include persulfates such as sodium persulfate, ammonium persulfate, and potassium persulfate; organic peroxides such as cumene hydroperoxide and t-butyl hydroperoxide; and hydrogen peroxide. Can be used. Further, a redox catalyst comprising a combination of a radical generator and a sulfite can also be used. These polymerization initiators are preferably used in an amount of about 0.1 to 2 parts based on 100 parts of a copolymer (resin solid content) dispersed in an aqueous medium.

In the emulsion polymerization, a chain transfer agent can be used. Examples of the chain transfer agent include n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, and trichlorobromomethane. The use amount of these chain transfer agents is usually set to about 0 to 2 parts with respect to 100 parts of the copolymer (resin solid content) dispersed in the aqueous medium.

Further, the one-part curable resin emulsion composition of the present invention may contain a light stabilizer, an ultraviolet absorber, an antioxidant, and the like, which are well known to those skilled in the art, for the purpose of improving weather resistance. can do.

In addition, a thickener, a dispersant, an antifoaming agent, a preservative, a film-forming auxiliary, etc., which are well known to those skilled in the art, may be added to the one-part curable resin emulsion composition of the present invention, if necessary. can do.

The one-part curable resin emulsion composition of the present invention is treated with ammonia, various organic amines, sodium hydroxide or the like to maintain the pH in the alkaline region in order to maintain stability.
It is desirable to adjust to.

The one-part curable resin emulsion composition of the present invention can be produced using the above-mentioned components, for example, as follows. That is, in the presence of water and a special emulsifier comprising at least one of a reactive surfactant and a water-soluble polymer compound, a dicyclopentadiene derivative (A component) and an alkoxylyl group-containing monomer (B component) Can be obtained by polymerizing a specific polymerizable monomer (component C) with a polymerization initiator or the like.

The one-part curable resin emulsion composition of the present invention thus obtained contains 0.5 to 40% of the structural unit derived from the component A in the copolymer, and the structural unit derived from the component B in the copolymer. It is necessary to set the structural unit to be 0.01 to 5% and the structural unit derived from the component C to be 55 to 99.49%. Incidentally, the ratio of the structural units derived from the above-mentioned components A to C is in accordance with the use amount of the components A to C described above.

The one-part curable resin emulsion composition of the present invention can be further formed into a coating using a commonly used pigment, surface treating agent, organic solvent and the like. The coating composition can be applied by a method such as dipping, brushing, spraying, or roll coating, and is made of wood, paper, fiber, plastic, ceramic, iron, non-ferrous metal, or the like. Etc. can be applied to the surface.

The one-part curable resin emulsion composition of the present invention can be used as a paint base, various coating agents, adhesives, pressure-sensitive adhesives, fiber treatment agents, paper processing agents and the like.

Next, examples will be described together with comparative examples.

First, prior to Examples and Comparative Examples, the following components were prepared.

[Dicyclopentadiene derivative (component A)] dicyclopentenyloxyethyl acrylate represented by the following structural formula (1a)

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[Alkoxylyl group-containing monomer (component B)] γ-methacryloxypropyltrimethoxysilane represented by the following structural formula (2a)

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[Reactive Surfactant] Ammonium = ω-
{[2-allyloxy-1- (nonylphenoxy) methyl] ethoxy} poly (ethoxy) sulfonate (Adecaria soap SE-10N, manufactured by Asahi Denka Kogyo KK)

[Water-soluble polymer compound] Sulfonic acid-modified polyvinyl alcohol (Gohselan L-3226, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

[Non-reactive surfactant * 1] Polyoxyethylene nonyl phenyl ether sulfate sodium salt

[Non-reactive surfactant * 2] Polyoxyethylene nonylphenyl ether

[0049]

Example 1 A special emulsion was prepared by mixing the emulsifiers shown in Table 1 below and other components in the proportions shown in the same table. That is, 1 part of the reactive surfactant is dissolved in 30 parts of water, and the dicyclopentadiene derivative (A component) 5
Parts, an alkoxylyl group-containing monomer (component B) 0.5 part,
Styrene 10 parts, methyl methacrylate 50.5 parts, 2
33 parts of ethylhexyl acrylate and 1 part of acrylic acid were blended and emulsified to prepare a special emulsion in advance.

On the other hand, a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube was charged with 70 parts of water and a reactive surfactant (Adecaria Soap SE-10N, manufactured by Asahi Denka Kogyo KK). The mixture was heated while stirring while blowing in nitrogen gas, and the liquid temperature was adjusted to 75 ° C. In this state, first, 7.5% of the special emulsion prepared above and 10% of an aqueous initiator solution (0.2 part of ammonium persulfate dissolved in 10 parts of water) were added. Then, after stirring, the remaining emulsion and the aqueous initiator solution are further added dropwise over 4 hours to react with each other, and at the same temperature (75 ° C.).
A complete reaction was performed for 5 hours. After cooling the obtained emulsion, 0.25 parts of aqueous ammonia was added to obtain a target resin emulsion composition.

[0051]

Examples 2 to 7 The types and proportions of emulsifiers and other components used in preparing special emulsions were changed as shown in Table 1 below. Otherwise in the same manner as in Example 1, a target resin emulsion composition was obtained.

[0052]

[Table 1]

[0053]

Comparative Examples 1 to 5 The types and blending ratios of emulsifiers and other components used in preparing special emulsions were changed as shown in Table 2 below. Otherwise in the same manner as in Example 1, a target resin emulsion composition was obtained.

(Comparative Example 1) Instead of using the dicyclopentadiene derivative (component A), the mixing ratio of methyl methacrylate was increased by 2 parts and the mixing ratio of 2-ethylhexyl acrylate by 3 parts.

Comparative Example 2 The mixing ratio of the alkoxylyl group-containing monomer (component B) was increased from 0.5 part to 10 parts without using the dicyclopentadiene derivative (component A).

Comparative Example 3 In place of 5 parts of the dicyclopentadiene derivative (component A), 2 parts of divinylbenzene was used.

Comparative Example 4 The mixing ratio of methyl methacrylate was increased by 0.5 part instead of using the alkoxylyl group-containing monomer (component B).

Comparative Example 5 A non-reactive surfactant * 1 and a non-reactive surfactant * 2 were used without using the dicyclopentadiene derivative (A component) and instead of the reactive surfactant.
Was used in combination.

[0059]

Comparative Examples 6 and 7 The types and proportions of emulsifiers and other components used in preparing special emulsions were changed as shown in Table 2 below. Otherwise in the same manner as in Example 1, a target resin emulsion composition was obtained.

[0060]

[Table 2]

Using the resin emulsion compositions of Examples and Comparative Examples, polymerization stability, film forming properties,
Comparative evaluation of water whitening resistance, solvent resistance and corrosion resistance was performed. The results are shown in Tables 3 and 4 below. In addition, each characteristic was measured as follows.

[Polymerization Stability] Comprehensive judgment was made on the basis of the mechanical stability, standing stability, machine soil, filtration residue and the like of each resin emulsion composition.

The evaluation results were displayed as follows. ◎: Very good ○: Good ×: Poor

[Film-forming property] To 100 parts of the resin emulsion composition, 8 parts of butyl cellosolve was added to prepare a test solution, and this test solution was placed on a glass plate to have a dry film thickness of about 2 parts.
0 μm using an applicator and apply 10 μm
The test piece was prepared by drying at 0 ° C. for 20 minutes. Then, the film formation state of this test piece (dry film) was visually evaluated.

The evaluation results were displayed as follows. ◎: A completely uniform film was formed. ：: Cracks were slightly generated. Δ: Cracks were partially generated. X: Many cracks were generated.

[Water resistance to whitening] Resin emulsion composition 1
Then, 8 parts of butyl cellosolve was added to 00 parts to prepare a test solution, and this test solution was placed on a glass plate to a dry film thickness of about 20 μm.
m using an applicator, 100 ° C
For 20 minutes to produce a test piece. This test piece was immersed in warm water at 40 ° C., and the degree of whitening of the coating film after 48 hours was visually observed.

The evaluation results are shown as follows. ◎: no change ：: slight whitening Δ: whitening was observed in the whole ×: completely whitened

[Solvent Resistance] The above test solution (100 parts of resin emulsion composition and 8 parts of butyl cellosolve added) was cast to a thickness of about 6 mil in a wet state on a commercially available polyethylene plate. After drying for days, a film was prepared. This was immersed in hot refluxing acetone (about 60 ° C.) for 1 hour, the elution weight was measured, and the insoluble content of the film was measured.

[Corrosion Resistance] The above test solution (100 parts of resin emulsion composition to which 8 parts of butyl cellosolve was added) was applied to a cold-rolled steel plate bright (JIS G31).
41 SPCC-SB 70 × 150 × 0.8 mm, manufactured by Nippon Test Panel Osaka Co., Ltd.)
Apply using an applicator so that
After drying for 30 minutes, a test plate was obtained. After sealing a portion of the test plate other than the coated surface with paraffin, a cross cut was made and 5% saline was sprayed according to JIS Z2371. Then, the appearance after spraying salt water at 35 ° C. for 72 hours was visually determined.

The evaluation results were displayed as follows. ：: No abnormality ○: Slight rust spots △: Many spot rust spots ×: Spot rust spots almost all over

[0071]

[Table 3]

[0072]

[Table 4]

From the results shown in Tables 3 and 4, all of the resin emulsion compositions of the examples have excellent polymerization stability and a coating film excellent in film forming property, water whitening resistance, solvent resistance and corrosion resistance. It can be seen that they can be formed.

On the other hand, the resin emulsion composition of Comparative Example 1 uses an alkoxylyl group-containing monomer (component B), but uses a dicyclopentadiene derivative (component A).
It was found that the solvent resistance was inferior due to the absence of the compound.
Further, the resin emulsion composition of Comparative Example 2 has improved solvent resistance because of a large amount of the alkoxyl group-containing monomer (component B), but, on the other hand, polymerization stability and film formation. It can be seen that they are inferior in water resistance, water whitening resistance and corrosion resistance. Since the resin emulsion composition of Comparative Example 3 uses divinylbenzene, the solvent resistance is improved,
On the other hand, it can be seen that the polymerization stability, film forming property, water whitening resistance and corrosion resistance are inferior. Although the resin emulsion composition of Comparative Example 4 uses a dicyclopentadiene derivative (component A), the alkoxyl group-containing monomer (B
It can be seen that the solvent resistance was slightly inferior because no component (A) was used in combination. Although the resin emulsion composition of Comparative Example 5 uses an alkoxylyl group-containing monomer (component B), it does not use a dicyclopentadiene derivative (component A), and therefore has poor solvent resistance. Since a non-reactive surfactant is used in place of the reactive surfactant, the non-reactive surfactant remains in the emulsion, indicating that the water-whitening resistance and the corrosion resistance are extremely poor. Since the content of the dicyclopentadiene derivative (component A) in the resin emulsion composition of Comparative Example 6 was lower than the specific value, it was found that the solvent resistance was significantly poor. The resin emulsion composition of Comparative Example 7 has no difference in performance from the resin emulsion composition of Example 3, but the content ratio of the dicyclopentadiene derivative (A component) exceeds a specific value, so that the cost becomes too high, and There is a problem of sex.

[0075]

As described above, the one-part curable resin emulsion composition of the present invention can be used in an aqueous medium containing an emulsifier comprising at least one of a reactive surfactant and a water-soluble polymer compound. A structural unit derived from a pentadiene derivative (component A), a structural unit derived from an alkoxylyl group-containing monomer (component B), and a polymerizable monomer copolymerizable with the above component A and component B ( C component)
A copolymer having a specific proportion of structural units derived from is dispersed. As a result, it is possible to significantly improve the solvent resistance without impairing the stability of the resin, and it is possible to increase the crosslink density without deteriorating the film-forming property, thereby further improving the water resistance (whitening) resistance and corrosion resistance. Can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 2/24 C08L 33/00-33/26 C08L 83/00-83/16

Claims (2)

(57) [Claims] 1. A structural unit derived from the following component (A) in an aqueous medium containing an emulsifier comprising at least one of a reactive surfactant and a water-soluble polymer compound:
A copolymer having a structural unit derived from the following component (B) and a copolymer having a structural unit derived from the following component (C) is dispersed, and the structural unit derived from the component (A) is dispersed in the copolymer. 0.5 to 40% by weight, the structural unit derived from the component (B) is 0.01 to 5% by weight in the copolymer, and the structural unit derived from the component (C) is 55 to 99. A one-part curable resin emulsion composition, which is set to 49% by weight. (A) represented by the following general formula (1)
Dicyclopentadiene derivatives. Embedded image (B) An alkoxyl group-containing monomer represented by the following general formula (2) . Embedded image (C) A polymerizable monomer copolymerizable with the above components (A) and (B). 2. The one-part curable resin emulsion composition according to claim 1, wherein the content of the emulsifier is set to 0.1 to 20 parts by weight with respect to 100 parts by weight of the copolymer (resin solid content). object.