JP5287555B2 - Emulsion composition - Google Patents

Description

  The present invention relates to an emulsion composition. More specifically, the present invention relates to an emulsion composition that forms a dry film having excellent storage stability and excellent adhesion, flexibility, durability, and adhesiveness.

In general, emulsion compositions are superior to solvent-based ones in terms of safety and hygiene. Adhesives, water-based paints, interior and exterior paints, inks, impregnation agents for fibers and paper, sealing agents, coatings Widely used in various fields such as pharmaceuticals.
In particular, acrylic resin emulsions are often used in these fields because of their good weather resistance. However, adhesives, paints, inks, and the like are required to have high adhesion to various substrates, but conventional acrylic resin emulsions have not been sufficiently satisfactory. In addition, paints and coating agents used for flexible materials such as fabrics, leather, and rubber products may cause cracking or peeling of the dried film if the flexibility of the resulting dried film cannot follow the deformation of the substrate used. There were also problems that occurred.
On the other hand, there is an attempt to improve adhesion, flexibility, and durability by a combination of an epoxy resin emulsion and a polyolefin resin emulsion instead of the conventional acrylic resin emulsion alone. However, simply blending an epoxy resin emulsion and a polyolefin resin emulsion may cause separation during storage, and the large amount of emulsifier used when producing an epoxy resin emulsion and a polyolefin resin emulsion may affect water resistance. There was also a case.
On the other hand, for example, Patent Document 1 discloses a method for producing an emulsion composition in which an acrylic monomer is emulsion-polymerized in the presence of an epoxy resin.
Patent Document 2 includes particles containing an olefin polymer and an acrylic polymer in the same particle, and two or more acrylic polymer particles are present in and / or on the surface of the olefin polymer particle. An emulsion composition characterized by being dispersed in water is disclosed.
Furthermore, it is a general tendency that an emulsion composition is inferior in water resistance compared with a solvent system. That is, the emulsion composition is most commonly one in which polymerizable fine particles are dispersed in an aqueous medium in the presence of an emulsifier, but the emulsifier contained therein is hydrophilic and has a hydrophilic functional group introduced. It was difficult to obtain high water resistance due to reasons such as unavoidable reasons. On the other hand, for example, in Patent Document 3, resin particles having a core / shell structure with an average particle diameter of 0.3 μm or less, the Tg of the resin constituting the core being 15 ° C. or more, and constituting the shell. An aqueous emulsion-type pressure-sensitive adhesive in which resin particles having a resin Tg of −30 ° C. or less are emulsified and dispersed in an aqueous medium is disclosed.

Japanese Patent Laid-Open No. 08-188605 JP 2005-146202 A JP 2003-292922 A

The emulsion composition disclosed in Patent Document 1 is characterized by a production method in which emulsion polymerization is performed by adjusting the pH of an aqueous medium to 5 to 8 when emulsion polymerization of an acrylic monomer in the presence of an epoxy resin is performed. There is. Although the water-based adhesive obtained from this emulsion composition is improved in adhesion and water resistance, the epoxy group in the epoxy resin and the carboxyl group in the acrylic resin are likely to react, and the storage stability of the emulsion composition is improved. There is a problem that it is not good. Moreover, the dry film obtained from this emulsion composition does not satisfy physical properties such as flexibility, adhesiveness, and durability.
Further, the emulsion composition disclosed in Patent Document 2 is an emulsion composition characterized by stabilizing the functional group in the acrylic by dispersing the acrylic polymer in the olefin polymer. . The dry film obtained from this emulsion composition is somewhat improved in terms of adhesion, durability and water resistance, but is still not fully satisfactory, and physical properties such as flexibility and adhesiveness are satisfactory. is not.
The aqueous emulsion type pressure-sensitive adhesive disclosed in Patent Document 3 is characterized by an acrylic emulsion having a core / shell structure. The dry film obtained from this water-based emulsion-type pressure-sensitive adhesive is improved in water resistance, but physical properties such as adhesion, flexibility and durability of the obtained dry film are not fully satisfactory.
An object of the present invention is to provide an emulsion composition that forms a dry film having excellent storage stability and excellent adhesion, flexibility, durability, and adhesiveness.

The present invention is shown below.
1. An emulsion composition in which polymer particles are dispersed in an aqueous medium,
The polymer particles are derived from 50 to 98% by mass of a structural unit (A) derived from an alkyl (meth) acrylate monomer having an alkyl group having 4 to 14 carbon atoms and an ethylenically unsaturated carboxylic acid monomer. Structural unit (B) 0.1 to 5% by mass, Structural unit derived from vinyl monomer having cyano group (C) 0.1 to 20% by mass, reaction of (meth) acrylic acid with monofunctional epoxy compound 1 to 20% by mass of the structural unit (D) derived from the monomer consisting of the product, and 0 to 50% by mass of the structural unit (E) derived from another monomer copolymerizable with the monomer. Contains ,
The monofunctional epoxy compound is a compound having a phenyl group,
Soluble matter for ethyl acetate of the dry film obtained by drying the emulsion composition, the emulsion composition characterized in der Rukoto than 30 wt%.
[However, the total of the structural unit (A), the structural unit (B), the structural unit (C), the structural unit (D), and the structural unit (E) is 100% by mass. ]
2. 1. The glass transition temperature of the polymer particles is from −80 ° C. to 0 ° C. The emulsion composition described in 1.
3 . 1. The polymer particles obtained by emulsion polymerization in the presence of a reactive emulsifier . Or 2. The emulsion composition described in 1.

According to the emulsion composition of the present invention, it is possible to obtain an emulsion composition which is excellent in storage stability and forms a dry film excellent in adhesion, flexibility, durability and adhesiveness.
Moreover, when the glass transition temperature of a polymer particle is -80 degreeC-0 degreeC, it can be set as the emulsion composition which forms the dry film which is more excellent in a softness | flexibility, durability, and adhesiveness.
Moreover, when the soluble content with respect to ethyl acetate of the hardened | cured material obtained by drying an emulsion composition is 30 mass% or less, it can be set as the emulsion composition excellent in cohesion force.
In addition, when the polymer particles are obtained by emulsion polymerization of the above monomer in the presence of a reactive emulsifier, the emulsion composition may further form a dry film having excellent water resistance. it can.
Moreover, when a monofunctional epoxy compound is a compound which has a phenyl group, it can be set as the emulsion composition which forms the dry film which is more excellent in cohesion force, and is more excellent in adhesiveness.

The emulsion composition of the present invention is an emulsion composition in which polymer particles are dispersed in an aqueous medium, and the polymer particles are (meth) acrylic acid alkyl esters having an alkyl group having 4 to 14 carbon atoms. Structural unit (A) derived from monomer (hereinafter also referred to as monomer (a)) 50 to 98% by mass, ethylenically unsaturated carboxylic acid monomer (hereinafter also referred to as monomer (b)) 0.1 to 5% by mass of the structural unit (B) derived from the above, 0 to 20% by mass of the structural unit (C) derived from the vinyl monomer having a cyano group (hereinafter also referred to as monomer (c)), 1 to 20% by mass of a structural unit (D) derived from a monomer (hereinafter also referred to as monomer (d)) composed of a reaction product of (meth) acrylic acid and a monofunctional epoxy compound, and the above-mentioned single amount Other monomer copolymerizable with the body (hereinafter also referred to as monomer (e)) From 0 to 50% by mass derived from the above [provided that the structural unit (A) + the structural unit (B) + the structural unit (C) + the structural unit (D) + the structural unit ( E) = 100 wt%], and
The monofunctional epoxy compound is a compound having a phenyl group,
Soluble matter for ethyl acetate of the dry film obtained by drying the emulsion composition, characterized in der Rukoto than 30 wt%.
Note that “(meth) acrylate” means acrylate and methacrylate, and “(meth) acryl” means acrylic and methacryl. The “dry film” means a film after the film is dried (cured) after the film is formed by coating the emulsion composition.

  The emulsion composition of the present invention is a dispersion (emulsion) in which polymer particles containing structural units (monomer units) formed of the above monomers are dispersed in an aqueous medium. As this aqueous medium, water alone or a mixture of water and a water-soluble organic solvent (alcohol, ketone, ether, dimethyl sulfoxide, dimethylformamide, etc.) can be used. When the aqueous medium is a mixture, the content of water is usually 30% by mass or more when the aqueous medium is 100% by mass (hereinafter, the same applies to the “aqueous medium”).

The polymer particle is a structural unit (A) derived from an alkyl (meth) acrylate monomer having an alkyl group having at least 4 to 14 carbon atoms, and a structural unit (B) derived from an ethylenically unsaturated carboxylic acid monomer. And a structural unit (C) derived from a vinyl monomer having a cyano group, and a structural unit (D) derived from a monomer comprising a reaction product of (meth) acrylic acid and a monofunctional epoxy compound. Polymer particles.
Furthermore, the polymer particles may be other monomers that can be copolymerized with the monomer [monomer (a), monomer (b), monomer (c), or monomer (d)]. It can contain at least one structural unit selected from structural units (E) derived from the body.

Moreover, the said polymer particle is a polymer which became a granular form in the state of at least 1 sort (s) of solid and a semi-solid (gel form).
The average particle diameter of the polymer particles is preferably 5 μm or less, more preferably 0.01 to 2 μm, and still more preferably 0.03 to 1 μm. When the average particle diameter of the polymer particles is within the above range, an emulsion composition having excellent storage stability can be obtained.

  As the alkyl (meth) acrylate monomer [(meth) acrylic acid alkyl ester] having an alkyl group having 4 to 14 carbon atoms that forms the structural unit (A), for example, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate , 2-methylpentyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylic acid n-nonyl, isononyl (meth) acrylate, 2-methyloctyl (meth) acrylate, (meth) acrylic acid Sil, (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl and (meth) acrylate isobornyl like. These may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated carboxylic acid monomer that forms the structural unit (B) include unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, and acryloxypropionic acid, maleic acid, Examples thereof include unsaturated dibasic acids such as itaconic acid, fumaric acid, mesaconic acid, citraconic acid and cyclohexanedicarboxylic acid, and unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride. . These may be used alone or in combination of two or more. Among these, (meth) acrylic acid is preferable because it is inexpensive and easily causes a copolymerization reaction with other various monomers.

  Examples of the vinyl monomer having a cyano group forming the structural unit (C) include acrylonitrile, methacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. It is done. These may be used alone or in combination of two or more.

The monomer comprising the reaction product of (meth) acrylic acid and a monofunctional epoxy compound that forms the structural unit (D) is preferably a compound having a (meth) acryloyl group and a hydroxy group. is there.
Examples of the monofunctional epoxy compound include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxy polyethylene glycol glycidyl ether, phenol polyethylene glycol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p- Examples thereof include methylphenyl glycidyl ether, p-ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, and p-tert-butylphenyl glycidyl. These may be used alone or in combination of two or more.

Of these monofunctional epoxy compounds, a monofunctional epoxy compound containing a phenyl group is used in the present invention . Specifically, phenol polyethylene glycol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-methylphenyl glycidyl ether, p-ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl, etc. Is mentioned.

Specifically, as a monomer comprising a reaction product of (meth) acrylic acid and a monofunctional epoxy compound, 2-hydroxy-3-phenoxypropyl acrylate represented by the following formula (1), the following formula (2) And 2-hydroxy-3-p-methylphenoxypropyl acrylate represented by the following formula (3) and 2-hydroxy-3--2-ethylhexyloxypropyl acrylate represented by the following formula (3). These may be used alone or in combination of two or more. Moreover, among these, as a monomer consisting of a reaction product of (meth) acrylic acid and a monofunctional epoxy compound used in the present invention, compounds represented by the following formula (1) and the following formula (2), etc. Is mentioned.

The other monomer (e) copolymerizable with the monomer forming the structural unit (E) is the monomer (a), the monomer (b), the monomer (c), or It is a monomer copolymerizable with the monomer (d). The monomer (e) is not particularly limited as long as it is an unsaturated compound having radical polymerizability. As this unsaturated compound, an alkyl (meth) acrylate monomer having an alkyl group having 1 to 3 carbon atoms, a vinyl monomer having a hydroxyl group (however, a monomer forming the structural unit (D) is excluded) ), Aromatic vinyl monomers, vinyl monomers having amino groups, vinyl monomers having amide groups, vinyl monomers having alkoxyl groups, conjugated diene monomers, maleimide monomers, vinyl Examples include ester monomers, vinyl ether monomers, vinyl monomers having a glycidyl group, monoalkyl esters of unsaturated dicarboxylic acids, dialkyl esters of unsaturated dicarboxylic acids, monomers having silicon-containing groups, and the like. These can be used alone or in combination of two or more.

  Examples of the alkyl (meth) acrylate monomer having an alkyl group having 1 to 3 carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Etc. These can be used alone or in combination of two or more.

  Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, Mono (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol, polypropylene glycol, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isoprop Alkenyl phenols and the like. These can be used alone or in combination of two or more.

  Examples of aromatic vinyl monomers include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-tert-butyl. Styrene, tert-butoxystyrene, vinyltoluene, divinyltoluene, benzyl (meth) acrylate, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, styrenesulfonic acid and salts thereof, α -Methyl styrene sulfonic acid, its salt, etc. are mentioned. These can be used alone or in combination of two or more.

  As vinyl monomers having an amino group, aminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) 2-diethylaminoethyl acrylate, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, (meth) acrylic acid 2- (di-n-propylamino) propyl, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 3- (di-n-propylamino) propyl (meth) acrylate, etc. Is mentioned. These can be used alone or in combination of two or more.

  Examples of the vinyl monomer having an amide group include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Examples include butoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-alkoxymethyl (meth) acrylamide. These can be used alone or in combination of two or more.

  Examples of vinyl monomers having an alkoxyl group include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, and (meth) acrylic acid. 2- (n-butoxy) ethyl, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- (N-butoxy) propyl and the like can be mentioned. These can be used alone or in combination of two or more.

  Conjugated diene monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3 butadiene, chloroprene (2-chloro-1,3-butadiene) ) And the like. These can be used alone or in combination of two or more.

  Examples of the maleimide monomer include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4 -Methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4- Hydroxyphenyl) maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These can be used alone or in combination of two or more.

  Examples of the vinyl ester monomer include methylene aliphatic monocarboxylic acid ester, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl butyrate, vinyl benzoate, vinyl formate, vinyl cinnamate, vinyl versatate, and the like. These can be used alone or in combination of two or more.

  Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like. These can be used alone or in combination of two or more.

Examples of the vinyl monomer having a glycidyl group include glycidyl (meth) acrylate, (meth) allyl glycidyl tether, (meth) acrylate β-methylglycidyl, 4-hydroxybutyl (meth) acrylate glycidyl, 3,4- Examples thereof include epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

Examples of monoalkyl esters of unsaturated dicarboxylic acids include monoalkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. . These can be used alone or in combination of two or more.
Examples of the dialkyl ester of unsaturated dicarboxylic acid include dialkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. These can be used alone or in combination of two or more.

  Examples of the monomer having a silicon-containing group include vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, and vinyltri-n-butoxysilane. , Vinyltris (2-hydroxymethoxyethoxy) silane, vinyltriacetoxysilane, vinyldiethoxysilanol, vinylethoxysiladiol, vinylmethyldiethoxysilane, vinyldimethiethoxysilane, vinylmethyldiacetoxysilane, allyltrimethoxysilane, allyl Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltris (2-methoxyethoxy) sila , 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl dimethyl ethoxysilane, 3-acryloxy propyl dimethoxysilane, and 2-acrylamide-ethyl triethoxysilane and the like. These can be used alone or in combination of two or more.

  Among these other monomers, an alkyl (meth) acrylate monomer having an alkyl group having 1 to 3 carbon atoms, a monomer having a hydroxyl group, and an aromatic vinyl monomer are preferable. By using these monomers, an emulsion composition having excellent adhesion, flexibility and cohesion can be obtained at low cost.

  The content of the structural unit (A) in the polymer particles is 100% by mass of the total amount of the structural unit (A), the structural unit (B), the structural unit (C), the structural unit (D), and the structural unit (E). When it is, it is 50-98 mass%. Preferably it is 55-95 mass%, More preferably, it is 60-93 mass%. When content of a structural unit (A) exists in the said range, it can be set as the emulsion composition from which the dry film excellent in a softness | flexibility and low temperature property is obtained.

  The content of the structural unit (B) in the polymer particles is 100% by mass of the total amount of the structural unit (A), the structural unit (B), the structural unit (C), the structural unit (D), and the structural unit (E). And 0.1 to 5% by mass. Preferably it is 0.1-3 mass%, More preferably, it is 0.3-2.5 mass%. When content of a structural unit (B) exists in the said range, it can be set as the emulsion composition from which the hardened | cured material which is excellent in cohesion force is obtained. On the other hand, when the amount is less than 0.1% by mass, the polymerization may not be stably performed. When the amount is more than 5% by mass, the viscosity may be increased when the emulsion is neutralized.

The content of the structural unit (C) in the polymer particles is 100% by mass of the total amount of the structural unit (A), the structural unit (B), the structural unit (C), the structural unit (D), and the structural unit (E). When it is, it is 0.1-20 mass%. Preferably it is 0.1-18 mass%, More preferably, it is 1-18 mass%. When content of a structural unit (C) exists in the said range, it can be set as the emulsion composition from which the dry film excellent in a softness | flexibility and rubber elasticity is obtained. On the other hand, if the content of the structural unit (C) exceeds 20% by mass, the water resistance may decrease.

  The content of the structural unit (D) in the polymer particles is 100% by mass of the total amount of the structural unit (A), the structural unit (B), the structural unit (C), the structural unit (D), and the structural unit (E). 1 to 20% by mass. Preferably it is 3-18 mass%, More preferably, it is 5-15 mass%. If the content of the structural unit (D) is less than 1% by mass, the adhesion is insufficient, and if it exceeds 20% by mass, the flexibility and the polymerization stability may be lowered.

The content of the structural unit (E) in the polymer particles is 100% by mass of the total amount of the structural unit (A), the structural unit (B), the structural unit (C), the structural unit (D), and the structural unit (E). 0 to 50% by mass. Preferably it is 0.3-45 mass%, More preferably, it is 0.4-40 mass%.
The content of the structural unit (E) being 0% by mass means that the structural unit (E) is not contained at all in the polymer particles. The structural unit (E) may or may not be contained in the polymer particles. When the structural unit (E) is contained, the content is 50% by mass or less, preferably 0.3 to 45% by mass, and more preferably 0.4 to 40% by mass.

  The glass transition temperature (Tg) of the polymer particles is not particularly limited, but is preferably -80 ° C to 0 ° C, more preferably -80 ° C to -5 ° C, and further preferably -80 ° C to -10. ° C. When the Tg of the polymer particles is within the above range, an emulsion composition can be obtained in which a dry film having excellent adhesiveness, adhesiveness, and low temperature properties can be obtained. The glass transition temperature (Tg) of the polymer particles can be measured by a differential scanning calorimeter (DSC).

The solid content concentration of the emulsion composition mainly includes the polymer particles, and the solid content concentration of the emulsion composition may be set to an appropriate solid content concentration. The solid content concentration of the emulsion composition is usually 10 to 90% by mass, preferably 20 to 85% by mass, and more preferably 30 to 80% by mass.
Moreover, the viscosity of an emulsion composition is not specifically limited, What is necessary is just to set it as an appropriate viscosity. The viscosity of the emulsion composition at a temperature of 25 ° C. is usually 1 to 5000 mPa · s, preferably 5 to 4000 mPa · s, and more preferably 10 to 3000 mPa · s. The viscosity of this emulsion composition can be measured with a BM viscometer.
Although the pH of an emulsion composition is not specifically limited, Usually, it exists in the range of 1-10.

The dry film obtained from the emulsion composition of the present invention can have a soluble content in ethyl acetate of 30% by mass or less. The soluble content is usually 0% or more, preferably 25% by mass or less, more preferably 20% by mass or less. When this soluble content is within the above range, an emulsion composition can be obtained in which a dry film having excellent durability, cohesive strength and water resistance can be obtained.
Soluble content in ethyl acetate can be measured using a high-speed solvent extraction apparatus. For example, a predetermined amount of a dry film obtained from the emulsion composition is precisely weighed to prepare a test body, and a sample in which Ottawa sand is mixed with the test body made of the dry film is prepared. The obtained sample is set in the high-speed solvent extraction apparatus, and the sample is extracted with ethyl acetate. After extraction, it is dried to remove ethyl acetate, and an ethyl acetate extract is obtained.
And ethyl acetate soluble part is computed by following formula (1) from the mass of the obtained ethyl acetate extract, and the mass of a specimen.
Ethyl acetate soluble matter (mass%) = mass of ethyl acetate extract (g) / mass of test specimen (g) × 100 (1)

  The emulsion composition may further contain other additives as long as the object of the present invention is achieved. As this additive, thickeners, antifoaming agents, pigments, pH adjusters, tackifiers, crosslinking agents, plasticizers, wetting agents, stabilizers, preservatives, antifungal agents, fillers, antifreeze agents, Solvent, Dispersant, Anti-settling agent, Antistatic agent, Antibacterial agent, Fragrance, UV absorber, UV stabilizer, Layered viscosity mineral, Aldehyde scavenger, Antioxidant, Textile aid, Cleaning agent, Leveling agent, Level dyeing Additives, adhesives, water-based paints, interior / exterior paints / coatings / waterproofing materials, inks, impregnating agents such as fibers and paper, sealing agents, and additives (materials) commonly added to coating agents Can be mentioned.

  Examples of the thickener include inorganic thickeners such as acrylic thickeners, urethane thickeners, polyether thickeners, polyvinyl alcohols, cellulose derivatives, bentonite, hectorite, and apatalite. Etc. These may contain only 1 type, or may contain 2 or more types.

  Examples of the defoaming agent component include silicone-based, oil-based, fatty acid-based, fatty acid ester-based, and phosphate ester-based defoaming agents, and those in which a part of the structure of these defoaming agents is modified. Can be mentioned. These may contain only 1 type, or may contain 2 or more types. Moreover, when 2 or more types are contained, it may be a combination of any antifoam component of silicone type, fat type, fatty acid type, fatty acid ester type and phosphate ester type.

  The pigment may be either an organic compound (organic pigment) or an inorganic compound (inorganic pigment). Organic pigments include insoluble azo pigments, condensed azo pigments, azo lakes, chelate azo pigments, etc .; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments And polycyclic pigments such as dye lakes, nitro pigments, nitroso pigments, aniline black, and fluorescent pigments. Of these, azo pigments, phthalocyanine pigments, and polycyclic pigments are preferred. Examples of inorganic pigments include titanium oxide, carbon black, red pepper, cadmium red, molybdenum orange, yellow iron oxide, yellow lead, titanium yellow, chrome green, chromium oxide, cobalt blue, and manganese violet.

  Examples of the tackifier include coumarone / indene resin, terpene resin, terpene / phenol resin, rosin resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, xylene / formaldehyde resin, petroleum hydrocarbon resin, Examples thereof include hydrogenated hydrocarbon resins and terpine resins. These may contain only 1 type, or may contain 2 or more types.

  Examples of the cross-linking agent include cross-linking agents having reactivity with carboxyl groups (mainly carboxyl groups possessed by (meth) acrylic acid), such as carbodiimide-based cross-linking agents, isocyanate-based cross-linking agents, and epoxy-based cross-linking agents. Oxazoline-based crosslinking agents, aziridine-based crosslinking agents, metal chelate-based crosslinking agents, and the like. As the crosslinking agent, for example, an oil-soluble or water-soluble crosslinking agent is used, or a crosslinking agent prepared as a water dispersion type (emulsion type) is also used. These may contain only 1 type, or may contain 2 or more types.

The manufacturing method of the emulsion composition of this invention is equipped with the superposition | polymerization process which superposes | polymerizes the said monomer. Through this polymerization step, the monomer is polymerized to form polymer particles dispersed in the aqueous medium. The polymerization method of the monomer in the polymerization step is not particularly limited, and a known polymerization method such as emulsion polymerization of a vinyl monomer can be used. Specifically, this polymerization step is performed in a heated reaction system in an aqueous medium while stirring and reflux cooling, and is exemplified below.
[1] An aqueous medium, a monomer mixture containing a part or all of the above monomers and / or a mixture of part or all of an emulsifier, a radical polymerization initiator, and the remaining monomer mixture and A method of polymerizing while adding the remaining emulsifier.
[2] Polymerization while adding a monomer mixture containing the above monomers, an emulsifier and a radical polymerization initiator individually or in combination of two or three of them to an aqueous medium how to.
In each of the above embodiments, the addition method of the raw material components may be any of a batch addition method, a continuous addition method and a divided addition method. In the case of the continuous addition method, the supply rate may be constant or indefinite. In addition, in the case of the divided addition method, the addition interval of the raw material components may be constant or indefinite.
Furthermore, in the polymerization step, the mass ratio of the monomer mixture and the aqueous medium in the reaction system is preferably 5 to 200 parts by mass of the aqueous medium when the amount of the monomer is 100 parts by mass. .

As the monomer used in the method for producing the emulsion composition, the description of the monomer described in the emulsion composition can be applied as it is. Moreover, the mass ratio of each structural unit which a monomer superpose | polymerizes can apply the compounding ratio of each monomer as it is.
That is, the emulsion composition (polymer particles) is 50 to 98% by mass (preferably 55 to 95% by mass, more preferably, the alkyl (meth) acrylate monomer (a) having an alkyl group having 4 to 14 carbon atoms. Is from 60 to 93% by mass), the ethylenically unsaturated carboxylic acid monomer (b) is from 0.1 to 5% by mass (preferably from 0.1 to 3% by mass, more preferably from 0.3 to 2.5% by mass). %), The vinyl monomer having a cyano group (c) 0.1 to 20% by mass (preferably 0.1 to 18% by mass, more preferably 1 to 18% by mass), (meth) acrylic acid and simple substance 1 to 20% by mass (preferably 3 to 18% by mass, more preferably 5 to 15% by mass) of the monomer (d) consisting of a reaction product with a functional epoxy compound, and copolymerizable with the monomer The other monomer (e) 0 to 50% by mass (preferably It is properly from 0.3 to 45 wt%, more preferably at a monomer mixture obtained by emulsion polymerization in an aqueous medium containing 0.4 to 40 mass%). However, the total of the monomer (a), the monomer (b), the monomer (c), the monomer (d) and the monomer (e) is 100% by mass.
The blending amount of the monomer ( e ) of 0% by mass means that the monomer ( e ) is not blended.

In the emulsion polymerization in the polymerization step, an emulsifier is used. As this emulsifier, a known emulsifier used in usual emulsion polymerization can be used. In the method for producing an emulsion composition of the present invention, it is preferable to use a reactive emulsifier.
This reactive emulsifier is an emulsifier having a functional group (reactive group) such as an ethylenically unsaturated double bond. Although it will not specifically limit as a reactive emulsifier if it is an emulsifier which has a reactive group, For example, the emulsifier shown by following formula 4-15 is mentioned. These can be used alone or in combination of two or more. When the polymer particles (emulsion composition) are obtained by emulsion polymerization in the presence of a reactive emulsifier, the emulsion composition can provide a dry film with excellent water resistance.

In the general formulas (4) to (15), R ¹ represents an alkyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group, n and m are integers of 1 or more, l and k are integers of 1 or more and 1 + k = 3, X represents a hydrogen atom, —SO ₃ NH ₄ or —SO ₃ Na, and Y represents —SO ₃ NH ₄ or —SO ₃ Na.

  Specific examples of emulsifiers other than reactive emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and zwitterionic emulsifiers. As anionic emulsifiers, dialkyl sulfosuccinate, alkylbenzene sulfonate, alkyl sulfate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl diphenyl ether sulfate, polyoxyethylene alkyl ether sulfate, alkyl diphenyl ether disulfonate And polymer emulsifiers. Nonionic emulsifiers include polyoxyethylene higher alcohol ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl diphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, acetylenic diol emulsifiers, sorbitan higher fatty acid esters. Polyoxyethylene sorbitan higher fatty acid esters, polyoxyethylene higher fatty acid esters, glycerin higher fatty acid esters, polycarboxylic acid-based polymer emulsifier, polyvinyl alcohol and the like. Examples of the cationic emulsifier include alkyl (amido) betaine and alkyl dimitylamine oxide.

Instead of the reactive emulsifier or together with the reactive emulsifier, an emulsifier other than the reactive emulsifier can be used alone or in combination of two or more.
In addition to the above-mentioned emulsifiers, fluorine emulsifiers and silicone emulsifiers can be used as special emulsifiers.
The amount of the emulsifier used (the total amount of the emulsifiers other than the reactive emulsifier and the reactive emulsifier) is selected depending on the type, polymerization conditions, and the like. 0.1 to 50 parts by mass.

In the polymerization step, the monomer is polymerized using a radical polymerization initiator such as a peroxide, a redox initiator in which a peroxide and a reducing agent are combined, or an azo compound. These radical polymerization initiators can be used in combination.
Examples of the peroxide include hydrogen peroxide; inorganic peroxides such as persulfates (sodium persulfate, ammonium persulfate, potassium persulfate, etc.); hydroperoxides (cumene hydroperoxide, paramentane hydroperoxide, tert -Butyl hydroperoxide, etc.), dialkyl peroxide (tert-butyl cumyl peroxide, dicumyl peroxide, etc.), diacyl peroxide, peroxy ester (tert-butyl peroxylaurate, tert-butyl peroxybenzoate, etc.) And organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid and persuccinic acid. These can be used alone or in combination of two or more.
As the redox initiator, a combination of the above peroxide and a reducing agent is used. This reducing agent includes ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, ferric chloride And the like.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (2-methylbutyronitrile). 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) ) -2-methylpropiondiamine] tetrahydrate and the like. These can be used alone or in combination of two or more.

  Although the usage-amount of the said radical polymerization initiator is selected by the kind, polymerization conditions, etc., when the said monomer is 100 mass parts, it is 0.01-10 mass parts normally.

Moreover, in the said polymerization process, a chain transfer agent (molecular weight regulator) etc. can be used according to the use etc. of the emulsion composition obtained.
As this chain transfer agent, a mercapto group-containing compound (ethanethiol, butanethiol, dodecanethiol, benzenethiol, toluenethiol, α-toluenethiol, phenethylmercaptan, mercaptoethanol, 3-mercaptopropanol, thioglycerin, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, α-mercaptoisobutyric acid, methyl mercaptopropionate, ethyl mercaptopropionate, thioacetic acid, thiomalic acid, thiosalicylic acid, octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, etc.), xanthogen disulfide compounds (dimethyloxa) Tonogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, etc.), thiuram disulfide compounds (tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, etc.), halogenated hydrocarbons (carbon tetrachloride, ethylene bromide, etc.), aromatic And hydrocarbon (pentaphenylethane, α-methylstyrene dimer, etc.). These can be used alone or in combination of two or more.

  The polymerization temperature in the polymerization step is appropriately selected depending on the type of monomer, the type of radical polymerization initiator, and the like, but is usually 60 to 95 ° C.

An emulsion composition is obtained by the polymerization step. The pH of the resulting emulsion composition is selected depending on the type of monomer or radical polymerization initiator, and further, after the completion of the polymerization step, depending on the use of the resulting emulsion composition, etc. A pH adjusting step for adjusting the pH can be provided.
In the pH adjusting step, a basic material is usually used when adjusting the pH of the reaction system. This basic material includes alkali metal compounds (sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal compounds (calcium hydroxide, calcium carbonate, etc.), ammonia, organic amine compounds (monomethylamine, dimethylamine, trimethylamine, Monoethylamine, diethylamine, methylethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, etc.). These can be used alone or in combination of two or more. These compounds may be used alone or in the form of an aqueous solution dissolved in water. Of these, ammonia is particularly preferred.

  In the pH adjustment step, the temperature of the reaction system when adjusting the pH of the reaction system is not particularly limited. This temperature can usually be made equal to or lower than the temperature of the reaction system at the end of the polymerization step.

  The use of the emulsion composition of the present invention is not particularly limited. Since the emulsion composition of the present invention is an emulsion composition that forms a dry film having excellent storage stability and excellent adhesion, flexibility, durability, and tackiness, for example, an adhesive, an aqueous paint, Examples include interior / exterior paints / coating materials / waterproofing materials, inks, impregnation agents such as fibers / paper, sealing agents, coating agents, and the like.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. Incidentally, "parts" and "%" in the experimental examples and comparative examples are by weight unless otherwise specified. Experimental examples 1-5, 1-11, 1-16, 2-5, 2-11 and 2-16 are reference examples, and other experimental examples are examples.
Further, in Experimental Examples and Comparative Examples, the glass transition temperature and average particle size of the polymer particles of the emulsion composition, the viscosity of the emulsion composition, the measurement of the ethyl acetate-soluble content of the cured product obtained from the emulsion composition, In addition, the storage stability of the emulsion composition was evaluated by the following method.

1-1. Properties and Evaluation Methods of Emulsion Composition (1) Glass Transition Temperature Using a differential scanning calorimeter “DSC5200” (manufactured by Seiko Instruments Inc.), the glass transition temperature ( Tg) was measured. In addition, the sample amount used for the measurement was 5 to 10 mg.

(2) Average particle diameter Using a laser diffraction / scattering particle size analyzer Microtrac MT-3000 (manufactured by Nikkiso Co., Ltd.), the average particle diameter was measured. The median diameter based on volume was defined as the particle diameter.
(3) Viscosity Using a BM viscometer, the viscosity was measured under the conditions of 12 rpm and 25 ° C.

(4) Ethyl acetate soluble matter (i) Preparation of sample In a box (length 15 cm x width 7.5 cm x height 3 cm) made of release paper, the thickness of the dried film obtained after drying is 1 mm. As described above, the emulsion composition was poured into a film made of the emulsion composition and dried at room temperature (about 18 ° C.) for 1 week to obtain a dry film.
(Ii) Extraction with ethyl acetate Extraction operation with ethyl acetate on the dried membrane obtained as described above was performed using a high-speed solvent extraction apparatus ASE-200 (manufactured by Nippon Dionex Co., Ltd.).
About 0.3 g of the dry film obtained as described above was precisely weighed and used as a test specimen. The test specimen was mixed with Ottawa sand and then filled into an 11 ml extraction cell. Next, the extraction cell filled with the test specimen and Ottawa sand was set in the high-speed solvent extraction apparatus, and extraction under the following conditions was repeated twice. Then, it was made to dry at 100 degreeC, ethyl acetate was removed, and the ethyl acetate extract was obtained.
PREHEAT: 0 min, HEAT: 6 min, STATIC: 10 min, FLUSH%: 100 vol, PURGE: 90 sec, CYCLES: 3, PRESSURE: 1500 psi, TEMPERATURE: 120 ° C.
The ethyl acetate soluble matter was calculated by the following formula.
Ethyl acetate soluble matter (mass%) = mass of ethyl acetate extract (g) / mass of test specimen (g) × 100

(5) Evaluation of storage stability About 100 ml of the emulsion composition was put into a 110 ml glass bottle, and then the glass bottle was sealed and allowed to stand at 50 ° C. for 1 month. After one month, the state of the emulsion composition in the glass bottle was visually observed and evaluated according to the following criteria.
○: No aggregation, thickening, precipitation, or separation was observed, which was good.
Δ: Any of aggregation, thickening, precipitation, and separation was observed.
X: Gelled.

〔但し、上記式（１６）において、ｎ、ｍは１以上の整数である。〕
乳化剤（２）：下記式（１７）に示される反応性乳化剤、株式会社ＡＤＥＫＡ製、商品名「アデカリアソープＳＲ−１０２５」、有効成分量２５質量％

〔但し、上記式（１７）において、Ｒ^５は、アルキル基を示し、ｎは１以上の整数である。〕
乳化剤（３）：下記式（１８）に示される反応性乳化剤、株式会社ＡＤＥＫＡ製、商品名「アデカリアソープＥＲ−３０」、有効成分量１００質量％

〔但し、上記式（１８）において、Ｒ^６は、アルキル基を示し、ｎは１以上の整数である。〕
乳化剤（４）：下記式（１９）に示される反応性乳化剤、第一工業製薬株式会社製、商品名「アクアロンＫＨ−１０２５」、有効成分量２５質量％

〔但し、上記式（１９）において、Ｒ^７は、アルキル基を示し、ｎは１以上の整数である。〕 1-2. Emulsifier and epoxy resin used for production of emulsion composition (1) The following emulsifier was used as an emulsifier.
Emulsifier (1): Reactive emulsifier represented by the following formula (16), manufactured by Kao Corporation, trade name “Latemul PD-104”, active ingredient amount 20% by mass

[However, in the above formula (16), n and m are integers of 1 or more. ]
Emulsifier (2): Reactive emulsifier represented by the following formula (17), manufactured by ADEKA Corporation, trade name “ADEKA rear soap SR-1025”, active ingredient amount 25% by mass

[In the above formula (17), R ⁵ represents an alkyl group, and n is an integer of 1 or more. ]
Emulsifier (3): Reactive emulsifier represented by the following formula (18), manufactured by ADEKA Corporation, trade name “ADEKA rear soap ER-30”, active ingredient amount 100% by mass

[In the above formula (18), R ⁶ represents an alkyl group, and n is an integer of 1 or more. ]
Emulsifier (4): Reactive emulsifier represented by the following formula (19), manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name “AQUALON KH-1025”, active ingredient amount 25% by mass

[However, in the above formula (19), R ⁷ represents an alkyl group, and n is an integer of 1 or more. ]

Emulsifier (5): sodium dodecylbenzenesulfonate, manufactured by Kao Corporation, trade name “Neopelex G-15”, active ingredient content 15% by mass
Emulsifier (6): Sodium alkyldiphenyl ether disulfonate, manufactured by Kao Corporation, trade name “Perex SSH”, active ingredient amount 50% by mass
Emulsifier (7): Sodium lauryl sulfate, manufactured by Kao Corporation, trade name “Emar 2F”, active ingredient amount 30% by mass

(2) The following were used as an epoxy resin.
Bisphenol A type epoxy resin represented by the following formula (20), manufactured by Japan Epoxy Resin Co., Ltd., trade name “JER828”, epoxy equivalent of 184 to 194 g / eq, molecular weight 370.

1-3. Preparation and evaluation of emulsion composition <Experimental Example 1-1>
A reaction vessel equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer, and a nitrogen introduction tube was charged with 25 parts of ion-exchanged water and heated to 80 ° C. with stirring while blowing nitrogen gas. On the other hand, in another container, 80.0 parts of 2-ethylhexyl acrylate, 1.0 part of methacrylic acid, 5.0 parts of acrylonitrile, 5.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, and methyl methacrylate 9 A monomer mixture composed of 0.0 part, an emulsified liquid composed of 15.0 parts of emulsifier (1) and 16.0 parts of ion-exchanged water, and these materials are stirred to prepare an emulsion containing monomers. Obtained. Subsequently, 0.3% of the obtained emulsion was added to the reaction vessel, and after 10 minutes, 4 parts of a 5% aqueous solution of ammonium persulfate was added to the reaction vessel. Further, after 10 minutes, the remaining emulsion and 6 parts of 5% ammonium persulfate aqueous solution were continuously dropped into the reaction vessel with a separate dropping funnel over 4 hours to carry out emulsion polymerization. After completion of the dropping, the inside of the reaction vessel was held at 80 ° C. for 1 hour, and then the reaction system was cooled to terminate the polymerization, thereby obtaining an emulsion composition (1) in which polymer particles were dispersed. About the obtained emulsion composition (polymer particles), the physical properties of glass transition temperature (Tg), average particle diameter, viscosity, ethyl acetate soluble content, pH, and solid content concentration are measured, and storage stability is further improved. evaluated. Raw materials were used in the experiment example 1-1, and shows the measured physical properties and evaluation results are shown in Table 1.

<Experimental Example 1-2>
Other than using 75.0 parts of 2-ethylhexyl acrylate, 1.0 part of methacrylic acid, 5.0 parts of acrylonitrile, 15.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts of methyl methacrylate as monomers. , in the same manner as experimental example 1-1 was obtained emulsion composition (2). Raw materials were used in the experiment example 1-2, as well as also shown the physical properties and evaluation results of the emulsion composition (2) in Table 1.

<Experimental Example 1-3>
The monomer was 71.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile, 19.0 parts 2-hydroxy-3-phenoxypropyl acrylate and 4.0 parts methyl methacrylate, and an emulsifier. the, the emulsifier (1) 10.0 parts of an emulsifier (5) 1.0 parts to further, and the amount of deionized water used in the emulsion was 18.0 parts, experimental examples 1-1 In the same manner as above, an emulsion composition (3) was obtained. Raw materials were used in the experiment example 1-3, as well as also shown the physical properties and evaluation results of the emulsion composition (3) in Table 1.

<Experimental Example 1-4>
The monomer is 86.0 parts of n-butyl acrylate, 0.5 part of acrylic acid, 3.0 parts of acrylonitrile, 10.0 parts of 2-hydroxy-3-phenoxypropyl acrylate and 0.5 part of hydroxyethyl acrylate. and, an emulsifier, and an emulsifier (1) 10.0 parts of an emulsifier (6) 1.0 parts to further, and the amount of deionized water used in the emulsion was 21.0 parts, experimental examples In the same manner as in 1-1, an emulsion composition (4) was obtained. Raw materials were used in the experiment example 1-4, as well as also shown the physical properties and evaluation results of the emulsion composition (4) in Table 1.

<Experimental Example 1-5>
The monomer is 85.0 parts of 2-ethylhexyl acrylate, 1.0 part of methacrylic acid, 10.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts of methyl methacrylate, and the emulsifier is an emulsifier (4 ) except for using 12.0 parts, in the same manner as in experiment example 1-1 to obtain an emulsion composition (5). Raw materials were used in the experiment example 1-5, as well as also shown the physical properties and evaluation results of the emulsion composition (5) in Table 1.

<Experimental Example 1-6>
The monomer was 75.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 10.0 parts acrylonitrile, 10.0 parts 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts styrene, and an emulsifier. , except that the emulsifier (4) 12.0 parts, in the same manner as in experiment example 1-1 to obtain an emulsion composition (6). Raw materials were used in the experiment example 1-6, as well as also shown the physical properties and evaluation results of the emulsion composition (6) in Table 1.

<Experimental Example 1-7>
The monomer is 92.0 parts of isononyl acrylate, 1.0 part of acrylic acid, 2.0 parts of acrylonitrile and 5.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, and the emulsifier is emulsifier (2) 8. 0 parts of an emulsifier (3) 1.0 parts in addition, except for using 22.0 parts amount of deionized water used in the emulsion, in the same manner as experimental example 1-1, the emulsion composition (7) was obtained. Raw materials were used in the experiment example 1-7, as well as also shown the physical properties and evaluation results of the emulsion composition (7) in Table 1.

<Experimental Example 1-8>
The monomers are n-butyl acrylate 64.0 parts, methacrylic acid 1.0 part, acrylonitrile 10.0 parts, 2-hydroxy-3-phenoxypropyl acrylate 10.0 parts and methyl methacrylate 15.0 parts, and an emulsifier. and the emulsifier (2) 8.0 parts of emulsifier (3) 1.0 parts to further, and the amount of deionized water used in the emulsion was 22.0 parts, experimental examples 1-1 In the same manner as above, an emulsion composition (8) was obtained. Raw materials were used in the experiment example 1-8, as well as also shown the physical properties and evaluation results of the emulsion composition (8) in Table 1.

<Experimental Example 1-9>
The monomer was 59.0 parts of 2-ethylhexyl acrylate, 20.0 parts of n-butyl acrylate, 1.0 part of methacrylic acid, 10.0 parts of acrylonitrile, 5.0 parts of 2-hydroxy-3-phenoxypropyl acrylate. and a methyl methacrylate 5.0 parts, an emulsifier, and an emulsifier (7) 10.0 parts, further, a except for using 18.0 parts amount of deionized water used in the emulsion, experimental example 1 In the same manner as in Example 1, an emulsion composition (9) was obtained. Raw materials were used in the experiment example 1-9, as well as also shown the physical properties and evaluation results of the emulsion composition (9) shown in Table 1.

<Experimental Example 1-10>
A reaction vessel equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer, and a nitrogen introduction tube was charged with 25 parts of ion-exchanged water and heated to 80 ° C. with stirring while blowing nitrogen gas. Meanwhile, in another container, 75.0 parts of 2-ethylhexyl acrylate, 1.0 part of methacrylic acid, 10.0 parts of acrylonitrile, 10.0 parts of 2-hydroxy-3-phenoxypropyl acrylate and methyl methacrylate 4 A monomer mixture composed of 0.0 part, an emulsified liquid composed of 10.0 parts of emulsifier (1) and 2.0 parts of emulsifier (5) and 18.0 parts of ion-exchanged water, and n-dodecyl mercaptan as a molecular weight regulator. 0.1 part was charged, and these raw materials were stirred to obtain an emulsion containing monomers. Subsequently, 0.3% of the obtained emulsion was added to the reaction vessel, and after 10 minutes, 4 parts of a 5% aqueous solution of ammonium persulfate was added to the reaction vessel. Further, after 10 minutes, the remaining emulsion and 6 parts of 5% ammonium persulfate aqueous solution were continuously dropped into the reaction vessel with a separate dropping funnel over 4 hours to carry out emulsion polymerization. After completion of the dropwise addition, the inside of the reaction vessel was held at 80 ° C. for 1 hour, and then the reaction system was cooled to terminate the polymerization to obtain an emulsion composition (10) in which polymer particles were dispersed. Raw materials were used in the experiments Example 1-10, as well as also shown the physical properties and evaluation results of the emulsion composition (10) in Table 1.

<Experimental Example 1-11>
The amount of molecular weight modifier n- dodecyl mercaptan, and 0.3 parts of an emulsifier, except that the emulsifier (4) 8.0 parts of an emulsifier (5) 2.0 parts, and experimental examples 1-10 Similarly, an emulsion composition (11) was obtained. Raw materials were used in the experiments Example 1-11, as well as also shown the physical properties and evaluation results of the emulsion composition (11) in Table 1.

<Experimental Example 1-12>
Other than using 80.0 parts of 2-ethylhexyl acrylate, 1.0 part of methacrylic acid, 5.0 parts of acrylonitrile, 3.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, and 11.0 parts of methyl methacrylate. , in the same manner as experimental example 1-1 was obtained emulsion composition (12). Raw materials were used in the experiments Example 1-12, and Table 2 shows the physical properties and evaluation results of the emulsion composition (12).

<Experimental Example 1-13>
Except for the monomer being 80.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile, 10.0 parts 2-hydroxy-3-phenoxypropyl acrylate and 4.0 parts methyl methacrylate. , in the same manner as experimental example 1-1 was obtained emulsion composition (13). Raw materials were used in the experiment example 1-13, as well as also shown the physical properties and evaluation results of the emulsion composition (13) shown in Table 2.

<Experimental Example 1-14>
Other than using 70.0 parts of 2-ethylhexyl acrylate, 1.0 part of methacrylic acid, 5.0 parts of acrylonitrile, 20.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts of methyl methacrylate as monomers. , in the same manner as experimental example 1-1 was obtained emulsion composition (14). Raw materials were used in the experiment example 1-14, as well as also shown the physical properties and evaluation results of the emulsion composition (14) shown in Table 2.

<Experimental Example 1-15>
The monomer was 80.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile, 10.0 parts 2-hydroxy-3-p-methylphenoxypropyl acrylate and 4.0 parts methyl methacrylate. except for using as the, in the same manner as in experiment example 1-1 to obtain an emulsion composition (15). Raw materials were used in the experiment example 1-15, as well as also shown the physical properties and evaluation results of the emulsion composition (15) shown in Table 2.

<Experimental Example 1-16>
The monomer was 80.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile, 10.0 parts 2-hydroxy-3--2-ethylhexyloxypropyl acrylate, and methyl methacrylate 4.0. except for using as the parts are, in the same manner as in experiment example 1-1 to obtain an emulsion composition (16). Raw materials were used in the experiments Example 1-16, as well as also shown the physical properties and evaluation results of the emulsion composition (16) shown in Table 2.

<Experimental Example 1-17>
The monomer was 80.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile, 10.0 parts 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts methyl methacrylate, , an emulsifier, except that the emulsifier (4) 12.0 parts, in the same manner as in experiment example 1-1 to obtain an emulsion composition (17). Raw materials were used in the experiment example 1-17, as well as also shown the physical properties and evaluation results of the emulsion composition (17) shown in Table 2.

<Experimental Example 1-18>
The monomer was 70.0 parts isononyl acrylate, 1.0 part methacrylic acid, 18.0 parts acrylonitrile, 10.0 parts 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts styrene, and an emulsifier. and except that the emulsifier (4) 12.0 parts, in the same manner as in experiment example 1-1 to obtain an emulsion composition (18). Raw materials were used in the experiment example 1-18, as well as also shown the physical properties and evaluation results of the emulsion composition (18) shown in Table 2.

<Experimental Example 1-19>
The monomer is 50.0 parts isononyl acrylate, 29.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 10.0 parts acrylonitrile and 10.0 parts 2-hydroxy-3-phenoxypropyl acrylate, an emulsifier, and an emulsifier (2) 8.0 parts of emulsifier (3) 1.0 parts to further, and the amount of deionized water used in the emulsion was 22.0 parts, experimental example 1 In the same manner as in Example 1, an emulsion composition (19) was obtained. Raw materials were used in the experiment example 1-19, as well as also shown the physical properties and evaluation results of the emulsion composition (19) shown in Table 2.

<Experimental Example 1-20>
The monomer was 53.0 parts of n-butyl acrylate, 2.0 parts of methacrylic acid, 10.0 parts of acrylonitrile, 10.0 parts of 2-hydroxy-3-phenoxypropyl acrylate and 25.0 parts of methyl methacrylate, and an emulsifier. and the emulsifier (2) 8.0 parts of emulsifier (3) 1.0 parts to further, and the amount of deionized water used in the emulsion was 22.0 parts, experimental examples 1-1 In the same manner as above, an emulsion composition (20) was obtained. Raw materials were used in the experiment example 1-20, as well as also shown the physical properties and evaluation results of the emulsion composition (20) shown in Table 2.

<Experimental Example 1-21>
The monomer was 59.0 parts 2-ethylhexyl acrylate, 20.0 parts n-butyl acrylate, 1.0 part methacrylic acid, 10.0 parts acrylonitrile, 5.0 parts 2-hydroxy-3-phenoxypropyl acrylate and and methyl methacrylate 5.0 parts, an emulsifier, and an emulsifier (5) 4.0 parts to further, and the amount of deionized water used in the emulsion was 24.0 parts, experimental examples 1-1 In the same manner as above, an emulsion composition (21) was obtained. Raw materials were used in the experiment example 1-21, as well as also shown the physical properties and evaluation results of the emulsion composition (21) shown in Table 2.

<Comparative Example 1-1>
The monomer, 2-ethylhexyl acrylate 80.0 parts, 1.0 parts of methacrylic acid, except that the acrylonitrile 5.0 parts of methyl methacrylate 14.0 parts, in the same manner as experimental example 1-1, the emulsion A composition (31) was obtained. Table 3 shows the raw materials used in Comparative Example 1-1 and the physical properties and evaluation results of the emulsion composition (31).

<Comparative Example 1-2>
The monomer was 65.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile, 25.0 parts 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts methyl methacrylate. It was carried out the polymerization in the same manner as in experimental example 1-1. However, aggregation occurred during the polymerization reaction, and the emulsion composition (32) was not obtained. The raw materials used in Comparative Example 1-2 are also shown in Table 3.

<Comparative Example 1-3>
The monomer is 64.0 parts of isononyl acrylate, 1.0 part of methacrylic acid, 25.0 parts of acrylonitrile and 10.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, and the emulsifier is an emulsifier (4). except for using 12.0 parts, in the same manner as in experiment example 1-1 to obtain an emulsion composition (33). The raw materials used in Comparative Example 1-3 and the physical properties and evaluation results of the emulsion composition (33) are also shown in Table 3.

<Comparative Example 1-4>
The monomer is 43.0 parts of n-butyl acrylate, 2.0 parts of methacrylic acid, 10.0 parts of acrylonitrile, 10.0 parts of 2-hydroxy-3-phenoxypropyl acrylate and 35.0 parts of methyl methacrylate, and an emulsifier. and except that the emulsifier (2) 8.0 parts of emulsifier (3) 1.0 parts was further usage of ion-exchanged water used for the emulsion and 22.0 parts, the experimental examples 1-1 Similarly, an emulsion composition (34) was obtained. The raw materials used in Comparative Example 1-4, and the physical properties and evaluation results of the emulsion composition (34) are also shown in Table 3.

<Comparative Example 1-5>
The monomer is 80.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile and 14.0 parts methyl methacrylate, the emulsifier is 10.0 parts emulsifier (1), and further emulsified. except that the amount of deionized water used in the solution was 18.0 parts, the same procedure as experimental example 1-1 was obtained emulsion composition (35). The raw materials used in Comparative Example 1-5 and the physical properties and evaluation results of the emulsion composition (35) are also shown in Table 3.

<Comparative Example 1-6>
The monomer was 65.0 parts 2-ethylhexyl acrylate, 1.0 part methacrylic acid, 5.0 parts acrylonitrile, 25.0 parts 2-hydroxy-3-phenoxypropyl acrylate, and 4.0 parts methyl methacrylate, and an emulsifier. the, the emulsifier (1) 10.0 parts to further the use of the ion-exchanged water used for the emulsion and 18.0 parts, in the same manner as experimental example 1-1, the emulsion composition (36 ) The raw materials used in Comparative Example 1-6 and the physical properties and evaluation results of the emulsion composition (36) are also shown in Table 3.

<Comparative Example 1-7>
The monomer is 44.0 parts of n-butyl acrylate, 1.0 part of methacrylic acid, 10.0 parts of acrylonitrile, 10.0 parts of 2-hydroxy-3-phenoxypropyl acrylate and 35.0 parts of methyl methacrylate, and an emulsifier. and the emulsifier (2) 8.0 parts of emulsifier (3) 1.0 parts to further, and the amount of deionized water used in the emulsion was 22.0 parts, experimental examples 1-1 In the same manner as above, an emulsion composition (37) was obtained. The raw materials used in Comparative Example 1-7 and the physical properties and evaluation results of the emulsion composition (37) are also shown in Table 3.

<Comparative Example 1-8>
The monomer, 2-ethylhexyl acrylate 84.0 parts, 1.0 parts of methacrylic acid, except that the acrylonitrile 5.0 parts of bisphenol A type epoxy resin 10.0 parts, in the same manner as experimental example 1-1 Thus, an emulsion composition (38) was obtained. The raw materials used in Comparative Example 1-8 and the physical properties and evaluation results of the emulsion composition (38) are also shown in Table 3.

<Comparative Example 1-9>
Monomers, except for using 2-ethylhexyl acrylate 81.0 parts, 6.0 parts of methacrylic acid, as acrylonitrile 5.0 parts and 8.0 parts of 2-hydroxy-3-phenoxypropyl acrylate, Experiment Example 1 In the same manner as in Example 1, an emulsion composition (39) was obtained. The raw materials used in Comparative Example 1-9 and the physical properties and evaluation results of the emulsion composition (39) are also shown in Table 3.

2. To evaluate the physical properties of the dry film obtained from the production and manufacturing and evaluation emulsion composition of the pressure-sensitive adhesive sheet of the adhesive composition, the experimental examples 1-1 to 1-11 and Comparative Example 1-1 to 1 Using the emulsion composition obtained in -4, a pressure-sensitive adhesive composition was produced, and the pressure-sensitive adhesive sheet (dry film) obtained from the pressure-sensitive adhesive composition was evaluated. By evaluating the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition, the physical properties and the like of the dry film obtained from the emulsion composition can be evaluated.
Further, in Experimental Examples and Comparative Examples, a method of manufacturing a test adhesive sheet for evaluating the adhesive composition and the adhesive strength of the adhesive sheet, waterproof adhesive strength, holding power, and the evaluation of the constant force peel strength Was carried out by the following method.

2-1. Production and manufacturing of the pressure-sensitive adhesive sheet of the adhesive composition <Experimental Example 2-1>
100 parts of the emulsion composition obtained by the experiment example 1-1, was added 25% aqueous ammonia as a neutralizing agent, and adjusted to pH 7.5. Further, 1.8 parts of an acrylic thickener [manufactured by Toagosei Co., Ltd. (trade name) “Aron B-500”] as a thickener was added and mixed to obtain a pressure-sensitive adhesive composition. The viscosity of the pressure-sensitive adhesive composition measured using a BM viscometer under the conditions of 12 rpm and 25 ° C. was 10,000 mPa · s.
Next, an adhesive sheet was produced from the adhesive composition obtained as described above according to the following evaluation method, and the adhesive strength, water-resistant adhesive strength, holding strength, and constant load peel strength of the adhesive sheet were evaluated. The evaluation results are shown in Table 4.

<Experimental example 2-2～2-11 and Comparative Examples 2-1 to 2-4>
As an emulsion composition (2) to (11), and (31), except that the use, the amount of raw material according to the formulations shown in Tables 4 and 5 (33) and (34), Experiment Example 2 A pressure-sensitive adhesive composition was produced in the same manner as in Example-1. And the adhesive sheet was produced according to the following evaluation method, and various evaluation was performed. The results are also shown in Tables 4 and 5.
In Comparative Example 2-2, since the emulsion composition (32) was not obtained in Comparative Example 1-2, the pressure-sensitive adhesive composition could not be produced.

2-2 Evaluation method of pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet and its evaluation (1) Production of test pressure-sensitive adhesive sheet Layer formed from the pressure-sensitive adhesive composition after drying on the surface of a polyethylene terephthalate film having a thickness of 100 μm (drying The pressure-sensitive adhesive composition was applied so that the thickness of the film was 50 μm, and a coating film was formed. Then, it dried for 3 minutes at 100 degreeC with the hot air circulation type dryer, and produced the adhesive sheet (dry film | membrane). For the evaluation of the following items, the pressure-sensitive adhesive sheet produced by the above method was used.

(2) Evaluation of Adhesive Strength Using the above adhesive sheet and a stainless steel plate (hereinafter also simply referred to as “SUS”) and a polypropylene plate (hereinafter also simply referred to as “PP”) as the adherend, The 180 degree peel strength was measured according to JIS Z-0237 under various temperature conditions and humidity of 50% RH, and the adhesive strength was evaluated.

(3) Water-resistant adhesive strength evaluation Using a stainless steel plate as the above-mentioned pressure-sensitive adhesive sheet and adherend, the paste was applied according to JIS Z-0237 under the conditions of a temperature of 23 ° C. and a humidity of 50% RH, and after 30 minutes of application, It was immersed in ion exchange water at 23 ° C. for 24 hours. After the elapse of 24 hours, a test piece subjected to immersion was taken out from ion-exchanged water, and after lightly wiping off moisture, the 180-degree peel strength was measured to evaluate water-resistant adhesive strength.

(4) Retention force evaluation The above adhesive sheet was affixed to a stainless steel plate so that the adhesion area would be 25 mm × 25 mm, and the time until it peeled off under a load of 1 kg at a temperature of 80 ° C. was measured. Evaluation of holding power was made. When it was kept for 24 hours or more, it was 1440 minutes. The higher the evaluation of the holding power, the better the cohesive force.

(5) Constant load peel strength evaluation Using the above-mentioned pressure-sensitive adhesive sheet, it was attached to a stainless steel plate so as to have an adhesive area of 25 mm × 50 mm under the conditions of 23 ° C. and 50% RH. Left for a minute. A load of 100 g was applied to one end portion of the short side of the pasted adhesive sheet in the 90-degree direction with respect to the adhesive sheet. At this time, the adhered adhesive sheet and adherend were fixed so as to be at an angle (horizontal) of 90 ° with respect to the direction of gravity. The distance at which the pressure-sensitive adhesive sheet peeled from the stainless steel plate after 1 hour from the load was measured. When it peeled within 1 hour, it was set to 50 mm.

3. To evaluate the physical properties of the dry film obtained from the production and manufacturing and evaluation emulsion composition of the dry film of the coating composition or the like, the experimental examples 1-12～1-21 and Comparative Example 1-5～1- A coating composition was produced using the emulsion composition obtained in 9, and the dried film obtained from the coating composition was evaluated. Moreover, the physical property etc. of the dry film obtained from an emulsion composition can be evaluated by evaluating the dry film obtained from this coating composition.
Further, in Experimental Examples and Comparative Examples, a method of manufacturing a dry film for evaluating the coating composition, as well as the adhesion of the dry film, bending peel strength, the thermal cycle test, and the evaluation of water resistance, the following It carried out by the method of.

3-1. Production manufacturing and dry film of the coating composition <Experimental Example 2-12>
100 parts of the emulsion composition obtained by the above experiment Example 1-12, was added 25% aqueous ammonia as a neutralizing agent, and adjusted to pH 8. Furthermore, 5 parts of titanium oxide (made by Ishihara Sangyo Co., Ltd., (trade name) “Typaque R930”) as a pigment, and a silicone antifoaming agent (made by Big Chemie Japan Co., Ltd., (trade name) “BYK-” 1650 "] was added and mixed to obtain a coating composition.
Next, a dry film was prepared from the coating composition obtained as described above according to the following evaluation method, and the adhesion, bending peel strength, repeated heating and cooling test, and water resistance of the dry film were evaluated. The evaluation results are shown in Table 6.

<Experimental example 2-13～2-21 and Comparative Example 2-5～2-9>
Except for using as an emulsion composition (13) to (21) and (35) - (39), the same procedure as experimental example 2-12 were prepared coating composition. And according to the following evaluation method, the dry film was produced and various evaluation was performed. The results are shown in Tables 6 and 7.
In Comparative Example 2-9, since the emulsion composition (39) was gelated during pH adjustment (at neutralization) to pH 8 with 25% aqueous ammonia, a coating composition was not obtained.

3-2. Evaluation method of coating composition (1) Production of dry film The coating composition was applied to the surface of natural leather so that the dry film formed from the coating composition after drying had a thickness of 30 μm. Formed. Next, the film was dried at room temperature for a whole day and night to prepare a dry film. The dry film produced by the above method was used for the evaluation of the following items.

(2) Evaluation of adhesion It measured according to the cross-cut tape method of JIS K-5400. The dried film produced as described above was cut into 100 squares of 1 mm square with a cutter knife using a cutter guide. And after crimping | bonding with the cellophane tape from the top, it peeled off instantaneously, the area where the dry film peeled off was observed visually, and the following reference | standard evaluated.
10: No peeling of the dry film is observed.
8: The area where the dry film was peeled off was within 5%.
6: The area where the dry film was peeled was 5 to 15%.
4: The area where the dry film was peeled was 15 to 35%.
2: The area where the dry film was peeled was 35 to 65%.
0: The area where the dry film was peeled was 65% or more.

(3) Evaluation of bending peel strength After the 180 degree bending was repeated 10 times for the dried film produced as described above, the degree of peeling was visually observed and evaluated according to the following criteria. It shows that it is excellent in adhesiveness and a softness | flexibility, so that evaluation of bending peeling strength is high.
○: Abnormalities such as cracking and peeling were not observed in the dry film.
Δ: Some abnormalities such as cracks and peeling were observed in the dried film.
X: Abnormality was observed.

(4) Evaluation of durability by repeated heating and cooling test The appearance of the dried film produced above was visually observed after 10 cycles in a cycle of -20 ° C for 1 hour and 50 ° C for 1 hour. It was evaluated by.
○: Abnormalities such as cloudiness, whitening, cracking, and peeling were not observed in the dried film.
Δ: Some abnormalities such as cloudiness, whitening, cracking, and peeling were observed in the dried film.
X: Abnormality was observed.

(5) Evaluation of water resistance 0.2 ml of ion-exchanged water was dropped on the dry film prepared above. After holding the water droplet for 1 hour, it was wiped off, and the state of peeling, swelling and whitening of the dried film after 30 minutes was observed visually and evaluated according to the following criteria.
○: Abnormalities such as cloudiness, whitening, and peeling were not observed in the dried film.
(Triangle | delta): Cloudiness and whitening were recognized by the dry film | membrane, but peeling was not recognized.
□: The dry film was cloudy, whitened, and partly peeled.
X: The dry film was completely peeled off.

From the results of Table 1 and Table 2, the emulsion composition of the present invention experimental examples 1-1～1-21 is found to be excellent in storage stability.
Further, from the results of Table 4, it is shown in experiments Examples 2-1 to 2-11, the dried film obtained from the emulsion composition of the present invention are all tack and cohesion, is excellent in water resistance I understand that.
Furthermore, from the results of Table 6, experiments example shown in 2-12～2-21, dry film obtained from the emulsion composition of the present invention are all adhesion, durability, flexibility and water resistance It turns out that it is excellent.

Claims (3)

An emulsion composition in which polymer particles are dispersed in an aqueous medium,
The polymer particles are derived from 50 to 98% by mass of a structural unit (A) derived from an alkyl (meth) acrylate monomer having an alkyl group having 4 to 14 carbon atoms and an ethylenically unsaturated carboxylic acid monomer. Structural unit (B) 0.1 to 5% by mass, Structural unit derived from vinyl monomer having cyano group (C) 0.1 to 20% by mass, reaction of (meth) acrylic acid with monofunctional epoxy compound 1 to 20% by mass of the structural unit (D) derived from the monomer consisting of the product, and 0 to 50% by mass of the structural unit (E) derived from another monomer copolymerizable with the monomer. Contains ,
The monofunctional epoxy compound is a compound having a phenyl group,
Soluble matter for ethyl acetate of the dry film obtained by drying the emulsion composition, the emulsion composition characterized in der Rukoto than 30 wt%.
[However, the total of the structural unit (A), the structural unit (B), the structural unit (C), the structural unit (D), and the structural unit (E) is 100% by mass. ]   The emulsion composition according to claim 1, wherein the polymer particles have a glass transition temperature of -80 ° C to 0 ° C. The emulsion composition according to claim 1 or 2 , wherein the polymer particles are obtained by emulsion polymerization in the presence of a reactive emulsifier.