JP4065737B2 - Multilayer polymer emulsion - Google Patents

Description

【００６１】
【表２】

【００６２】
性能試験および凍結融解安定性試験
上記の通り製造したエマルションについて、最低造膜温度、塗面不粘着性、弾性率、引張り強さおよび凍結融解安定性を、下記の通り試験した。試験結果は表３の通りであった。
【００６３】
（＊３）最低成膜温度（ＭＦＴ）：日本理学工業(株)製の最低成膜温度測定機を使用して測定した。
【００６４】
（＊４）塗面不粘着性：５ｍｉｌドクターブレードを用いて、エマルション試料をガラス板上に塗布し、２０℃で７日間乾燥後、塗面を指でおさえて評価した。評価基準は次の通りである。
◎：粘着感がない
○：やや粘着感がある
×：強い粘着感がある
【００６５】
（＊５）弾性率，引張り強さ：５ｍｉｌドクターブレードを用いて、エマルション試料を脱脂したブリキ板上に塗布し、２０℃で７日間乾燥後、水銀を用いて塗膜を剥利した。剥離塗膜について、(株)島津製作所製のＥＺ Ｔｅｓｔによって測定した。
【００６６】
（＊６）凍結融解安定性：蓋付きの１００ｍｌポリエチレン製広口びんにエマルション試料５０ｇを入れ、次のサイクルで試験を行なった。
（−１０℃×１６時間 〜 ２５℃×５時間）× ３サイクル
【００６７】
試験後の試料の状態を次の評価基準に従って評価した。
◎：試験前と比べて、殆ど変化がない
○：試験前と比べて、わずかに粘度増加がある
△：少量の凝集物の生成がある
×：相当量の凝集物の生成がある。
【００６８】
【表３】

[0001]
BACKGROUND OF THE INVENTION
The present invention is a multilayer polymer emulsion capable of forming a film excellent in film forming property at low temperature without a film forming auxiliary, and excellent in strength and surface non-adhesiveness, and contains this emulsion, particularly for building interior and exterior It is related with the water-based emulsion paint useful as.
[0002]
[Prior art and problems]
Conventionally, in general-purpose aqueous emulsion paints, an organic solvent having a relatively high boiling point has been used as a film forming aid in order to ensure film forming properties at a low temperature. (VOC) and volatilization causes adverse effects on the environment such as air pollution. In addition, the aqueous emulsion paint that does not contain a film-forming aid cannot be used as a general-purpose aqueous emulsion paint because the use conditions are greatly restricted. This situation is described in detail as follows.
[0003]
A water-based emulsion paint that does not contain a film-forming aid becomes unusable because of poor film formation under a low-temperature environment of 5 to 10 ° C. Therefore, the coating under the temperature condition must be avoided, and the paint becomes greatly restricted in handling.
[0004]
An object of the present invention is to provide a multilayer polymer emulsion that can form a film excellent in film forming property at a low temperature and having excellent strength and surface non-adhesiveness without using a film forming aid. It is.
[0005]
Another object of the present invention is to use the above-mentioned multilayer polymer emulsion to form a coating film having excellent film forming properties and excellent strength and surface non-adhesiveness without using a film forming aid. It is to provide an aqueous emulsion paint. Furthermore, it is providing the water-based emulsion coating material which has these performances and was excellent in freezing stability, even if it does not use an antifreezing agent.
[0006]
[Means for Solving the Problems]
The inventors have a high glass transition temperature of the polymer constituting the innermost layer, a low glass transition temperature of the polymer constituting the intermediate layer, and a high glass transition temperature of the polymer constituting the outermost layer.And a specific monomer was used as at least a part of the polymerizable unsaturated monomer forming the polymer constituting the outermost layer.The inventors have found that the above object can be achieved by a multilayer polymer emulsion, and have completed the present invention.
That is, the present invention is a multilayer polymer emulsion containing substantially no volatile organic compound, wherein the polymer constituting the innermost layer has a glass transition temperature of 35 to 120 ° C., and the polymer constituting the intermediate layer Of the polymer constituting the outermost layer is in the range of 35 to 120 ° C, and the weight ratio of the polymer of the innermost layer, the intermediate layer and the outermost layer ( Solid content) is in the range of innermost layer / intermediate layer / outermost layer = 3-30 / 50-92 / 5-40,The polymer constituting the outermost layer is a copolymer of at least one hydrophilic polymerizable monomer selected from a sulfonic acid monomer, an amide monomer, and a polyoxyethylene macromonomer and another polymerizable monomer,And the emulsion particle diameter exists in the range of 0.20-2.0 micrometers, and the multilayer polymer emulsion characterized by the above-mentioned, and the water-based emulsion coating material containing this are provided.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The multilayer polymer emulsion of the present invention contains substantially no volatile organic compound (VOC). Here, the volatile organic compound (VOC) is usually a compound having a boiling point of 250 ° C. or lower.
[0008]
The multilayer polymer emulsion of the present invention comprises multilayer particles having an average particle diameter of 0.20 to 2.0 μm, preferably 0.25 to 1.0 μm. The multilayer particle is a multilayer structure particle in which at least three layers are overlapped from the center layer to the outer shell layer. It is also possible to form another layer between each layer. When the average particle size is smaller than 0.20 μm, the dispersion stability such as freezing stability and mechanical stability is inferior, and when the average particle size is larger than 2.0 μm, the standing stability and the film forming property are deteriorated.
[0009]
The emulsion composed of the multilayer particles is usually synthesized by a seed emulsion polymerization method or a multistage emulsion polymerization method. In the case of the three-layer structure particles, first, a first-stage polymerizable unsaturated monomer (one or two) that forms a polymer (which constitutes the innermost layer) having a glass transition temperature of 35 to 120 ° C., preferably 40 to 110 ° C. A seed mixture is prepared by emulsion polymerization of a mixture of at least seeds, and then a polymer having a glass transition temperature of −65 to 0 ° C., preferably −55 to −5 ° C. is formed in the presence of the seed. ) To form a second stage polymerizable unsaturated monomer (one kind or a mixture of two or more kinds), and then emulsion polymerization, and then a glass transition temperature of 35 to 120 ° C., preferably 40 to 110 ° C. Emulsion particles having a three-layer structure are obtained by emulsion polymerization of the third-stage polymerizable unsaturated monomer (one type or a mixture of two or more types) forming a coalescence (which constitutes the outermost layer).
[0010]
In this specification, when the absolute temperature of the glass transition temperature Tg (° C.) of each copolymer is Tg ″, it can be calculated as follows.
[0011]
1 / Tg "= W1 '/ T1 + W2' / T2 ... + Wn '/ Tn
(W1 ', W2' ... Wn 'is the weight fraction of each monomer to the total total monomers used in the production of the copolymer, T1, T2, ... Tn is the glass transition temperature of the homopolymer of each monomer. (Absolute temperature)
[0012]
The weight ratio (solid content) of the innermost layer / intermediate layer / outermost layer polymer is the innermost layer / intermediate layer / outermost layer = 3-30 / 50-92 / 5-40, preferably 5-25 / 60- Within the range of 87 / 8-35. Outside this range, the film formability at low temperatures is poor, or a film having poor strength and surface tackiness is formed, which is not desirable.
[0013]
Specific examples of the polymerizable unsaturated monomer include, for example, aromatic monovinyl compounds such as styrene, ethyl vinyl benzene, α-methyl styrene and fluorostyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl acrylate and ethyl Acrylate, butyl acrylate, 2-ethylhexyl acrylate, β-acryloyloxyethyl hydrogen phthalate, 2-hydroxyethyl acrylate, 2-acryloyloxy-2-hydroxyethylphthalic acid, 2-hydroxy-3-phenoxypropyl acrylate, glycidyl acrylate, Acrylic acid ester monomers such as N, N-dimethylaminoethyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ester Methacrylic acid ester monomers such as tilhexyl methacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 2-methacryloyloxy-2-hydroxypropyl phthalate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, N, N-dimethylaminoethyl acrylate; Carboxy group-containing unsaturated monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and their anhydrides; sulfoethyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, sodium methacryloyloxysulfonate, and the like Unsaturated monomer containing sulfonic acid group or sulfate ester group; acrylamide, methacrylamide Amide monomers such as N, N-dimethylacrylamide; Silicon-modified monomers; Polyoxyalkylene macromonomers such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; Divinylbenzene, 1,6-hexanediol diacrylate and the like Examples thereof include a polyvinyl compound.
[0014]
In the present invention, the polymer of the intermediate layer can be made into a crosslinked polymer by using the polyvinyl compound as at least a part of the polymerizable unsaturated monomer forming the polymer constituting the intermediate layer. This is advantageous. On the other hand, the polymer constituting the outermost layer has an acid value of 4 to 80 mgKOH / g, preferably 5 to 60 mgKOH / g. If the acid value is less than 4 mgKOH / g, the dispersion stability of the particles is insufficient, and there is a risk of problems in mechanical stability and freezing stability. If the acid value exceeds 80 mgKOH / g, the water resistance of the coating film is deteriorated. Not desirable.
[0015]
Further, as at least a part of the polymerizable unsaturated monomer forming the polymer constituting the outermost layer, at least one hydrophilic polymerizable unsaturated monomer selected from the sulfonic acid monomer, amide monomer and polyoxyalkylene macromonomer is used. Use is advantageous in terms of the freeze stability of the resulting emulsion.
[0016]
The emulsion polymerization is usually performed in the presence of water and an emulsifier. The emulsifier is not particularly limited as long as it does not contain a volatile organic compound, and a known anionic surfactant, nonionic surfactant, cationic surfactant, reactive emulsifier, and a mixture thereof are used. Can do.
[0017]
Examples of the anionic surfactant include various fatty acid salts, higher alcohol sulfates, alkylbenzene sulfonates, polyoxyethylene alkylphenyl ether sulfates, polycarboxylic acid type polymer surfactants, and the like. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, and the like. Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts. The reactive emulsifier is a surfactant having a polymerizable group in the molecule. Specific examples thereof include “ADEKA rear soap SE-10N” (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), “AQUALON HS-10”. (Daiichi Kogyo Seiyaku Co., Ltd., trade name).
[0018]
The amount of these emulsifiers used is suitably 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of monomers used.
[0019]
In the above-mentioned emulsion polymerization, an emulsifier may be added afterward from the viewpoint of enhancing the dispersion stability of the particles such as freezing stability. As the emulsifier to be added later, a sorbitan nonionic surfactant is suitable.
[0020]
In order to polymerize the polymerizable unsaturated monomer in the emulsion polymerization, a polymerization initiator is usually added. As the polymerization initiator, any conventionally known one can be used without particular limitation as long as it does not generate a volatile organic compound and itself does not correspond to a volatile organic compound. Examples of such water-soluble inorganic peroxides include persulfates such as potassium persulfate and ammonium persulfate, and these can be used alone or in combination of two or more. The amount used is preferably 0.1 to 2% by weight based on the amount of polymerizable unsaturated monomer used. In addition, you may perform redox polymerization by using a peroxide type polymerization initiator, a metal ion, or a reducing agent together as a polymerization initiator.
[0021]
In the above emulsion polymerization, if necessary, a continuous transfer agent such as mercaptans; a buffering agent such as sodium bicarbonate may be used. However, it is desirable not to use those that generate volatile organic compounds or those that themselves correspond to volatile organic compounds.
[0022]
The aqueous emulsion paint of the present invention contains a multilayer polymer emulsion obtained as described above as a binder component, ethylene glycol monobutyl acetate, ethylene glycol monobutyl ether conventionally used as a film-forming aid, Effectively contains volatile organic compounds with a boiling point of 250 ° C or lower such as organic solvents such as diethylene glycol monobutyl ether and water-soluble low molecular weight organic solvents having hydroxyl groups such as ethylene glycol and propylene glycol that have been used as freeze stabilizers It is something that does not.
[0023]
The coating composition of the present invention may further contain other water-soluble or water-dispersible resins, plasticizers, pigments, pigment dispersants, antifoaming agents, preservatives, ultraviolet absorbers, light stabilizers, oxidation agents as necessary. An inhibitor, a thickener, an anti-settling agent and the like may be appropriately contained. However, it is desirable not to use those that generate the volatile organic compounds or those that themselves correspond to volatile organic compounds.
[0024]
【The invention's effect】
According to the present invention, a particle emulsion having a specific multilayer structure in which an intermediate layer is soft is obtained, and an aqueous emulsion paint using the multilayer polymer emulsion is a film forming aid corresponding to VOC or antifreezing. Even without the use of an agent, it is possible to form a coating film having excellent film-forming properties at low temperatures and freezing stability, as well as excellent strength and surface tackiness, and a zero VOC coating can be obtained.
[0025]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that the scope of the present invention is not limited to these examples. Further, “parts” and “%” in the examples represent “parts by weight” and “% by weight”, respectively.
[0026]
Manufacture of multilayer polymer emulsion
Example 1
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 57 parts of deionized water, 0.5 part of sodium dodecylbenzenesulfonate, and 0.4 part of ammonium peroxodisulfate, stir well and foam, 78 parts of styrene and 20 parts of n-butyl acrylate. Then, 2 parts of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 30 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour.
[0027]
Next, in a separate container, 343 parts of deionized water, 2.9 parts of sodium dodecylbenzenesulfonate, and 2.4 parts of ammonium peroxodisulfate are added, and the mixture is thoroughly stirred and foamed. In this, 60 parts of styrene, 103 parts of methyl methacrylate are added. Part, n-butyl acrylate 419 parts, 2-hydroxyethyl acrylate 12 parts and acrylic acid 6 parts were added and stirred to prepare an emulsion. The prepared emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0028]
Next, 166 parts of deionized water, 8.6 parts of sodium dodecylbenzenesulfonate, and 1.2 parts of ammonium peroxodisulfate are added to another container, and the mixture is thoroughly stirred and foamed. In that, 30 parts of styrene, methyl methacrylate 192 are added. Part, n-butyl acrylate 63 parts, 2-hydroxyethyl acrylate 6 parts and acrylic acid 9 parts were added and stirred to make an emulsion, which was continuously added dropwise into the reactor in 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 25 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of three-layer structured particles. The obtained emulsion had a solid content concentration of 49.9%, a viscosity of 77 cps, a pH of 7.8, a particle size of 316 nm, and an MFT of 0 ° C. or lower.
[0029]
Example 2
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 34 parts of deionized water, 0.3 part of sodium dodecylbenzenesulfonate, 0.24 part of ammonium peroxodisulfate, stir well and foam, in which 47 parts of styrene, 12 parts of n-butyl acrylate Then, 1 part of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 30 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour.
[0030]
Next, in a separate container, 343 parts of deionized water, 2.9 parts of sodium dodecylbenzenesulfonate, and 2.4 parts of ammonium peroxodisulfate are added, and the mixture is thoroughly stirred and foamed. In this, 60 parts of styrene, 103 parts of methyl methacrylate are added. Part, n-butyl acrylate 419 parts, 2-hydroxyethyl acrylate 12 parts and acrylic acid 6 parts were added and stirred to prepare an emulsion. The prepared emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0031]
Next, 189 parts of deionized water, 8.8 parts of sodium dodecylbenzenesulfonate, and 1.36 parts of ammonium peroxodisulfate are added to a separate container, stirred well and bubbled, and 34 parts of styrene and methyl methacrylate 218 are added therein. Part, 71 parts of n-butyl acrylate, 7 parts of 2-hydroxyethyl acrylate and 10 parts of acrylic acid were added and stirred to form an emulsion, which was continuously added dropwise into the reactor over 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 27 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of three-layer structured particles. The obtained emulsion had a solid content concentration of 50.0%, a viscosity of 82 cps, a pH of 7.9, a particle size of 318 nm, and an MFT of 0 ° C. or lower.
[0032]
Example 3
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 34 parts of deionized water, 0.3 part of sodium dodecylbenzenesulfonate, 0.24 part of ammonium peroxodisulfate, stir well and foam, in which 47 parts of styrene, 12 parts of n-butyl acrylate Then, 1 part of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 30 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour.
[0033]
Next, in a separate container, 366 parts of deionized water, 3.1 parts of sodium dodecylbenzenesulfonate, 2.56 parts of ammonium peroxodisulfate are added, and the mixture is thoroughly stirred and foamed. In this, 64 parts of styrene, methyl methacrylate 110 Part, n-butyl acrylate 447 parts, 2-hydroxyethyl acrylate 13 parts and acrylic acid 6 parts were added and stirred to prepare an emulsion. The prepared emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0034]
Next, 166 parts of deionized water, 8.6 parts of sodium dodecylbenzenesulfonate, and 1.2 parts of ammonium peroxodisulfate are added to another container, and the mixture is thoroughly stirred and foamed. In that, 30 parts of styrene, methyl methacrylate 192 are added. Part, n-butyl acrylate 63 parts, 2-hydroxyethyl acrylate 6 parts and acrylic acid 9 parts were added and stirred to make an emulsion, which was continuously added dropwise into the reactor in 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 25 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of three-layer structured particles. The obtained emulsion had a solid content concentration of 49.9%, a viscosity of 78 cps, a pH of 7.8, a particle size of 318 nm, and an MFT of 0 ° C. or lower.
[0035]
Example 4
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 57 parts of deionized water, 0.5 part of sodium dodecylbenzenesulfonate, and 0.4 part of ammonium peroxodisulfate, stir well and foam, 78 parts of styrene and 20 parts of n-butyl acrylate. Then, 2 parts of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 30 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour.
[0036]
Next, in a separate container, 400 parts of deionized water, 3.4 parts of sodium dodecylbenzenesulfonate, and 2.8 parts of ammonium peroxodisulfate are added, stirred well and bubbled. In that, 70 parts of styrene, 120 parts of methyl methacrylate are added. Part, n-butyl acrylate 489 parts, 2-hydroxyethyl acrylate 14 parts and acrylic acid 7 parts were added and stirred to prepare an emulsion. The prepared emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0037]
Next, in a separate container, 109 parts of deionized water, 8.1 parts of sodium dodecylbenzenesulfonate, and 0.8 parts of ammonium peroxodisulfate are added and stirred well, and 20 parts of styrene and 128 parts of methyl methacrylate are added to it. Part, 42 parts of n-butyl acrylate, 4 parts of 2-hydroxyethyl acrylate and 6 parts of acrylic acid were added and stirred to form an emulsion, which was continuously dropped into the reactor in 40 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, cooled to 40 ° C., and 22 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of three-layer structured particles. The obtained emulsion had a solid content concentration of 49.9%, a viscosity of 70 cps, a pH of 7.9, a particle diameter of 320 nm, and an MFT of 0 ° C. or lower.
[0038]
Example 5
An emulsion was prepared in the same manner as in Example 4 except that the monomer composition in Example 4 was that in Table 1. The property values of the obtained emulsion were as shown in Table 1.
[0039]
Examples 6-8 and Comparative Examples 5-7
An emulsion was prepared in the same manner as in Example 1 except that the monomer composition and the amount of the 20% aqueous sodium hydroxide solution in Example 1 were those shown in Table 1. The property values of the obtained emulsion were as shown in Table 1.
[0040]
Example 9
An emulsion was prepared in the same manner as in Example 1 except that the monomer composition and the amount of 20% aqueous sodium hydroxide solution in Example 1 were those shown in Table 1. Thereafter, an aqueous emulsifier solution “50% Newcol 95FJ” (manufactured by Nippon Emulsifier Co., Ltd., polyoxyalkylene sorbitan fatty acid ester) was added and mixed and stirred. The property values of the finally obtained emulsion were as shown in Table 1.
[0041]
Comparative Example 1
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 400 parts of deionized water, 3.4 parts of sodium dodecylbenzenesulfonate and 2.8 parts of ammonium peroxodisulfate, stir well and foam, in which 70 parts of styrene, 120 parts of methyl methacrylate, n -489 parts of butyl acrylate, 14 parts of 2-hydroxyethyl acrylate, and 7 parts of acrylic acid were added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0042]
Next, 166 parts of deionized water, 8.6 parts of sodium dodecylbenzenesulfonate, and 1.2 parts of ammonium peroxodisulfate are added to another container, and the mixture is thoroughly stirred and foamed. In that, 30 parts of styrene, methyl methacrylate 192 are added. Part, n-butyl acrylate 63 parts, 2-hydroxyethyl acrylate 6 parts and acrylic acid 9 parts were added and stirred to make an emulsion, which was continuously added dropwise into the reactor in 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 25 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of two-layer structured particles. The obtained emulsion had a solid content concentration of 49.9%, a viscosity of 77 cps, a pH of 7.7, a particle size of 325 nm, and an MFT of 0 ° C. or lower.
[0043]
Comparative Example 2
The reactor of Comparative Example 1 was charged with 327 parts of deionized water and the internal air was replaced with nitrogen, and then the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 343 parts of deionized water, 2.9 parts of sodium dodecylbenzenesulfonate, 2.4 parts of ammonium peroxodisulfate, stir well and foam, in which 60 parts of styrene, 103 parts of methyl methacrylate, n -419 parts of butyl acrylate, 12 parts of 2-hydroxyethyl acrylate and 6 parts of acrylic acid were added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0044]
Next, 223 parts of deionized water, 9.1 parts of sodium dodecylbenzenesulfonate, and 1.6 parts of ammonium peroxodisulfate are added to another container, and the mixture is thoroughly stirred and foamed. In that, 40 parts of styrene, 256 of methyl methacrylate are added. Part, 84 parts of n-butyl acrylate, 8 parts of 2-hydroxyethyl acrylate and 12 parts of acrylic acid were added and stirred to form an emulsion, which was continuously added dropwise into the reactor in 1 hour and 20 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, cooled to 40 ° C., and 29 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of two-layer structured particles. The obtained emulsion had a solid content concentration of 50.0%, a viscosity of 88 cps, a pH of 7.8, a particle diameter of 320 nm, and an MFT of 4 ° C.
[0045]
Comparative Example 3
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 229 parts of deionized water, 1.94 parts of sodium dodecylbenzenesulfonate, 1.6 parts of ammonium peroxodisulfate, stir well and foam, in which 312 parts of styrene, 80 parts of n-butyl acrylate Then, 8 parts of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 1 hour and 20 minutes. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0046]
Next, 337 parts of deionized water, 10.06 parts of sodium dodecylbenzenesulfonate, and 2.4 parts of ammonium peroxodisulfate are added to a separate container, and the mixture is thoroughly stirred and foamed. In that, 60 parts of styrene, 91 of methyl methacrylate are added. Part, 419 parts of n-butyl acrylate, 12 parts of 2-hydroxyethyl acrylate and 18 parts of acrylic acid were added and stirred to make an emulsion, which was continuously added dropwise into the reactor over 2 hours. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 30 parts of a 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of two-layer structured particles. The obtained emulsion had a solid content concentration of 50.0%, a viscosity of 108 cps, a pH of 7.8, a particle size of 324 nm, and MFT of 2 ° C.
[0047]
Comparative Example 4
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 286 parts of deionized water, 2.43 parts of sodium dodecylbenzenesulfonate, 2.0 parts of ammonium peroxodisulfate, stir well and whisk, 390 parts of styrene, 100 parts of n-butyl acrylate. Then, 10 parts of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 1 hour 30 minutes. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0048]
Next, 280 parts of deionized water, 9.57 parts of sodium dodecylbenzenesulfonate, and 2.0 parts of ammonium peroxodisulfate are added to another container, and the mixture is thoroughly stirred and foamed. In that, 50 parts of styrene and 76 parts of methyl methacrylate are added. Parts, 349 parts of n-butyl acrylate, 10 parts of 2-hydroxyethyl acrylate and 15 parts of acrylic acid were added and stirred to form an emulsion, which was continuously added dropwise into the reactor over 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 25 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of two-layer structured particles. The obtained emulsion had a solid content concentration of 49.8%, a viscosity of 74 cps, a pH of 7.9, a particle size of 324 nm, and an MFT of 48 ° C. or lower.
[0049]
Comparative Example 8
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 200 parts of deionized water, 1.7 parts of sodium dodecylbenzenesulfonate and 1.4 parts of ammonium peroxodisulfate, stir well and whisk, 273 parts of styrene, 70 parts of n-butyl acrylate. Then, 7 parts of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor over 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour.
[0050]
Next, in a separate container, 200 parts of deionized water, 1.7 parts of sodium dodecylbenzenesulfonate, and 1.4 parts of ammonium peroxodisulfate are added and stirred well, and 35 parts of styrene and 60 parts of methyl methacrylate are added therein. Part, 244 parts of n-butyl acrylate, 7 parts of 2-hydroxyethyl acrylate and 4 parts of acrylic acid were added and stirred to prepare an emulsion. The prepared emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0051]
Next, 166 parts of deionized water, 8.6 parts of sodium dodecylbenzenesulfonate, and 1.2 parts of ammonium peroxodisulfate are added to another container, and the mixture is thoroughly stirred and foamed. In that, 30 parts of styrene, methyl methacrylate 192 are added. Part, n-butyl acrylate 63 parts, 2-hydroxyethyl acrylate 6 parts and acrylic acid 9 parts were added and stirred to make an emulsion, which was continuously added dropwise into the reactor in 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, cooled to 40 ° C., and 22 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of three-layer structured particles. The obtained emulsion had a solid content concentration of 49.8%, a viscosity of 71 cps, a pH of 7.9, a particle size of 316 nm, and an MFT of 50 ° C. or higher.
[0052]
Comparative Example 9
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 57 parts of deionized water, 0.5 part of sodium dodecylbenzenesulfonate, and 0.4 part of ammonium peroxodisulfate, stir well and foam, 78 parts of styrene and 20 parts of n-butyl acrylate. Then, 2 parts of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 30 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour.
[0053]
Next, in a separate container, 492 parts of deionized water, 4.2 parts of sodium dodecylbenzenesulfonate, and 3.4 parts of ammonium peroxodisulfate were added and stirred well, and then 86 parts of styrene and 148 parts of methyl methacrylate were added. Part, 600 parts of n-butyl acrylate, 17 parts of 2-hydroxyethyl acrylate and 9 parts of acrylic acid were added and stirred to prepare an emulsion. The prepared emulsion was continuously dropped into the reactor over 3 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0054]
Next, add 17 parts of deionized water, 7.3 parts of sodium dodecylbenzenesulfonate, and 0.2 part of ammonium peroxodisulfate to a separate container, stir well and foam, in which 4.0 parts of styrene, methyl Add 25.6 parts of methacrylate, 8.4 parts of n-butyl acrylate, 0.8 part of 2-hydroxyethyl acrylate, and 1.2 parts of acrylic acid to make an emulsion, which takes 10 minutes. It was continuously dropped into the inside. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 16 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of three-layer structured particles. The obtained emulsion had a solid content concentration of 49.9%, a viscosity of 65 cps, a pH of 8.0, a particle size of 319 nm, and an MFT of 0 ° C. or lower.
[0055]
Comparative Example 10
A condenser, thermometer, and dropping funnel were attached to a 2-liter 4-necked flask, charged with 327 parts of deionized water, the air inside was replaced with nitrogen, and the internal temperature was raised to 80 ° C. while stirring. In a separate container, add 58 parts of deionized water, 2.4 parts of sodium dodecylbenzenesulfonate, and 0.4 parts of ammonium peroxodisulfate and stir well. In that, 78 parts of styrene and 20 parts of n-butyl acrylate Then, 2 parts of 2-hydroxyethyl acrylate was added and stirred to prepare an emulsion. The deionized water in the reactor was stirred, and 44 parts of the prepared emulsion was charged therein, and stirring was continued for 20 minutes. Thereafter, the remaining emulsion was continuously dropped into the reactor in 30 minutes. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour.
[0056]
Next, in a separate container, 350 parts of deionized water, 14.8 parts of sodium dodecylbenzenesulfonate and 2.4 parts of ammonium peroxodisulfate are added, and the mixture is thoroughly stirred and foamed. Parts, 419 parts of n-butyl acrylate, 12 parts of 2-hydroxyethyl acrylate, and 6 parts of acrylic acid were added and stirred to prepare an emulsion. The prepared emulsion was continuously dropped into the reactor over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 1 hour, and 100 parts of deionized water was added all at once.
[0057]
Next, 166 parts of deionized water, 2.8 parts of sodium dodecylbenzenesulfonate, and 1.2 parts of ammonium peroxodisulfate are added to a separate container, and the mixture is thoroughly stirred and foamed. Part, 63 parts of n-butyl acrylate, 6 parts of 2-hydroxyethyl acrylate and 9 parts of acrylic acid were added and stirred to make an emulsion, which was continuously dropped into the reactor over 1 hour. After completion of dropping, the mixture was stirred at 80 ° C. for 1 hour, then cooled to 40 ° C., and 27 parts of 20% aqueous sodium hydroxide solution was added to the reactor to obtain an emulsion composed of three-layer structured particles. The obtained emulsion had a solid content concentration of 50.0%, a viscosity of 160 cps, a pH of 7.9, a particle size of 188 nm, and an MFT of 0 ° C. or lower.
[0058]
In the above Examples and Comparative Examples, the residual monomer amount in the emulsion was 0.1% or less. In addition, (Note 1) and (Note 2) in Table 1 and Table 2 are as follows, and the viscosity and particle diameter of the emulsion were measured as follows.
(Note 1) “Antox MS-2N”: manufactured by Nippon Emulsifier Co., Ltd., sodium methacryloyloxysulfonate
(Note 2) “MA-150MF”: manufactured by Nippon Emulsifier Co., Ltd., polyethylene glycol methacrylate
[0059]
Measurement of emulsion properties
(* 1) Viscosity: Measured with a B-type viscometer (60 rpm, 20 ° C.).
(* 2) Particle size: Measured using a COUTER N4 type submicron particle analyzer manufactured by Nikki Co., Ltd., and the MEAN value was shown.
[0060]
[Table 1]

[0061]
[Table 2]

[0062]
Performance test and freeze-thaw stability test
The emulsion produced as described above was tested for the minimum film-forming temperature, coating surface tack-free property, elastic modulus, tensile strength and freeze-thaw stability as follows. The test results are shown in Table 3.
[0063]
(* 3) Minimum film formation temperature (MFT): Measured using a minimum film formation temperature measuring machine manufactured by Nippon Rigaku Corporation.
[0064]
(* 4) Non-tackiness of coated surface: An emulsion sample was applied on a glass plate using a 5 mil doctor blade, dried at 20 ° C. for 7 days, and then the coated surface was evaluated with a finger. The evaluation criteria are as follows.
A: No sticky feeling
○: Slightly sticky
X: Strong adhesion
[0065]
(* 5) Elastic modulus, tensile strength: The emulsion sample was coated on a degreased tin plate using a 5 mil doctor blade, dried at 20 ° C. for 7 days, and then the coating film was stripped using mercury. The release coating film was measured by EZ Test manufactured by Shimadzu Corporation.
[0066]
(* 6) Freeze-thaw stability: A 50 ml emulsion sample was placed in a 100 ml polyethylene wide-mouthed bottle with a lid, and the test was performed in the following cycle.
(−10 ° C. × 16 hours to 25 ° C. × 5 hours) × 3 cycles
[0067]
The state of the sample after the test was evaluated according to the following evaluation criteria.
A: Almost no change compared to before the test
○: There is a slight increase in viscosity compared to before the test.
Δ: A small amount of aggregate is formed
X: A considerable amount of aggregates are formed.
[0068]
[Table 3]

Claims (3)

It is a multilayer polymer emulsion substantially free of volatile organic compounds, the glass transition temperature of the polymer constituting the innermost layer is 35 to 120 ° C., and the glass transition temperature of the polymer constituting the intermediate layer is − The glass transition temperature of the polymer constituting the outermost layer is in the range of 35 to 120 ° C, and the weight ratio (solid content) of the polymer of the innermost layer, the intermediate layer and the outermost layer is the highest. Inner layer / intermediate layer / outermost layer = 3-30 / 50-92 / 5-40, and the polymer constituting the outermost layer is at least selected from a sulfonic acid monomer, an amide monomer, and a polyoxyethylene macromonomer a copolymer of one hydrophilic polymerizable monomer and other polymerizable monomer, and multilayered polymer emulsion emulsion particle size is characterized to be within the scope of 0.20~2.0μm 2. The multilayer polymer emulsion according to claim 1, wherein the polymer constituting the outermost layer is a polymer having an acid value in the range of 4 to 80 mgKOH / g. A water-based emulsion paint containing the multilayer polymer emulsion according to claim 1 or 2 .