JP2003003035A - Aqueous emulsion composition - Google Patents

Abstract

(57) [Problem] To provide an aqueous emulsion composition which can lengthen a drying time and can freely adjust the length of the drying time. An aqueous emulsion composition containing heterophasic structure particles obtained by a multi-stage emulsion polymerization method and a wetting agent having a slow evaporation rate, wherein the heterophasic structure particles have a total number of added moles in one molecule. Ethylene oxide chain of 15 mol or more, reactive nonionic emulsifier having a propylene oxide chain 0.5 to 20 parts by mass and obtained by multi-stage emulsion polymerization of an aqueous emulsion containing 100 parts by mass of ethylenically unsaturated monomer, heterophase structure particles The polymer which forms the outermost phase of the hetero-phase structured particles contains at least 20% by mass of the monomer units composed of all ethylenically unsaturated monomers and the monomer units composed of styrene or its derivatives, and Temperature is -50 to 15
Aqueous emulsion composition, wherein the glass transition temperature of the polymer forming at least one phase inside the outermost phase of the heterophasic structure particles is 50 to 150 ° C, and the minimum film forming temperature of the aqueous emulsion composition is 30 ° C or less. .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous emulsion composition, and more particularly to an aqueous emulsion composition, which can have a long drying time and can be freely adjusted in length. Aqueous coating composition,
Regarding aqueous ink.

[0002]

2. Description of the Related Art In recent years, volatile organic compounds (hereinafter referred to as VOCs)
Say. ) And environmental regulations for reducing toxicity, etc., and from the perspective of resource conservation, the paint industry is changing from solvent-based paints that use organic solvents as solvents to water-based paints that use water. is there. As a typical paint thereof, there is an aqueous emulsion paint using an aqueous resin emulsion as a binder.

However, the aqueous resin emulsion has an inherent minimum film-forming temperature (hereinafter referred to as MFT),
Therefore, in order to be able to form a film even when the temperature of the surface to be coated is MFT or lower, it was necessary to add an organic solvent to the aqueous resin emulsion as a film forming aid.

Further, in the aqueous emulsion paint,
Since the time until the resin hardens is too short, the workability may be poor, or nozzle clogging may occur when used as ink. That is, there is a problem in that the workability is poor and the work operation becomes impossible because the resin is hardened by early drying on a plate, a screen, a roll, a spray, a brush, a roller, a nozzle and the like.

[0005]

The present invention has been made against the background of the problems of the prior art as described above, and uses a VOC such as a film-forming auxiliary which becomes a source of environmental pollution and odor. Even without, even if used, with a small amount of addition, it is possible to lengthen the drying time, also the aqueous emulsion composition that can be freely adjusted the length of the drying time,
For example, it is an object to provide an aqueous coating composition such as an aqueous paint and an aqueous ink composition such as a printing ink.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, by using a specific heterophasic structure particle obtained by a multistage emulsion polymerization method and a specific wetting agent in combination, The present invention has been completed by finding that the above object can be achieved with certainty.

That is, the aqueous emulsion composition of the present invention comprises heterophase structured particles obtained by a multistage emulsion polymerization method,
An aqueous emulsion composition containing a wetting agent having an evaporation rate of 30 or less calculated with the evaporation rate of butyl acetate being 100, wherein (1) the heterostructure particles have an average number of added moles in one molecule. By multistage emulsion polymerization of an aqueous emulsion containing 0.5 to 20 parts by weight of a reactive nonionic emulsifier having a total of 15 moles or more of ethylene oxide chains and / or propylene oxide chains and 100 parts by weight of ethylenically unsaturated monomers. (2) The polymer forming the heterophasic structure particles contains 20% by mass or more of monomer units made of all ethylenically unsaturated monomers and monomer units made of styrene or a derivative thereof. (3) the glass transition temperature of the polymer forming the outermost phase of the heterophase structured particles is -50 to 15 ° C, and (4) the glass transition temperature is inside the outermost phase of the heterophase structured particles. The glass transition temperature of the polymer to form a one-phase even without is 50 to 150 ° C., wherein the (5) minimum film forming temperature of the aqueous emulsion composition is 30 ° C. or less.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Aqueous emulsion composition of the present invention, heterophasic structure particles obtained by multistage emulsion polymerization of an aqueous emulsion containing the specific reactive nonionic emulsifier and the ethylenically unsaturated monomer described above (hereinafter, heterophasic structure emulsion particles And a specific wetting agent.

In the multistage emulsion polymerization method, an aqueous emulsion containing an ethylenically unsaturated monomer is used, and a conventionally known emulsion polymerization method is usually repeated in 2 to 5 steps to give a heterophase structure, that is, characteristics. Is an emulsion polymerization method in which particles composed of an outermost phase different from each other and one or more internal phases are formed. As a typical example of the multi-stage emulsion polymerization method, an aqueous emulsion containing an ethylenically unsaturated monomer is used, and an emulsifier and a polymerization initiator, and if necessary, a chain transfer agent and an emulsion stabilizer are present. And usually 60
An emulsion polymerization method in which emulsion polymerization is performed under heating at up to 90 ° C and this step is repeated a plurality of times is carried out.

In the present invention, as an essential ethylenically unsaturated monomer used for forming emulsion particles having a heterophasic structure, styrene and / or methylstyrene, chloro, and / or chlorostyrene are used to improve the water resistance of the resulting coating film. A styrene derivative such as styrene or methoxystyrene is contained in an amount of 20% by mass or more of the total ethylenically unsaturated monomer, preferably 25 to 8
Used in an amount of 0% by weight.

In the present invention, in addition to styrene and / or styrene derivatives, various ethylenically unsaturated monomers conventionally used in the production of acrylic resins can be used in combination. There is no particular limitation on the saturated monomer. Examples of the comonomer which is an ethylenically unsaturated monomer other than styrene include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and n.
-Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, α-chloroethyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylic monomers such as acrylate, phenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate; (meth) acrylic Acid and carboxyl group-containing monomers such as crotonic acid, itaconic acid, itaconic acid half ester, maleic acid, maleic acid half ester; 2-hydroxyethyl (meth)
Hydroxyl group-containing monomers such as acrylate, 2 (3) -hydroxypropyl (meth) acrylate, and 4-hydroxybutyl acrylate; (meth) acrylamide,
Amide group-containing monomers such as maleinamide; 2-aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, vinylpyridine Amino group-containing monomers such as; glycidyl (meth) acrylate, allyl glycidyl ether, epoxy obtained by reacting an epoxy compound having two or more glycidyl groups with an ethylenically unsaturated monomer having an active hydrogen atom Group-containing monomers and oligomers; N-methylol acrylamide having other N-methylol groups; 4- (meth) -acryloyloxy-
2,2,6,6-tetramethylpiperidine, 4- (meth) -acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) -acryloyloxy-
UV-stable monomers such as 1,2,2,6,6-pentamethylpiperidine; 2- [2'-hydroxy-5 '-(
Methacryloyloxymethyl) phenyl] -2H-benzotriazole and 2- [2'-hydroxy-5'-
UV-absorbing monomers such as (methacryloyloxyethyl) phenyl] -2H-benzotriazole; vinyl acetate, vinyl chloride, ethylene, butadiene, acrylonitrile, dialkyl fumarate and the like can be mentioned as typical ones. .

As described above, these comonomers have a glass transition temperature (hereinafter referred to as Tg) of the polymer forming the outermost phase of the heterophase emulsion particles of -50 to 15 ° C. It may be used in an appropriate combination so that the Tg of the polymer forming at least one phase of the internal phase becomes 50 to 150 ° C. and the MFT of the aqueous emulsion composition becomes 30 ° C. or less.

In the present invention, the polymer forming at least one phase inside the outermost phase of the emulsion particles of different phase structure preferably has an internal crosslinked structure. The polymer having an internal crosslinked structure is a molecule such as divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate as a part of the ethylenically unsaturated monomer. Emulsion polymerization using a monomer having two or more polymerizable unsaturated double bonds therein; a combination of monomers having functional groups that react with each other at the temperature during the emulsion polymerization reaction, for example, carboxyl Of emulsion polymerization using a monomer mixture containing selectively an ethylenically unsaturated monomer having a functional group such as a group and a glycidyl group or a combination of a hydroxyl group and an isocyanate group; hydrolysis condensation reaction occurs ( (Meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, (meth) acryloxypropyiene It can be prepared by methods such as; a method of emulsion polymerization using a monomer mixture which contains a silyl group-containing ethylenically unsaturated monomers such as methyl dimethoxy silane.

In the present invention, the outermost phase of the emulsion particles of different phase structure has 1 to 25 mass of the monomer unit composed of the ethylenically unsaturated monomer having a carbonyl group and the monomer unit composed of all the ethylenically unsaturated monomers. %, It is preferably a reaction product of a polymer and a compound having two or more hydrazide groups in the molecule. This polymer having a carbonyl group can be produced by emulsion-polymerizing an ethylenically unsaturated monomer having a carbonyl group and another ethylenically unsaturated monomer.

Examples of the ethylenically unsaturated monomer having a carbonyl group include acrolein, diacetone (meth) acrylamide, (meth) acryloxyalkylpropanal, diacetone (meth) acrylate,
Acetonyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate-acetylacetate and butanediol-1,4-acrylate-acetylacrylate, vinyl ethyl ketone, vinyl isobutyl ketone and the like can be mentioned. it can. Among these, acrolein, diacetone acrylamide, and vinyl ethyl ketone are particularly preferable.

In the present invention, the monomer unit composed of an ethylenically unsaturated monomer having a carbonyl group is one of the monomer units composed of all ethylenically unsaturated monomers forming the outermost phase of the heterophase emulsion particles. 25% by mass,
It is desirable to occupy 2 to 20% by mass. When the amount is less than 1% by mass, crosslinking between particles tends to be insufficient, while when it exceeds 25% by mass, water resistance and the like tend to deteriorate.

Examples of compounds containing two or more hydrazide groups in the molecule include carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and dodecane didecane. Examples thereof include acid dihydrazide, isophthalic acid dihydrazide, citric acid trihydrazide, 1,2,4-benzene trihydrazide and thiocarbodihydrazide. Among these, carbohydrazide, adipic acid dihydrazide, and succinic acid dihydrazide are preferable from the viewpoint of the balance of dispersibility in emulsion and water resistance.

The amount of the hydrazide group-containing compound to be added when the polymer having a carbonyl group and the hydrazide group-containing compound are reacted with respect to the outermost phase of the emulsion particles having a heterophase structure is such that the carbonyl group in the polymer having a carbonyl group is 1 It is suitable that the amount is 0.1 to 2.0 equivalents, preferably 0.3 to 1.2 equivalents of hydrazide group, based on the equivalents. When the amount of the hydrazide group-containing compound is less than the above range, the reaction with the carbonyl group in the emulsion particles of different phase structure becomes insufficient and the coating film hardness is not improved so much. On the other hand, when the amount is excessive, unreacted hydrazide group-containing compound remains, and the water resistance tends to deteriorate.

In the present invention, as the emulsifier, a reactive nonionic emulsifier having an ethylene oxide chain and / or a propylene oxide chain whose average addition mole number in one molecule is 15 moles or more in total, preferably 20 to 50 moles is used. . The reactive nonionic emulsifier is a compound having a polymerizable unsaturated group, a hydrophilic group and a hydrophobic group, which is copolymerizable with the ethylenically unsaturated monomer described later.

Commercially available products of reactive nonionic emulsifiers satisfying the above requirements include, for example, "Adecaria Soap N".
"E-20", "Adeka Rear Soap NE-30", "Adeka Rear Soap NE-40" [above Asahi Denka Kogyo Co., Ltd.], "Aqualon RN-20", "Aquaron RN-30", " Aqualon RN-50 "[above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] and the like.

By using a reactive nonionic emulsifier satisfying the above requirements, the viscosity of the coating material does not increase even if the powder of the base material to be coated is mixed into the coating material, and the stability is maintained. In addition, since the reactive nonionic emulsifier is incorporated into the polymer skeleton and uniformly distributed in the coating film, it becomes possible to form a coating film having excellent water resistance and the like. For that purpose, the reactive nonionic emulsifier is added in an amount of 0.1% by weight per 100 parts by mass of the ethylenically unsaturated monomer described later.
It is necessary to mix 5 to 20 parts by mass, preferably 2 to 15 parts by mass. The amount of the reactive nonionic emulsifier blended was 0.
If it is less than 5 parts by mass, the stability of the coating composition tends to deteriorate, and if it exceeds 20 parts by mass, the water resistance of the coating film tends to deteriorate, such being undesirable.

In the present invention, as the emulsifier,
It is also possible to use in combination with the reactive nonionic emulsifier that satisfies the above requirements, other reactive emulsifiers that do not satisfy the above requirements, such as anionic emulsifiers and anionic emulsifiers. Examples of such anionic emulsifiers include fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfate ester salts, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfate, polyoxynonyl phenyl ether. Examples thereof include ammonium sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, and so-called reactive emulsifiers having a sulfonic acid group or a sulfate ester group and a polymerizable unsaturated group in the molecule.

As the above-mentioned polymerization initiator, those generally used for radical polymerization can be used, and among them, water-soluble ones are preferable. For example, persulfates such as potassium persulfate and ammonium persulfate; 2,
Azo such as 2'-azobis (2-aminodipropane) hydrochloride, 4,4'-azobis-cyanovaleric acid, and 2,2'-azobis (2-methylbutanamide oxime) dihydrochloride tetrahydrate Examples of compounds include hydrogen peroxide solution and peroxides such as t-butyl hydroperoxide.
Further, a redox system in which a reducing agent such as L-ascorbic acid or sodium thiosulfate is combined with ferrous sulfate can also be used.

As the above-mentioned chain transfer agent, for example, n-
Long chain alkyl mercaptans such as dodecyl mercaptan, aromatic mercaptans, halogenated hydrocarbons and the like can be mentioned. As the emulsion stabilizer described above,
Examples thereof include polyvinyl alcohol, hydroxyethyl cellulose, polyvinylpyrrolidone and the like.

As the above-mentioned emulsion polymerization method, a monomer batch charging method in which monomers are charged all at once, a monomer dropping method in which monomers are continuously added dropwise, a monomer, water and an emulsifier are used. Examples of the method include a pre-emulsion method in which and are mixed and emulsified in advance and then added dropwise, or a method in which these are combined.

In the present invention, when the emulsion particles of different phase structure are produced by the above method, the theoretical Tg obtained from the formula of FOX of the polymer forming the outermost phase of the emulsion particles of different phase structure is -50 to 15 ° C., It is necessary to appropriately select the combination of ethylenically unsaturated monomers added in the final stage of the multistage emulsion polymerization so that the temperature is preferably −30 to 10 ° C. Further, it is necessary to appropriately select the combination of ethylenically unsaturated monomers so that the theoretical Tg of the polymer forming at least one of the internal phases is 50 to 150 ° C, preferably 55 to 100 ° C. .

When the Tg of the polymer forming the outermost phase of the heterophase emulsion particles is less than -50 ° C, the resulting coating film tends to have poor stain resistance and hot water resistance. When it exceeds the above range, the film-forming property tends to deteriorate at low temperature, which is not preferable. If the Tg of the polymer forming the internal phase is less than 50 ° C., the resulting coating film tends to have poor blocking resistance and physical properties.
On the contrary, if the temperature exceeds 150 ° C, the curing reaction does not proceed, which is not preferable.

In the present invention, the aqueous emulsion composition of the present invention has an MFT of 30 ° C. or lower, preferably -10 to 10.
It is necessary to appropriately select the combination of ethylenically unsaturated monomers so that the temperature is 20 ° C. If the MFT of the aqueous emulsion composition exceeds 30 ° C., the film-forming property deteriorates unless a large amount of film-forming aid is used, which is not preferable.

When the aqueous emulsion composition of the present invention satisfies the above-mentioned characteristics and conditions, it can be used as a VOC such as a film-forming aid.
Even if it is not used, or even if it is used, it is possible to form a film with a small amount of addition, and it is possible to form a coating film having excellent properties such as high water resistance.

The aqueous emulsion composition of the present invention has a pH of 6 with ammonia or amines such as triethylamine, trimethylamine and dimethylethanolamine in order to improve freeze-thaw stability and storage stability.
It is preferable to adjust it to 10.

The butyl acetate evaporation rate used in the aqueous emulsion composition of the present invention was calculated to be 3 and calculated as 3
As a wetting agent having an evaporation rate of 0 or less, glycerin,
Glycols such as ethylene glycol; carbitols such as methyl carbitol and ethyl carbitol acetate; pyrrolidones such as N-methyl-2-pyrrolidone and 2-pyrrolidone; water-soluble wetting agents such as DMSO (dimethyl sulfoxide). However, the type is not particularly limited. In the present invention, the emulsion particles of different phase structure, the wetting agent and the water are the emulsion particles of different phase structure / wetting agent / water = 1 to 20 / 0.01 to 50 /
It is mixed in a ratio of 30 to 99 (mass%).

The aqueous emulsion composition of the present invention contains a wetting agent having an evaporation rate of 30 or less when the evaporation rate of heterophase emulsion particles obtained by the above-mentioned multistage emulsion polymerization method and butyl acetate is calculated as 100. This aqueous emulsion composition can be used as it is as a clear paint or clear ink. Further, in order to impart various functions as a paint or ink, as necessary, an antifoaming agent, an antiseptic agent, an antifungal agent, a thickener, a freeze stabilizer, a wetting agent, an ultraviolet absorber, a light stabilizer. Well-known additives such as pigments and dyes can be blended. When blending the pigments and dyes, it is preferable to blend well-known additives such as dispersants and anti-settling agents.

The aqueous emulsion composition thus obtained is an inorganic type, a metal type, a wood type, a plastic type,
It can be applied to various base materials such as paper. In particular, it is suitable as a base treatment agent for ink, paint, etc., an overcoat agent for printing / painting, and a surface treatment agent. By naturally drying or forced drying, the drying time can be extended and the drying time can be freely set. It is possible to adjust.

[0034]

EXAMPLES The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited thereto. In addition, "part" in an Example and a comparative example is shown on a mass basis.

<Production of Aqueous Emulsions A, B and C Containing Emulsion Particles of Different Phase Structure> In a reactor equipped with a stirrer, a thermometer, a cooling pipe and a dropping device, ion-exchanged water 40
0 part, sodium hydrogencarbonate (pH adjuster) 1 part, reactive nonionic emulsifier "Adecaria Soap NE-20" (manufactured by Asahi Denka Co., Ltd.) [α- (1- (allyloxy) methyl-2- (nonyl) Phenoxy) ethyl) 80% aqueous solution of ω-hydroxypolyoxyethylene; ethylene oxide average addition mole number 20 moles] 5 parts, reactive anion emulsifier "Adekaria Soap SE-10N" (manufactured by Asahi Denka Kogyo KK) [α- Sulfo-ω- (1- (nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy-
2 parts of ammonium salt of polyoxy-1,2-ethanediyl); average number of moles of ethylene oxide added: 10 moles] were charged respectively, and while replacing the inside of the reactor with nitrogen, 8
The temperature was raised to 0 ° C.

Then, potassium persulfate (polymerization initiator) 1
Then, an emulsion (A) having the composition shown in Table 1 (numerals indicate the number of parts), which had been stirred and mixed in a separate container in advance, was added.
Was continuously added dropwise over 2 hours. The reaction temperature was lowered to 75 ° C. in 1 hour after the completion of the dropping in the first step. Then 1
The emulsion (B) having the composition shown in Table 1 (numerals indicate the number of parts), which had been stirred and mixed in advance as in the first step, was continuously added dropwise over 2 hours. After the dropwise addition was completed, the mixture was aged at 75 ° C. for 2 hours with continuous stirring, cooled to 40 ° C., and 50% dimethylethanolamine was added to adjust the pH to 9.0. Further, a hydrazide group-containing compound shown in Table 1 (numbers indicate the number of parts) was added, and aqueous emulsions A and B in which emulsion particles having a heterophasic structure each consisting of two phases were dispersed
And C were obtained. However, the Tg of the polymer forming the outermost phase of the emulsion particles of different phase structure in the aqueous emulsion C was 26 ° C. (higher than the upper limit of the range specified in the present invention).

<Production of Aqueous Emulsion D Containing Emulsion Particles of Different Phase Structure> In a reactor equipped with a stirrer, a thermometer, a cooling pipe and a dropping device, 200 parts of ion-exchanged water, 1 part of sodium hydrogen carbonate, a reactive nonionic emulsifier As
5 parts of "ADEKA REASOAP NE-20", as a reactive anionic emulsifier, "ADEKA REASOAP SE-10N" 2
Each part was charged, while replacing the inside of the reactor with nitrogen,
The temperature was raised to 80 ° C.

Then, potassium persulfate (polymerization initiator) 1
Then, an emulsion (A) having the composition shown in Table 1 (numerals indicate the number of parts), which had been stirred and mixed in a separate container in advance, was added.
Was continuously added dropwise over 4 hours. After dropping is completed, 8
The mixture was aged at 0 ° C. for 2 hours with stirring, cooled to 40 ° C., and then 50% dimethylethanolamine was added to p.
It was adjusted to H9.0. Further, a hydrazide group-containing compound shown in Table 1 (numbers indicate the number of parts) was added to obtain an aqueous emulsion D in which emulsion particles were dispersed. In this case, the obtained emulsion particles did not have a heterophasic structure.

The abbreviations of the respective raw materials shown in Table 1 have the following meanings, and the temperature in parentheses after the respective raw materials is the homopolymer of each monomer used in calculating Tg. The Tg of is shown. <Ethylenically unsaturated monomer> ST: Styrene (100 ° C) MMA: Methyl methacrylate (105 ° C) BA: Butyl acrylate (-54 ° C) MAA: Methacrylic acid (185 ° C) 2EHA: Acrylic acid-2 -Ethylhexyl (-50
AA: Acrylic acid (106 ° C.) DVB: Divinylbenzene (116 ° C.) GMA: Glycidyl methacrylate (41 ° C.) DAAM: Diacetone acrylamide (65 ° C.) AAEM: Acetoacetoxyethyl methacrylate (1)
1 ° C.) <hydrazide group-containing compound> ADH: adipic acid dihydrazide CH: carbohydrazide

[Tg (total,
C.) "is the" Tg of the polymer obtained when the mixture of the emulsion (A) and the emulsion (B) is emulsion polymerized in one stage ", and" Tg (core / shell, ° C. ) ”Is“ T of the polymer which is the internal phase obtained when the emulsion A is polymerized alone.
g / Tg of polymer as an external phase obtained by polymerizing Emulsion B alone.

[0041]

[Table 1]

An aqueous emulsion composition was prepared by blending any of the aqueous emulsions A to D shown in Table 1 and the wetting agent shown in Table 2 so as to obtain the composition shown in Table 2. Were prepared, and the tests of solidification of the brush and the clogging of the nozzle were carried out on the aqueous emulsion compositions. The results are shown in Table 2.

The test method and evaluation were carried out as follows. <Brush solidification> Using a brush made by Ginza Sakurai, soaked in an aqueous emulsion composition having the composition shown in Table 2 for 5 minutes, then pulled up and allowed to stand at 20 ° C and a humidity of 60% for half a day to visually solidify the brush. confirmed. <Evaluation Criteria> Good: The brush was not solidified and the surface was in a smooth state. X: The brush was solidified.

<Nozzle clogging property> Using Epson printer: PM-770C, the nozzle clogging was visually confirmed after standing for 7 days. <Evaluation Criteria> A: No nozzle clogging occurred, and continuous use was possible. C: Nozzle clogging occurred, and continuous use was difficult.

[0045]

[Table 2]

As is clear from the evaluation results shown in Table 2,
The aqueous emulsion composition of the present invention was excellent in solidifying the brush and clogging of the nozzle. On the other hand, in the case of using the emulsion C containing the emulsion particles of different phase structure having a high Tg of the shell which is the outermost phase and the case of using the emulsion D containing the particles of the single phase, the solidification of the brush and the clogging of the nozzle were observed. Sexuality has occurred.

[0047]

INDUSTRIAL APPLICABILITY The aqueous emulsion composition of the present invention can have a long drying time, and the length of the drying time can be freely adjusted.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 11/00 C09D 11/00 125/04 125/04 151/00 151/00 (72) Inventor Yuji Yamazaki 4-78-24 Tomiokanishi, Kanazawa-ku, Yokohama-shi, Kanagawa 4-78-24 (72) Inventor Masaaki Kunimatsu 36 10 F-term of 36, 3 Kumizawa, Totsuka-ku, Yokohama-shi, Kanagawa (reference) 4J002 BC031 BN201 EC046 EC056 ED026 EU026 EV216 FD206 GH01 HA04 4J011 KA14 KA15 KB13 KB19 KB29 4J026 AA17 AA44 BA30 BA32 BA38 BB07 DB04 FA07 GA09 4J038 CC021 CE052 CG001 CG172 MA08 MA10 4J039 AD03 AD09 AD10 BE22

Claims (4)

[Claims] 1. An aqueous emulsion composition comprising particles of a heterogeneous structure obtained by a multi-stage emulsion polymerization method, and a wetting agent having an evaporation rate of 30 or less when the evaporation rate of butyl acetate is 100. 1) The heterophasic structure particles have a reactive nonionic emulsifier having an ethylene oxide chain and / or a propylene oxide chain whose total number of added moles in one molecule is 15 moles or more in total.
It is obtained by multistage emulsion polymerization of an aqueous emulsion containing 5 to 20 parts by mass and 100 parts by mass of an ethylenically unsaturated monomer, and (2) the polymer forming the heterophase structure particles is all ethylene. Containing 20% by mass or more of the monomer unit composed of a polyunsaturated monomer, a monomer unit composed of styrene or a derivative thereof, and (3) the glass transition temperature of the polymer forming the outermost phase of the heterophase structured particles is -50 to 15 ° C., and (4) the glass transition temperature of the polymer forming at least one phase inside the outermost phase of the heterophase structure particles is 50 to 15
0 ° C., and (5) the minimum film forming temperature of the aqueous emulsion composition is 30.
A water-based emulsion composition having a temperature of at most 0 ° C. 2. The aqueous emulsion composition according to claim 1, wherein the polymer forming at least one phase inside the outermost phase of the particles of different phase structure has an internal crosslinked structure. 3. The outermost phase of the particles having a heterophasic structure comprises a monomer unit composed of an ethylenically unsaturated monomer having a carbonyl group and a monomer unit composed of all ethylenically unsaturated monomers.
The aqueous emulsion composition according to claim 1 or 2, which is a reaction product of a polymer containing 25% by mass and a compound having two or more hydrazide groups in the molecule. 4. An aqueous coating composition comprising the aqueous emulsion composition according to claim 1.