JP3660343B2 - Method for producing amphoteric emulsion resin composition - Google Patents

Description

【００３１】
実施例４
（アニオン性の重合性水溶性ポリマー（Ｂ₂）の製造）
攪拌機、滴下ロート、冷却管、温度計を備えたフラスコにエタノール５部を仕込み窒素雰囲気中で８０℃まで昇温し下記の組成物を滴下ロートに仕込み３時間で等速に滴下した。
組成物Ｉ’
アゾビスイソブチロニトリル １．０部
メタクリル酸メチル ６．０部
アクリル酸ブチル １０．０部
アクリル酸 ４．０部
滴下終了後、攪拌しながらさらに２時間８０℃で反応させた後５０℃まで冷却しメタアクリル酸ジメチルアミノエチル８．０部を加え１０分間エージングし蒸留水６６．０部で希釈しアニオン性重合性水性ポリマー（Ｂ₂）を得た。
【００３２】
（両性エマルジョン樹脂組成物の製造）
二重結合含有アニオン性水性ポリマー（Ｂ₂）を５０．０部仕込みアスコルビン酸ナトリウム０．１部と硫酸第一鉄の５％水溶液を０．１部加え、窒素気流下で80℃まで昇温し下記の組成物Ｂと組成物Ｃをそれぞれ滴下ロートに仕込み同時に二時間で等速にて滴下した。
組成物ＩＩ
メタクリル酸メチル １０．０部
アクリル酸ブチル ５．０部
スチレン ５．０部
組成物ＩＩＩ
３５％過酸化水素水 ０．１部
蒸留水 ５．０部
滴下終了後、３時間80℃に保ち、蒸留水２４．７部で希釈し両性エマルジョンを得た。
【００３３】
比較例１
攪拌機、滴下ロート、冷却管、温度計を備えたフラスコにエタノール５部を仕込み窒素雰囲気中で８０℃まで昇温し下記の組成物を混合し滴下ロートに仕込み３時間で等速に滴下した。
組成物Ｉ”
アゾビスイソブチロニトリル １．０部
メタクリル酸メチル ７．０部
アクリル酸ブチル ８．０部
メタクリル酸ジメチルアミノエチル ５．０部
滴下終了後、さらに２時間 ８０℃で反応させた後５０℃まで冷却し酢酸１．９部を加え１０分間エージングし蒸留水７２．１部で希釈しカチオン性水性ポリマーを得た。
【００３４】
次いで、カチオン性水性ポリマーをフラスコに５０．０部仕込み、アスコルビン酸ナトリウム０．１部と硫酸第一鉄の５％水溶液を０．１部加え、窒素気流下で80℃まで昇温し下記の組成物Ｂと組成物Ｃをそれぞれ滴下ロートに仕込み同時に二時間で等速に滴下した。
組成物ＩＩ
メタクリル酸メチル １０．０部
アクリル酸ブチル ５．０部
スチレン ５．０部
組成物ＩＩＩ
３５％過酸化水素水 ０．１部
蒸留水 ５．０部
滴下終了後、３時間80℃に保ち、蒸留水２４．７部で希釈しエマルジョンを得た。
【００３５】
比較例２〜４
組成物Ｉ”及びＩＩの組成及び酢酸の量を表２のとおりに変更したことを除いて、比較例１と同様にエマルジョン樹脂組成物を得た。

【００３６】
上記実施例及び比較例で得られた両性エマルジョン樹脂組成物の各性能を以下の方法により評価した。評価結果を表３に示す。
（付着性）
表３に挙げる各基材に固形分を２０％に調整した上記の実施例の両性エマルジョン樹脂組成物及び比較例のエマルジョン樹脂組成物を１００ｇ／ｍ²の量で塗布し、室温で２４時間放置した後、カッターナイフで塗装膜上に１ｍｍ×１ｍｍの１００個の方眼を刻み付け、得られた碁盤目に２５ｍｍ巾のセロハンテープを十分圧着して貼り付け、次いで引き剥がして欠落しないで残存する目の数を計測することにより付着性を評価する付着性試験を行い、以下の基準で評価した。
◎：１００個
○：９９〜９０個
△：８９〜８０個
×：７９〜７０個
××：６９個以下
【００３７】
（耐水性）
ガラス板に固形分を２０％に調整した上記の実施例の両性エマルジョン樹脂組成物及び比較例のエマルジョン樹脂組成物を１００ｇ／ｍ²塗布し、室温で２４時間放置した後水道水に１０日間浸し耐水性試験を行った。ブリスターの数に基づいて、以下の通りに評価した。
◎：ブリスター０個（変化なし）
○：ブリスター１〜５個
△：ブリスター６〜１５個
×：ブリスター１６〜２０個
××：ブリスター２１個以上
【００３８】
（金属腐食性）
固形分を２０％に調整した上記の実施例の両性エマルジョン樹脂組成物及び比較例のエマルジョン樹脂組成物を３００ｍｌのビーカーに１００ｍｌ秤取り、ブリキ板をエマルジョンに浸し、常温で錆が発生するまでの時間を測定し金属腐食テストを行った。以下の基準で評価した。
◎：１０日以上
○：９〜７日
△：６〜３日
×：２〜１日
××：１日以下
【００３９】

【００４０】
【発明の効果】
本発明の両性エマルジョンを用いれば、紙、プラスチックフィルム、及び無機基材への良好な付着性と耐水性を発現せしめ、インキ、塗料の汎用用途に使用できる他金属への腐食が少ない効果により、建材ライン用シーラー及びプライマーとして使用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an aqueous resin composition that can be used as a coating material for metals, paper, plastic films, inorganic base materials for building materials, and the like. More specifically, the present invention relates to an aqueous resin composition containing both amino groups and acid groups having conflicting properties, and exhibits adhesion, water resistance or corrosion resistance to various substrates shown when the resin is coated. By controlling the amount and position of the resin in the resin with respect to the amino group and acid group, which are functional groups that affect the properties, the paper can eventually overcome the disadvantage of being aqueous. The present invention relates to a method for producing an amphoteric emulsion resin composition having excellent compatibility with films, building materials and metals.
[0002]
[Prior art]
As a material to be applied to the surface of the base material to form a coating film, great efforts have been paid to the technology to overcome the weakness in performance due to being aqueous due to environmental problems and safety problems in recent years, As a result, it is a well-known fact that the use of water-soluble resins and emulsion resin compositions is increasing.
[0003]
One of the development trends of coating film forming materials in recent years is focusing on cationic water-based resins having excellent properties that can easily overcome weaknesses in water, and this seems to be the mainstream.
One example is a water-based material that has room temperature crosslinkability and can form a dense coating film, and a cationic microemulsion containing fine particles with a particle size of 0.1 microns or less is proposed as a resin having a gloss similar to that of a solvent system. Has been.
However, it is usual that an organic acid is used as a neutralizing agent for a cationic aqueous resin capable of exhibiting excellent properties. Therefore, the organic acid, which is a neutralizing agent, is inevitably accompanied by volatilization when the coating film is cured, and its use is accompanied by prevention processing such as corrosion to metals, or use for materials that are not corroded. The actual situation is that there are constraints such as.
[0004]
On the other hand, another development tendency is to employ an aqueous amphoteric resin, thereby developing a product using a neutralizing agent-free aqueous resin that does not use a volatile neutralizing agent. Several products are also provided for this.
For example, a neutral-agent-free core-shell type emulsion produced by reversed-phase core-shell polymerization and employing an aqueous amphoteric electrolyte resin for the shell and a hydrophobic resin for the core (see Patent Documents 1 to 3), etc. It is.
[0005]
However, these prior art products are limited by their applications, and in particular, they do not meet the requirement of sufficiently imparting water resistance and corrosion resistance to metal substrates after curing at room temperature.
[0006]
[Patent Document 1]
JP 2000-26560 A [Patent Document 2]
JP 2000-248019 A [Patent Document 3]
Japanese Patent Laid-Open No. 2000-119141
[Problems to be solved by the invention]
An object of the present invention is to provide an amphoteric emulsion resin composition having good adhesion, water resistance and corrosion resistance not only to paper, plastic films and inorganic substrates, but also to metal substrates.
[0008]
[Means for Solving the Problems]
In order to solve this problem, the present inventors have analyzed why a reversed-phase core-shell amphoteric emulsion using a neutralizing agent-free amphoteric electrolyte aqueous polymer as a shell component has insufficient water resistance and corrosion resistance. By doing research,
1) From the shell component, which is the original amphoteric polymer, one of the functional groups, either acid groups or amino groups, is transferred to the core component, and the opposite ionic functional groups are localized.
2) As a technique for achieving 1), an ionic polymerizable polymer containing only one functional group of either an acid group or an amino group is used alone as a shell component, and a polymerizable acid monomer is used as a core component during polymerization. Introduce.
3) The reaction for imparting a polymerizable function to the acid group or amino group-containing polymer in the synthesis of the shell component is not a reaction for introducing a polymerizable double bond group into the polymer by a covalent bond, but a conflicting acid or base. The reaction in which the monomer is neutralized at a predetermined ratio is used, and the monomer that will remain unneutralized is used as the core component. By taking the following means, the amphoteric emulsion resin composition was successfully obtained and the present invention was completed. In the present specification, the “amphoteric emulsion resin composition” is a resin composition in the form of an emulsion having a core part and a shell part having ionic properties in which fine particles constituting the emulsion are opposite to each other. means.
[0009]
That is, the present invention
(1) Polymer A having a weight average molecular weight of 5000 to 50,000 obtained by solution polymerization of at least one amino group-containing polymerizable compound A and at least one polymerizable compound C containing neither an organic acid group nor an amino group ₁ is reacted with at least one organic acid group-containing polymerizable compound B in an equivalent ratio range of 0.1 to 1.5 with respect to 1 equivalent of the amino group in the polymer A ₁ to form a cationic polymerizable water-soluble compound. A step of obtaining a polymer A ₂ ; and polymerization capable of copolymerization with the cationic polymerizable water-soluble polymer A ₂ , an unreacted organic acid group-containing polymerizable compound B, and the cationic polymerizable water-soluble polymer A _2. An emulsion compound of at least one polymerizable compound C that is an acidic compound and contains neither an acid group nor an amino group, and the organic acid group-containing polymerizable compound B and the compound C are co-polymerized using the A ₂ as a cationic shell component. Polymer is anionic A step of obtaining a reversed-phase core-shell emulsion having as a component;
A process for producing an amphoteric emulsion resin composition, comprising:
(2) Weight average molecular weight of 5000 to 50,000 obtained by solution polymerization of at least one organic acid group-containing polymerizable compound B and at least one polymerizable compound C containing neither an organic acid group nor an amino group An anionic polymerizable water solution is prepared by reacting polymer B ₁ with at least one amino group-containing polymerizable compound A in an equivalent ratio range of 0.1 to 1.5 with respect to 1 equivalent of the organic acid group in the polymer B _1. A step of obtaining a polymerizable polymer B ₂ ; and a polymerization copolymerizable with the anionic polymerizable water-soluble polymer B ₂ , an unreacted amino group-containing polymerizable compound A, and the anionic polymerizable water-soluble polymer B _2. Of at least one polymerizable compound C, which is an organic compound and does not contain an amino group, and polymerizes the amino acid-containing polymerizable compound A and the compound C using B ₂ as an anionic shell component. Click copolymer A step of obtaining a reversed-phase core-shell emulsion having an on-core component;
A process for producing an amphoteric emulsion resin composition,
Moreover, it is related with the resin composition manufactured by those manufacturing methods.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The embodiment of the present invention will be described in more detail.
In the present invention, the amino group-containing polymerizable compound A is preferably an α, β-ethylenic polymerizable compound having an amino group, and is not limited to these, but dimethylaminomethyl acrylate, diethylaminomethyl acrylate, dibutylaminomethyl acrylate, Acrylates such as dihexylaminomethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, di (t-butyl) aminoethyl acrylate, diisohexylaminoethyl acrylate, dihexylaminopropyl acrylate, and di (t-butyl) aminohexyl acrylate; Corresponding methacrylates and the like are included. These compounds may be used alone or in a complex system.
[0012]
The organic acid group-containing polymerizable compound B of the present invention is preferably an α, β-ethylenic polymerizable compound having an organic acid group, such as acrylic acid, itaconic acid, maleic acid, t-butylacrylamide sulfonic acid, Examples include acrylates such as 2-acryloyloxyethyl succinic acid and 2-acryloyloxyethyl phthalic acid, and corresponding methacrylates. These may be used alone or in a complex system.
[0013]
The polymerizable compound C containing no organic acid group and amino group of the present invention is preferably an α, β ethylenic polymerizable compound having no organic acid group and amino group, such as alkyl or acrylic acid or methacrylic acid alkyl or Cycloalkyl ester, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl Monomers such as methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate; styrene, vinyl toluene, α-methyl styrene, Vinyl monomers such as vinyl acetate, acrylonitrile, methacrylonitrile, etc .; hydroxyalkyl esters of acrylic acid or methacrylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc. The body is included. These may be used alone or in a complex system.
[0014]
In the present invention, the polymer A ₁ is obtained by a conventionally known solution polymerization method using an amino group-containing polymerizable compound A and a polymerizable compound C not containing an organic acid group and an amino group using a known polymerization initiator. A polymer having a weight average molecular weight of 5000 to 50,000. Preferably, the solution polymerization is performed at a temperature of 70 to 180 ° C.
[0015]
On the other hand, in the present invention, the polymer B ₁ is a conventionally known solution polymerization method using an organic acid group-containing polymerizable compound B and a polymerizable compound C containing no organic acid group and amino group, using a known polymerization initiator. Is a polymer having a weight average molecular weight of 5,000 to 50,000. Preferably, the solution polymerization is performed at a temperature of 70 to 180 ° C.
[0016]
In the solution polymerization to the polymers A ₁ and B ₁ , the compounding amount of the amino group-containing polymerizable compound A is at least 5% by weight to 60% by weight of the total constituents of the polymer A ₁ and contains organic acid groups. The compounding amount of the polymerizable compound B is preferably at least 5% by weight and not more than 60% by weight of all the constituent elements of the polymer B ₁ . In either case, when these compounds are less than 5% by weight of the constituent elements, the emulsifying power may not be produced at all or may not be sufficient in the subsequent emulsion polymerization. On the other hand, when the amount is more than 60% by weight, performance such as water resistance of the corner may be impaired. Further, it is preferably 5 to 40% by weight.
[0017]
In the present invention, the polymerization initiator for solution polymerization of the polymer A ₁ or the polymer B ₁ is not particularly limited, but an azo polymerization initiator such as azobisisobutyronitrile, or a peroxide polymerization such as benzoyl peroxide. Initiators and the like are included. These polymerization initiators may be used alone or in a composite system.
[0018]
In the present invention, examples of the solvent that can be used for the solution polymerization include aromatics such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as normal butanol, isobutanol, and isopropyl alcohol; ethyl acetate , Esters such as n-butyl acetate, and the like. These may be used alone or in a complex system. Alcohols having good solubility for the polymer A ₁ are preferred.
[0019]
In the present invention, the cationic polymerizable water-soluble polymer A ₂ is obtained by reacting an organic acid-containing polymerizable compound B in a ratio range of 0.5 to 1.5 equivalents with respect to 1 equivalent of the amino group of the polymer A ₁ . By the above reaction, the amino acid group in the polymer A ₁ is partially neutralized by the organic acid-containing polymerizable compound B to be a cationic polymerizable water-soluble polymer A ₂ . Since the unreacted organic acid group-containing polymerizable compound B becomes a core component, there is no problem.
[0020]
On the other hand, in the present invention, the anionic polymerizable water-soluble polymer B ₂ is obtained by reacting an amino group-containing polymerizable compound A in a ratio range of 0.5 to 1.5 equivalents with respect to 1 equivalent of the organic acid group of the polymer B _1. . By the above reaction, the organic acid group in the polymer B ₁ is partially neutralized by the amino group-containing polymerizable compound B to become an anionic polymerizable water-soluble polymer A ₂ . Since the unreacted amino group-containing polymerizable compound A becomes a core component, there is no problem.
[0021]
The amphoteric emulsion resin composition of the present invention comprises:
Cationic polymerizable water-soluble polymer A ₂ , unreacted organic acid group-containing polysynthetic compound B, and copolymerizable with the cationic polymerizable water-soluble polymer A ₂ , containing an organic acid group and an amino group Or an anionic polymerizable water-soluble polymer B ₂ , an unreacted amino group-containing polymerizable compound A, and the anionic polymerizable water-soluble polymer B ₂ . By emulsion polymerization with a polymerizable compound C that is polymerizable and does not contain organic acid groups and amino groups,
can get.
[0022]
In the above emulsion polymerization, the water-soluble polymer A ₂ or B ₂ also serves as an emulsifier. Although it does not specifically limit as a polymerization initiator for emulsion polymerization, A well-known redox polymerization initiator can be used, For example, hydrogen peroxide is included. As an emulsion polymerization medium, water is preferably used. Moreover, it is preferable to perform emulsion polymerization at the temperature of 60 to 90 degreeC.
The polymerizable compound C used in the emulsion polymerization may be the same as or different from the polymerizable compound C that does not contain an acid group and amino group used in the synthesis of the polymer A ₁ or B _1. Good.
[0023]
Therefore, the method for producing the amphoteric emulsion resin composition of the present invention comprises:
Cationic polymerizable aqueous polymer A ₂ as a shell component and a copolymer of anionic organic acid group-containing polymerizable compounds B and C as a core; or Anionic polymerizable aqueous polymer B ₂ as a shell component, A copolymer of cationic amino group-containing polymerizable compounds A and C as a core component;
This is a method for producing an amphoteric emulsion composition having opposite ionic properties in the core and the shell, respectively.
[0024]
There is no particular limitation on how much the core / shell ratio should be set in this manufacturing method. It may be determined according to the required performance.
[0025]
In the amphoteric emulsion resin composition of the present invention, the cationic aqueous polymer and the anionic aqueous polymer are localized in the core part and the shell part, respectively, and the stability depends on whether the shell is an anion or a cation. It has been found that there is no difference in adhesion, water resistance and corrosion resistance to various base materials, and it can be made extremely excellent.
[0026]
The amphoteric emulsion resin composition of the present invention can be used as a sealer due to its excellent adhesion to inorganic base materials for building materials with strong alkalinity, and furthermore, coating on paper and plastic films due to its excellent water resistance and gloss. It is also suitable as a resin.
[0027]
【Example】
The following examples further illustrate aspects of the present invention. These examples are intended to illustrate the invention and not to limit it.
[0028]
Example 1
(Production of cationic polymerizable water-soluble polymer (A ₂ ))
A flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer was charged with 5 parts of ethanol, heated to 80 ° C. in a nitrogen atmosphere, the following composition was mixed, charged into the dropping funnel and added dropwise at a constant rate in 3 hours. .
Composition I
Azobisisobutyronitrile 1.0 part Methyl methacrylate 7.0 parts butyl acrylate 8.0 parts dimethylaminoethyl methacrylate 5.0 parts After completion of dropping, the mixture was further reacted at 80 ° C. for 2 hours with stirring.
Thereafter, the product was cooled to 50 ° C., 2.3 parts of acrylic acid was added, aged for 10 minutes, and diluted with 71.7 parts of distilled water to obtain a cationic polymerizable aqueous polymer (A ₂ ).
[0029]
(Production of amphoteric emulsion resin composition)
50.0 parts of the obtained cationic polymerizable aqueous polymer (A ₂ ) was placed in a flask, and 0.1 part of sodium ascorbate and 0.1 part of a 5% aqueous solution of ferrous sulfate were added. The temperature was raised to 80 ° C. under a nitrogen stream, and the following composition B and composition C were respectively charged into a dropping funnel and simultaneously dropped at a constant rate in 2 hours.
Composition II
Methyl methacrylate 10.0 parts butyl acrylate 5.0 parts styrene 5.0 parts Composition III
35 parts hydrogen peroxide solution 0.1 parts distilled water 5.0 parts After completion of dropping, the mixture was kept at 80 ° C. for 3 hours with stirring and diluted with 24.7 parts of distilled water to obtain an amphoteric emulsion.
[0030]
Examples 2-3
The following emulsion composition was obtained in the same manner as in Example 1 except that the compositions I and II and the amount of acrylic acid were as shown in Table 1.

[0031]
Example 4
(Production of anionic polymerizable water-soluble polymer (B ₂ ))
A flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer was charged with 5 parts of ethanol, heated to 80 ° C. in a nitrogen atmosphere, and the following composition was charged into the dropping funnel and dropped at a constant rate in 3 hours.
Composition I ′
Azobisisobutyronitrile 1.0 part Methyl methacrylate 6.0 parts Butyl acrylate 10.0 parts Acrylic acid 4.0 parts After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 2 hours with stirring, until 50 ° C. After cooling, 8.0 parts of dimethylaminoethyl methacrylate was added, aged for 10 minutes, and diluted with 66.0 parts of distilled water to obtain an anionic polymerizable aqueous polymer (B ₂ ).
[0032]
(Production of amphoteric emulsion resin composition)
50.0 parts of double bond-containing anionic aqueous polymer (B ₂ ) is added, 0.1 part of sodium ascorbate and 0.1 part of 5% aqueous solution of ferrous sulfate are added, and the temperature is raised to 80 ° C. under a nitrogen stream. Then, the following composition B and composition C were respectively charged into a dropping funnel and simultaneously dropped at a constant speed in 2 hours.
Composition II
Methyl methacrylate 10.0 parts butyl acrylate 5.0 parts styrene 5.0 parts Composition III
35 parts hydrogen peroxide solution 0.1 parts distilled water 5.0 parts After completion of dropping, the mixture was kept at 80 ° C. for 3 hours and diluted with 24.7 parts distilled water to obtain an amphoteric emulsion.
[0033]
Comparative Example 1
A flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer was charged with 5 parts of ethanol, heated to 80 ° C. in a nitrogen atmosphere, the following composition was mixed, charged into the dropping funnel and added dropwise at a constant rate in 3 hours.
Composition I "
Azobisisobutyronitrile 1.0 part Methyl methacrylate 7.0 parts Butyl acrylate 8.0 parts Dimethylaminoethyl methacrylate 5.0 parts After the completion of the dropwise addition, the reaction was continued at 80 ° C. for 2 hours until 50 ° C. The mixture was cooled, added with 1.9 parts of acetic acid, aged for 10 minutes, and diluted with 72.1 parts of distilled water to obtain a cationic aqueous polymer.
[0034]
Next, 50.0 parts of a cationic aqueous polymer was charged into the flask, 0.1 part of sodium ascorbate and 0.1 part of a 5% aqueous solution of ferrous sulfate were added, and the temperature was raised to 80 ° C. under a nitrogen stream. Composition B and Composition C were respectively charged into a dropping funnel and simultaneously dropped at a constant rate in 2 hours.
Composition II
Methyl methacrylate 10.0 parts butyl acrylate 5.0 parts styrene 5.0 parts Composition III
35 parts hydrogen peroxide solution 0.1 part distilled water 5.0 parts After completion of dropping, the mixture was kept at 80 ° C. for 3 hours and diluted with 24.7 parts distilled water to obtain an emulsion.
[0035]
Comparative Examples 2-4
An emulsion resin composition was obtained in the same manner as in Comparative Example 1 except that the compositions I ″ and II and the amount of acetic acid were changed as shown in Table 2.

[0036]
Each performance of the amphoteric emulsion resin compositions obtained in the above Examples and Comparative Examples was evaluated by the following methods. The evaluation results are shown in Table 3.
(Adhesiveness)
The amphoteric emulsion resin composition of the above-mentioned example and the emulsion resin composition of the comparative example, each having a solid content adjusted to 20%, were applied to each substrate listed in Table 3 in an amount of 100 g / m ² and left at room temperature for 24 hours. After that, 100 squares of 1 mm × 1 mm are engraved on the coating film with a cutter knife, and a cellophane tape having a width of 25 mm is sufficiently applied to the obtained grid, and then peeled off and remains without missing. An adhesion test for evaluating adhesion by measuring the number of eyes was performed, and evaluation was performed according to the following criteria.
◎: 100 ◯: 99 to 90 Δ: 89 to 80 ×: 79 to 70 ××: 69 or less
(water resistant)
A glass plate was coated with 100 g / m ² of the amphoteric emulsion resin composition of the above example and the comparative example adjusted to a solid content of 20%, allowed to stand at room temperature for 24 hours, and then immersed in tap water for 10 days. A water resistance test was conducted. Based on the number of blisters, the evaluation was as follows.
A: 0 blister (no change)
○: 1 to 5 blisters △: 6 to 15 blisters ×: 16 to 20 blisters XX: 21 or more blisters
(Metal corrosive)
100 ml of the amphoteric emulsion resin composition of the above example and the comparative example emulsion resin composition adjusted to 20% solids were weighed in a 300 ml beaker, the tin plate was immersed in the emulsion, and rust was generated at room temperature. Time was measured and a metal corrosion test was performed. Evaluation was made according to the following criteria.
◎: 10 days or more ○: 9 to 7 days Δ: 6 to 3 days ×: 2 to 1 day × ×: 1 day or less

[0040]
【The invention's effect】
By using the amphoteric emulsion of the present invention, it exhibits good adhesion and water resistance to paper, plastic film, and inorganic base material, and due to the effect of less corrosion on other metals that can be used for general purposes of inks and paints, Can be used as a sealer and primer for building material lines.

Claims (4)

A polymer A ₁ having a weight average molecular weight of 5000 to 50,000 obtained by solution polymerization of at least one amino group-containing polymerizable compound A and at least one polymerizable compound C containing neither an organic acid group nor an amino group; Cationic polymerizable water-soluble polymer A ₂ is reacted with at least one organic acid group-containing polymerizable compound B in an equivalent ratio range of 0.1 to 1.5 with respect to 1 equivalent of amino group in polymer A _1. And a cationic polymerizable water-soluble polymer A ₂ , an unreacted organic acid group-containing polymerizable compound B, and a polymerizable compound copolymerizable with the cationic polymerizable water-soluble polymer A _2. A copolymer of an organic acid group-containing polymerizable compound B and a compound C by emulsion polymerization of at least one polymerizable compound C containing neither an organic acid group nor an amino group, and using the A ₂ as a cationic shell component Anionic core Obtaining a reversed-phase core-shell emulsion having as a component,
A process for producing an amphoteric emulsion resin composition. A polymer B ₁ having a weight average molecular weight of 5000 to 50,000 obtained by solution polymerization of at least one organic acid group-containing polymerizable compound B and at least one polymerizable compound C containing neither an organic acid group nor an amino group; The anionic polymerizable water-soluble polymer B ₂ is obtained by reacting at least one amino group-containing polymerizable compound A in an equivalent ratio range of 0.1 to 1.5 with respect to 1 equivalent of the organic acid group in the polymer B _1. And an anionic polymerizable water-soluble polymer B ₂ , an unreacted amino group-containing polymerizable compound A, and a polymerizable compound copolymerizable with the anionic polymerizable water-soluble polymer B _2. And at least one polymerizable compound C containing neither an organic acid group nor an amino group is subjected to emulsion polymerization, and a copolymer of the amino group-containing polymerizable compound A and the compound C is prepared using the B ₂ as an anionic shell component. Cationic Having as A component, reverse-phase core - to obtain a shell emulsion,
A process for producing an amphoteric emulsion resin composition. An amphoteric emulsion resin composition obtained by the production method of claim 1, wherein the core part is anionic and the shell part is cationic. An amphoteric emulsion resin composition obtained by the production method of claim 2, wherein the core part is cationic and the shell part is anionic.