JP3130563B2 - Emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention has a long pot life,
The present invention relates to an emulsion composition having a self-crosslinking property, which forms a crosslinked structure at the time of forming a coating film even at ordinary temperature, and provides a good crosslinked coating film. This emulsion can be suitably used in a wide range of fields such as paints, adhesives, paper processing, textile processing, printing inks, cement admixtures and the like.

[0002]

2. Description of the Related Art Conventionally, various emulsions have been used for a wide range of applications. In order to improve the performance of these coatings, emulsions having a cross-linking property have been used. In recent years, emulsions which react at lower temperatures and have good stability have been demanded. As the emulsion having such a cross-linking property, a two-pack type emulsion has been generally used, but there is a drawback in workability that the two-package must be mixed at the time of use. Therefore, in order to eliminate this drawback, a one-part type emulsion having self-crosslinking properties has been developed. However, such emulsions have mutually reactive functional groups in the same particle.
Therefore, in conventional batch polymerization, a crosslinking reaction easily occurs in the particles during storage, shortening the pot life of the emulsion, effectively reducing the film-forming properties and effectively acting on the durability of the coating film. There are various problems such as absence. Also, when trying to increase the stability of the emulsion, the crosslinking reactivity decreases,
In particular, the reactivity at low temperatures is poor, and a heat treatment is required for the crosslinking reaction.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to stably maintain a copolymer having mutually reactive functional groups in the same particle, stably polymerize, and have excellent storage stability. It is an object of the present invention to provide an emulsion composition which is a liquid type, has a long pot life, and causes a sufficient crosslinking reaction even at ordinary temperature at the time of forming a coating film to give a crosslinked coating film having good durability.

[0004]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have introduced monomers having functional groups that react with each other into separate phases,
Furthermore, they have found that the fact that a certain amount of a specific functional group that increases the reactivity during the formation of a coating film is effective is effective, and completed the present invention. That is, the present invention provides an emulsion-dispersed particle in which an ethylenically unsaturated monomer (M ₁ ) having an epoxy group in a molecule and a radically polymerizable ethylenically unsaturated monomer (M ₂ ) which does not react with an epoxy group. A-phase comprising a copolymer of (E) and an ethylenically unsaturated monomer (M ₃ ) having a carboxyl group capable of reacting with an epoxy group in the molecule and a radically polymerizable ethylenically unsaturated monomer a copolymer of (M ₄₎ B- be composed of two phases of phase
The total ethylenic unsaturation in the emulsion composition
(M ₁ + M ₂ ) is 5 to 100 parts by weight of the sum monomer.
70 parts by weight, and the (M ₃ + M ₄₎ is 30 to 95 parts by weight
In there, and in the emulsion composition, relative to the epoxy groups to 1 mole, sulfonate ion (-SO ₃ ^-) and / or sulfuric acid ester ion (-OSO ₃ ^-) a one-pack type which comprises 0.01 to 0.5 mole It is an emulsion composition.

Hereinafter, the emulsion composition obtained by the present invention will be described. The ethylenically unsaturated monomers used for producing various copolymers of the emulsion composition of the present invention are roughly classified into the following four types. here,
(Meth) acrylate, (meth) acrylic acid, (meth)
Acrylonitrile and (meth) acrylamide mean methacrylate, acrylate; methacrylic acid, acrylic acid; methacrylonitrile, acrylonitrile; methacrylamide, acrylamide.

First, examples of the ethylenically unsaturated monomer (M ₁ ) having an epoxy group in the molecule include epoxy derivatives such as glycidyl (meth) acrylate and allyl glycidyl ether. These may be used alone or in combination of two or more. Next, as the ethylenically unsaturated monomer (M ₃ ) having a carboxyl group capable of reacting with an epoxy group in the molecule, (meth) acrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its Examples include ethylenically unsaturated carboxylic acids such as monoalkyl esters, fumaric acid and monoalkyl esters thereof. These may be used alone or in combination of two or more.

Further, other ethylenically unsaturated monomers,
That is, a radically polymerizable ethylenically unsaturated monomer (M ₂ ) that does not react with an epoxy group and an ethylenically unsaturated monomer (M ₃ ) having a carboxyl group that can react with an epoxy group in the molecule. Examples of the radically polymerizable ethylenically unsaturated monomer (M ₄ ) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate,
n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) (Meth) acrylic esters such as acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylonitrile Styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene,
Aromatic vinyls such as divinylbenzene; amides such as (meth) acrylamide, N-methylol (meth) acrylamide and diacetone acrylamide; vinylidene halides such as vinylidene chloride and vinylidene fluoride; ethylene, propylene, isoprene, butadiene , Vinylpyrrolidone, vinyl chloride, vinylamide, chloroprene and the like. These may be used alone or in combination of two or more.

In forming the B-phase, as a radically polymerizable ethylenically unsaturated monomer (M ₄ ), an ethylenically unsaturated monomer having, in addition to a carboxyl group, a functional group capable of reacting with an epoxy group in the molecule. It is also possible to use saturated monomers. For example, alkylamino esters of (meth) acrylic acid such as N-methylaminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate containing an amino group; monovinylpyridines such as vinylpyridine; and dimethylaminoethyl vinyl ether and the like Vinyl ethers having an alkylamino group; unsaturated amides having an alkylamino group such as N- (2-dimethylaminoethyl) (meth) acrylamide; These may be used alone or in combination of two or more.

The amount of the ethylenically unsaturated monomer (M ₁ + M ₂ ) used to form the A-phase is based on 100 parts by weight of the total ethylenically unsaturated monomer in the emulsion composition. , 5 to 70 parts by weight. In this case, even if the amount of the A-phase is small or large, a sufficient crosslinking effect cannot be obtained at the time of forming a coating film. The amount of ethylenically unsaturated monomer (M ₃ + M ₄ ) used to form the B-phase is also based on 100 parts by weight of total ethylenically unsaturated monomer in the emulsion composition.
30 to 95 parts by weight.

The amount of the ethylenically unsaturated monomer (M ₁ ) having an epoxy group in the molecule is 0.1% to 100 parts by weight of all the ethylenically unsaturated monomers (M _{1 to} M ₄ ). ~ 40 parts by weight. On the other hand, the amount of the ethylenically unsaturated monomer (M ₃ ) having a carboxyl group capable of reacting with an epoxy group in the molecule is based on 100 parts by weight of all the ethylenically unsaturated monomers (M _{1 to} M ₄ ). 0.1 to 40 parts by weight. The molar ratio of the ethylenically unsaturated monomer (M ₁ ) having an epoxy group in the molecule and the ethylenically unsaturated monomer (M ₃ ) having a carboxyl group capable of reacting with the epoxy group in the molecule is , 0.1-10
Is appropriate. Each ethylenically unsaturated monomer (M ₁ , M ₃ )
In both cases, if the amount decreases, the crosslinking density during film formation decreases,
If the amount is too large, the stability at the time of polymerization decreases.

In the structure of the emulsion composition of the present invention, the A-phase and the B-phase are phase-separated in one emulsion particle. For example, various forms such as particles having an A-phase inside and a B-phase outside, or a reversed phase structure thereof, and a structure in which the A-phase is scattered in the B-phase can be employed. A-phase and B-
In order to increase the stability of the phase, when forming the A-phase and the B-phase, other ethylenic phase may be used as an intermediate phase as a phase inert to both epoxy groups and carboxyl groups capable of reacting with epoxy groups. The intermediate phase can also be prepared by using one or more unsaturated monomers (M ₂ ) as a raw material.

Promotes the reaction between the epoxy group and the carboxyl group
Sulfonate ion (-SO_Three ^-)
And / or sulfate ion (-OSO_Three ^-Emulsi)
When introduced into a solution, sulfate ion is present in the molecule.
Radical polymerization initiator (I ₁) And / or sulfone
Interface having acid ion or sulfate ion in the molecule
Activator (S₁).

Examples of the radical polymerization initiator (I ₁ ) having a sulfate ion in the molecule include persulfates such as ammonium persulfate and potassium persulfate. Examples of the surfactant (S ₁ ) having a sulfonate ion or a sulfate ion in the molecule include sodium dodecylbenzenesulfonate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dioctyl sulfosuccinate; lauryl sulfate Sodium and sodium polyoxyethylene alkyl ether sulfate.

The total number of moles of sulfonic acid ions and / or sulfate ions used in the emulsion composition is as follows:
For 1 mol of epoxy group in the emulsion composition,
It is 0.01 to 0.5 mol. If this ratio is less than 0.01 mol, the reactivity between the epoxy group and the functional group capable of reacting with the epoxy group is poor, and sufficient cross-linking coating properties cannot be obtained. On the other hand, if this ratio exceeds 0.5 mol, the hydrophilicity of the resulting coating film increases, and the water resistance and the like decrease. The radical polymerization initiator (I ₁ ) having a sulfate ion in the molecule and the surfactant (S ₁ ) having a sulfonic acid ion or a sulfate ion in the molecule may be used in combination. If the required number of moles is obtained, it can be used alone. The surfactant (S ₁ ) having a sulfonic acid ion or a sulfate ion in the molecule may be used during the polymerization or may be added after the polymerization.

Further, as a radical polymerization initiator, a radical polymerization initiator (I) having a sulfate ion in the molecule.
₁₎ In addition, there is what can be used in the present invention (I _2). Examples include hydrogen peroxide; azo initiators such as azobisisobutyronitrile; organic peroxides such as cumene hydroperoxide and t-butyl hydroperoxide. In particular, when the ratio of the ethylenically unsaturated monomer (M ₁ ) having an epoxy group in the molecule is large in the A-phase, the radical polymerization initiator (I It is preferable to use ₂ ). Further, in some cases, there is a redox initiator prepared by combining a persulfate or a peroxide with a metal ion such as an iron ion, or a reducing agent such as sodium sulfoxylate, sodium pyrosulfite, or L-ascorbic acid.

The surfactant (S ₂ ) other than the surfactant (S ₁ ) having a sulfonic acid ion or a sulfate ion in the molecule is required for the emulsion polymerization and the stability of the particles. Can be used. For example, anionic surfactants such as sodium dialkyl sulfosuccinate, sodium stearate, and sodium oleate; polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, Nonionic surfactants such as oxyethylene / oxypropylene block copolymer; and cationic surfactants such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride.

The emulsion composition of the present invention is produced according to a known emulsion polymerization method. The method of adding the ethylenically unsaturated monomer (M _{1 to} M ₄ ) can be added all at once, continuously or dividedly. In this case, the monomer may be mixed with water and a surfactant in advance and dropped as an emulsion. When the second and subsequent phases are polymerized, a new polymerization initiator may be added. The polymerization temperature varies depending on the type of the monomer to be used, the type of the polymerization initiator, and the like, but a temperature range of usually 30 to 90 ° C is appropriate. Furthermore, a chain transfer agent such as mercaptans can be added when performing emulsion polymerization as required. The particle size of the obtained emulsion composition is 0.
When the reactivity between the epoxy group and the carboxyl group is considered, the range of 01 to 0.5 μm, preferably about 0.05 to 0.3 μm is optimal.

The emulsion composition obtained by emulsion polymerization is finally neutralized with a basic substance. The pH value is preferably set to 6 or more. At this time, if the pH is less than 6, the crosslinking reaction during the formation of the coating film is not sufficiently performed.
As the base substance used, ammonia, potassium hydroxide, sodium hydroxide, monomethylamine, monoethylamine, dimethylamine, diethylamine, monoethanolamine, trimethylamine, triethylamine, dimethylethanolamine, diethylethanolamine,
Triethanolamine and the like.

Further, in the emulsion composition of the present invention,
As long as the desired effect is not impaired, ordinary emulsion additives such as defoamers, dispersants, thickeners, pigments, film-forming aids, organic solvents, plasticizers, preservatives, antibacterial agents, Addition of a rust agent etc. does not hurt at all.

[0020]

The present invention will be described below in detail with reference to examples. In the examples, the following abbreviations are used for the ethylenically unsaturated monomer, polymerization initiator and surfactant used. GMA: glycidyl methacrylate, MAc: methacrylic acid, ST: styrene, n-BA: n-butyl acrylate, MMA: methyl methacrylate, 2-EHA: 2-ethylhexyl acrylate, AAM: acrylamide,
KPS: potassium persulfate, AIBN: azobisisobutyronitrile, DBS: sodium dodecylbenzenesulfonate. The evaluation method of the obtained emulsion composition is as follows. Acid value: The emulsion composition is dissolved in a mixed solvent of n-butanol and xylene (volume ratio = 1: 1), and titrated with N / 10-KOH (alcohol solution) using 1% phenolphthalein as an indicator. . Film strength and elongation: The emulsion composition was applied on a Teflon plate and dried at room temperature for 7 days to produce a film, which was used as a sample for evaluation. The strength and elongation of this sample were measured. Water resistance: The sample was immersed in water for 3 days, and its whitening state was visually observed. The result of the whitening state is ◎ (excellent)> ○
(Good)> △ (Normal)> × (Poor) Water absorption: The sample was immersed in water for 3 days, and the weight increase was measured. Gel content: After measuring the weight (W ₁ ) of the above sample, it was immersed in toluene for 3 days, and calculated from the weight (W ₂ ) of the solid content dissolved in toluene by the following equation. Gel content (%) = {(W ₁ −W ₂ ) / W ₁ } × 100

Example 1 557.5 g of pure water and D were added to a reaction vessel (capacity: 2 lit; equipped with a stirrer, reflux condenser, dropping device, and thermometer).
Charge 0.5 g of BS and stir in a nitrogen atmosphere at a temperature of 70
At 25 ° C., 2.5 g of KPS were added. Next, as the A-phase, S
A solution obtained by emulsifying 35 g of T, 50 g of n-BA and 15 g of GMA with 40 g of pure water and 0.4 g of DBS was continuously dropped into the reaction vessel over 2 hours. After completion of dropping, the mixture was aged for 1 hour. Further, as the B-phase, ST 180 g, n-BA 210
g and 10 g of MAc emulsified with 160 g of pure water and 1.6 g of DBS were continuously dropped into the reaction vessel over 3 hours. After completion of dropping, the mixture was aged for 1 hour. Then, cool to room temperature, add ammonia water as a neutralizing agent and adjust the pH.
Was adjusted to 7.5 to obtain an emulsion composition. The composition of the used raw materials is shown in Table 1, and the evaluation results of the obtained emulsion composition are shown in Table 2.

Example 2 In the same reaction vessel as in Example 1, 561.3 g of pure water and DBS
Charge 0.5g, and stir in a nitrogen atmosphere at a temperature of 70 ° C.
2.5 g of IBN were added. Next, ST 6
A mixture of 1.5 g, 38.5 g of 2-EHA and 50 g of GMA emulsified with 60 g of pure water and 1.35 g of DBS was continuously dropped into the reaction vessel over 2 hours. After completion of dropping, the mixture was aged for 1 hour. Further, as the B-phase, ST 107.5 g, n-BA 21
What emulsified 2.5g and 30g of MAc with 140g of pure water and 3.15g of DBS was dripped continuously into the reaction vessel over 3 hours. After completion of dropping, the mixture was aged for 1 hour. afterwards,
Cool to room temperature, add aqueous ammonia as a neutralizing agent and add
H was adjusted to 7.5 to obtain an emulsion composition. The composition of the used raw materials is shown in Table 1, and the evaluation results of the obtained emulsion composition are shown in Table 2.

Example 3 In the same reaction vessel as in Example 1, 568.8 g of pure water and DBS
Charge 0.5g, K at a temperature of 70 ° C under stirring in a nitrogen atmosphere.
2.5 g of PS were added. Next, as the A-phase, MMA 55
g, n-BA 70g, GMA 25g, pure water 60g and DBS
What was emulsified with 2.85 g was dripped continuously into the reaction vessel over 2 hours. After completion of dropping, the mixture was aged for 1 hour. Further, as the B-phase, 137.5 g of MMA, n-BA 18
7.5g, MAc 15g, AAM 10g, pure water 140g and DB
The mixture emulsified with 6.65 g of S was dropped into the reaction vessel continuously over 3 hours. After completion of dropping, the mixture was aged for 1 hour. Thereafter, the mixture was cooled to room temperature, dimethylethanolamine was added as a neutralizing agent to adjust the pH to 7.5, and an emulsion composition was obtained. The composition of the used raw materials is shown in Table 1, and the evaluation results of the obtained emulsion composition are shown in Table 2.

Example 4 In the same reaction vessel as in Example 1, 568.8 g of pure water and DBS
Charge 0.5g, K at a temperature of 70 ° C under stirring in a nitrogen atmosphere.
2.5 g of PS were added. Next, as the A-phase, ST60 g,
90 g of n-BA, 50 g of GMA, 80 g of pure water and 3.8 of DBS
The emulsion emulsified with g was continuously dropped into the reaction vessel over 2 hours. After completion of dropping, the mixture was aged for 1 hour. Further, as the B-phase, ST 107.5 g, n-BA 162.5 g, M
What emulsified 30 g of Ac with 120 g of pure water and 5.7 g of DBS was continuously dropped into the reaction vessel over 3 hours. After completion of dropping, the mixture was aged for 1 hour. Thereafter, the mixture was cooled to room temperature, and ammonia water was added as a neutralizing agent to adjust the pH to 7.5.
To obtain an emulsion composition. The composition of the used raw materials is shown in Table 1, and the evaluation results of the obtained emulsion composition are shown in Table 2.

Example 5 557.5 g of pure water and DBS were placed in the same reaction vessel as in Example 1.
Charge 0.5g, K at a temperature of 70 ° C under stirring in a nitrogen atmosphere.
2.5 g of PS were added. First, as the B-phase, ST 175
g, n-BA 210g, MAc 15g, pure water 160g and DB
The mixture emulsified with 1.6 g of S was dropped into the reaction vessel continuously over 3 hours. After completion of dropping, the mixture was aged for 1 hour. Next, as the A-phase, ST 30 g, n-BA 45 g, G
A solution obtained by emulsifying 25 g of MA with 40 g of pure water and 0.4 g of DBS was continuously dropped into the reaction vessel over 2 hours.
After completion of dropping, the mixture was aged for 1 hour. Thereafter, the mixture was cooled to room temperature, the pH was adjusted to 7.5 by adding aqueous ammonia as a neutralizing agent, and an emulsion composition having a structure in which A-phases were scattered in B-phases was obtained. Table 1 shows the composition of the raw materials used.
Table 2 shows the evaluation results of the obtained emulsion compositions.

Comparative Example 1 557.5 g of pure water and DBS were placed in the same reaction vessel as in Example 1.
Charge 0.5g, K at a temperature of 70 ° C under stirring in a nitrogen atmosphere.
2.5 g of PS were added. Next, ST 205g, n-BA 25
5g, GMA 25g, MAc 15g, pure water 200g and DB
The emulsion emulsified with 2.0 g of S was dropped into the reaction vessel continuously over 4 hours. After completion of dropping, the mixture was aged for 1 hour. Thereafter, the mixture was cooled to room temperature, ammonia water was added as a neutralizing agent to adjust the pH to 7.5, and an emulsion composition was obtained. The composition of the used raw materials is shown in Table 1, and the evaluation results of the obtained emulsion composition are shown in Table 2.

Comparative Example 2 557.5 g of pure water and DBS were placed in the same reaction vessel as in Example 1.
Charge 0.5g, K at a temperature of 70 ° C under stirring in a nitrogen atmosphere.
2.5 g of PS were added. Next, as A-phase, ST 48.5
g and 51.5 g of n-BA emulsified with 40 g of pure water and 0.4 g of DBS were continuously dropped into the reaction vessel over 2 hours. After completion of dropping, the mixture was aged for 1 hour. Furthermore, B-
As a phase, 175 g of ST, 210 g of n-BA, and 15 g of MAc emulsified with 160 g of pure water and 1.6 g of DBS were continuously dropped into the reaction vessel over 3 hours. After completion of dropping, the mixture was aged for 1 hour. Thereafter, the mixture was cooled to room temperature, ammonia water was added as a neutralizing agent to adjust the pH to 7.5, and an emulsion composition was obtained. Table 1 shows the composition of the raw materials used.
Table 2 shows the evaluation results of the obtained emulsion composition.

Comparative Example 3 562 g of pure water and 0.2 g of DBS were placed in the same reaction vessel as in Example 1.
5 g, AI in a nitrogen atmosphere under stirring at a temperature of 70 ° C
2.5 g of BN were added. Next, as A-phase, ST 61.5
g, 28.5 g of 2-EHA and 50 g of GMA were emulsified with 60 g of pure water and 1.5 g of Emulgen 920 (trade name, polyoxyethylene nonyl phenyl ether, manufactured by Kao Corporation) and reacted continuously for 2 hours. It was dropped into the container.
After completion of dropping, the mixture was aged for 1 hour. Further, as the B-phase,
ST 107.5g, n-BA 212.5g, MAc 30g pure water 1
40 g and 3.5 g of Emulgen 920 emulsified in 3
It was dropped into the reaction vessel continuously over time. After completion of dropping, the mixture was aged for 1 hour. After that, it was cooled down to room temperature, adjusted to pH 7.5 by adding ammonia water as a neutralizing agent,
An emulsion composition was obtained. Table 1 shows the composition of the raw materials used.
Table 2 shows the evaluation results of the obtained emulsion composition.

Comparative Example 4 In the same reaction vessel as in Example 1, 557.5 g of pure water and DBS
Charge 0.5g, K at a temperature of 70 ° C under stirring in a nitrogen atmosphere.
5.0 g of PS was added. Next, as the A-phase, ST 35
g, n-BA 50g, GMA 15g, pure water 40g and DBS
What was emulsified with 2.9 g was continuously dropped into the reaction vessel over 2 hours. After completion of dropping, the mixture was aged for 1 hour.
Further, as the B-phase, ST 180 g, n-BA 210 g, MA
A solution obtained by emulsifying 10 g of c with 160 g of pure water and 11.6 g of DBS was continuously dropped into the reaction vessel over 3 hours.
After completion of dropping, the mixture was aged for 1 hour. Thereafter, the mixture was cooled to room temperature, ammonia water was added as a neutralizing agent to adjust the pH to 7.5, and an emulsion composition was obtained. The composition of the used raw materials is shown in Table 1, and the evaluation results of the obtained emulsion composition are shown in Table 2.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

According to the present invention, an emulsion composition which is a one-part type and has a long pot life, which has not been achieved by the prior art, and which causes a sufficient crosslinking reaction at the time of forming a coating film even at room temperature was obtained. By this crosslinking reaction, a film having excellent strength, water resistance and solvent resistance is formed, so that the emulsion composition of the present invention can be used for paints, adhesives, paper processing, textile processing, printing ink, cement admixture, etc. Useful over a wide range of fields.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08F 220/32 C08F 220/32 265/00 265/00 C08G 59/42 C08G 59/42 C09D 133/00 C09D 133/00 (56 References JP-A-47-3344 (JP, A) JP-A-52-145450 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 33/00 C08F 2/26 C08F 2/44 C08F 220/06 C08F 220/18 C08F 220/32 C08G 59/42 C09D 133/00

Claims (1)

(57) [Claims] An emulsion-dispersed particle comprising an ethylenically unsaturated monomer having an epoxy group in the molecule (M ₁ ) and a radically polymerizable ethylenically unsaturated monomer which does not react with the epoxy group (M ₂ ) And an ethylenically unsaturated monomer having a carboxyl group capable of reacting with an epoxy group in the molecule (M ₃ ) and a radically polymerizable ethylenically unsaturated monomer ( And a B-phase consisting of a copolymer with M ₄ ), wherein the above (M ₁ + M ₂ ) is based on 100 parts by weight of all ethylenically unsaturated monomers in the emulsion composition. 5-70 parts by weight, and the (M ₃ + M ₄₎ is in the 30 to 95 parts by weight, and Emarushi
During ® emission composition, with respect to epoxy groups to 1 mole, sulfonate ion (-SO ₃ ^-) and / or sulfuric acid ester ion (-
One-pack type emulsion composition containing 0.01 to 0.5 mol of OSO ₃ ⁻ ).