JPS59152910A - Oxidative polymerization-type aqueous emulsion and its production - Google Patents

Abstract

PURPOSE:To provide the titled emulsion giving a coating film having especially excellent corrosion resistance and water resistance, by carrying out the emulsion polymerization of a specific monomer modified with a fatty acid and a copolymerizable ethylenic unsaturated monomer at a specific ratio in an aqueous medium. CONSTITUTION:(A) 2-60pts.wt. of a fatty acid-modified monomer obtained by reacting (i) a drying oil fatty acid and/or a semidrying oil fatty acid (e.g. tall oil fatty acid) with (ii) an aziridinylalkyl ester of an alpha,beta-ethylenic unsaturated acid (e.g. aziridinylmethyl acrylate) and (B) 98-40pts.wt. of an alpha,beta-ethylenic unsaturated monomer copolymerizable with the component (A) are subjected to emulsion polymerization in an aqueous medium, preferably in the presence of a nonionic surface active agent, etc. to obtain the objective emulsion containing a copolymer composed of the components (A) and (B) and having an average molecular weight of 5,000-500,000, as a disperse phase. EFFECT:The obtained coating film is excellent also in solvent resistance, hardness, etc.

Description

【発明の詳細な説明】 本発明は酸化重合型水性エマルションならびにその製造
方法に係り、さらに詳しくは乾性油脂肪酸および／また
は半乾性油脂肪酸の残基が分子内に組みこまれた重合体
エマルションで酸化重合により耐食性、耐水性の特にす
ぐれた塗膜を与えることのできる水性エマルションなら
びにその製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oxidatively polymerized aqueous emulsion and a method for producing the same, and more specifically to a polymer emulsion in which residues of drying oil fatty acids and/or semi-drying oil fatty acids are incorporated into the molecule. The present invention relates to an aqueous emulsion that can provide a coating film with particularly excellent corrosion resistance and water resistance through oxidative polymerization, and a method for producing the same.

α、β−エチレン性不飽和単量体を乳化重合して得られ
るアクリルエマルションは非溶剤型の塗料ベースとして
有用である。しかしながらこういったエマルションは塗
膜物性をエマルション’ｆｌｒ　ＩＩＲの分子量のみに
依存しているため耐水性、耐溶剤性、耐薬品性、硬度等
の点で問題があり、特に耐食性の点では溶剤型、就中ア
ルキド樹脂塗料には遠く及ばない。Acrylic emulsions obtained by emulsion polymerization of α,β-ethylenically unsaturated monomers are useful as non-solvent type paint bases. However, these emulsions have problems in terms of water resistance, solvent resistance, chemical resistance, hardness, etc. because the physical properties of the coating film depend only on the molecular weight of emulsion 'flr IIR. However, it is still far behind alkyd resin paints.

高分子量でしかも酸化硬化型の樹脂を乳化重合の乳化剤
として使用し酸化硬化型のビニル系重合体エマルション
を得る試みも種々行われており、例えばマレイン化ポリ
ブタジェン、マレイン化油、マレイン化アルキド樹脂、
水溶性アルキド樹脂などを乳化剤としたエマルションが
知られている。Various attempts have been made to obtain oxidation-curable vinyl polymer emulsions by using high-molecular-weight, oxidation-curable resins as emulsifiers in emulsion polymerization, such as maleated polybutadiene, maleated oil, maleated alkyd resin,
Emulsions using water-soluble alkyd resins as emulsifiers are known.

しかしながらこれらは耐候性、安定性、着色等それぞれ
に欠点がある。最近こういった欠点を克服覆るものとし
て、アクリル重合体の側鎖に乾性油−９＝ 脂肪酸および／または半乾性油脂肪酸の残基を有づる構
造をもつ脂肪酸変性アクリル重合体の水溶化物を乳化剤
としてビニル単量体を乳化重合させ酸化重合型ビニル重
合体エマルションを得ることが提案されている（特開昭
５２−１０８４７１号）。しかし該エマルションは前述
のような安定性、着色等の問題は解決し得ても、分散安
定剤とエマルションの核を形成する高分子との化学的な
結合がないため物性はもっばら量的に多い核を形成する
高分子に依存し、耐溶剤性、耐薬品性、防食性におとり
、また分散安定剤はその性質上、限られた構造に限定さ
れ樹脂設計が狭くなり、しかも樹脂の酸価が高いため耐
水性の劣ったものしか得られない。従って本発明の目的
は耐水性、耐薬品性、耐溶剤性、硬度の改善された、特
に耐食性に優れたエマルションを提供するにある。本発
明のさらに別の目的は酸化重合で樹脂ビヒクルたるポリ
マーが三次元化され、それにより上記の如き優れた諸特
性の塗膜を与えつる水性エマルションを提供するにある
。さらにまた別の目的は上記水性エマ−１〇− ルションの製造方法を提供するにある。However, these have drawbacks in terms of weather resistance, stability, coloring, etc. Recently, as a method to overcome these drawbacks, an aqueous emulsifier of a fatty acid-modified acrylic polymer having a structure in which the side chain of the acrylic polymer has residues of drying oil-9=fatty acid and/or semi-drying oil fatty acid has been developed. As a method of emulsion polymerization of vinyl monomers, it has been proposed to obtain an oxidatively polymerized vinyl polymer emulsion (Japanese Unexamined Patent Publication No. 108471/1983). However, although such emulsions can solve the above-mentioned problems such as stability and coloring, their physical properties are mostly limited because there is no chemical bond between the dispersion stabilizer and the polymer that forms the core of the emulsion. Due to their nature, dispersion stabilizers are limited to a limited structure, making resin design narrower, and the acid resistance of the resin Due to its high value, only products with poor water resistance can be obtained. Therefore, an object of the present invention is to provide an emulsion having improved water resistance, chemical resistance, solvent resistance, and hardness, and particularly excellent corrosion resistance. Still another object of the present invention is to provide an aqueous emulsion in which the resin vehicle polymer is made three-dimensional by oxidative polymerization, thereby providing a coating film with excellent properties as described above. Yet another object is to provide a method for producing the above aqueous emulsion.

従来、アクリルエマルションの耐水性、その他の物性が
悪いのは界面活性剤あるいは乳化安定剤に関係が深いと
考えられており、改良はもっばら乳化安定剤に絞られて
いた。しかしながら本発明者らは乳化剤をいかように改
良してもその効果は乳化剤機能の改善にとどまり、アク
リル樹脂自体に起因する性能面での欠点は改良されぬ点
に着目し、アクリルエマルションの樹脂そのものを改質
するための研究を続けた結果、本発明に到達した。Conventionally, it has been thought that the poor water resistance and other physical properties of acrylic emulsions are closely related to surfactants or emulsion stabilizers, and improvements have been focused mostly on emulsion stabilizers. However, the present inventors focused on the fact that no matter how much the emulsifier was improved, the effect was only to improve the emulsifier function, and the performance defects caused by the acrylic resin itself were not improved. As a result of continuing research to improve the property, we have arrived at the present invention.

すなわち本発明に従えば、乾性油脂肪酸および／または
半乾性油脂肪酸とα、β−エチレン性不性用飽和酸アジ
リジニルアルキルエステル応で１ｑられる脂肪酸変性単
量体２〜６０重量部、および該脂肪酸変性単量体と共重
合可能な伯のα、β−エチレン性不性用飽和単量体９８
〜４０重量部得られる数平均分子量約５，０００〜５０
０．０００の共重合体を水中に分散させてなる酸化重合
型水性エマルションが提供される。That is, according to the present invention, 2 to 60 parts by weight of a fatty acid-modified monomer that can be obtained by reacting drying oil fatty acid and/or semi-drying oil fatty acid with α, β-ethylenically unsaturated saturated acid aziridinyl alkyl ester, and α,β-ethylenically unsaturated saturated monomer 98 copolymerizable with the fatty acid-modified monomer
~40 parts by weight, resulting in a number average molecular weight of approximately 5,000-50
An oxidative polymerization type aqueous emulsion is provided in which 0.000 of a copolymer is dispersed in water.

アクリルエマルションにおいては共重合体の平均分子量
が例えば１００．０００〜６００，０００の如くかなり
大であることが塗膜性能面上必要とされており、平均分
子量が小さいと乾燥性、耐水性などが劣ると考えられて
いる。しかしながら本発明にかかるアクリル共重合体は
その特異な構造組成から、塗装後に酸化重合によりポリ
マー自身三次元化され高分子化されるため、エマルショ
ン自体が高分子量である必要はなく、数平均分子量で約
５，０００程度のものであれば充分にその効果があられ
れる。またあまり高分子量のものはかえって製造が困難
であるとの理由から、共重合体の数平均分子量は５００
．０００程度まで゛の範囲に設計ゼられる。しかしなが
らエマルション樹脂の数平均分子量は乳化剤等信の共存
物質によっても左右されるので上記は絶対的なものでは
なく、ある程度の変動は許容されるものと解されるべき
である。本発明にかかる酸化重合型水性エマルション〈
アクリルエマルション）の共重合体を構成する成分の１
つは、乾性油脂肪酸および／または半乾性油脂肪酸とα
、β、β−エチレン飽和酸のアジリジニルアルキルエス
テルとの反応で得られる脂肪酸変性単量体である。かか
る単量体は例えば乾性油脂肪酸および／または半乾性油
脂肪酸に対しα、β、β−エチレン飽和酸のアジリジニ
ルアルキルエステルを重合禁止剤の存在下に４０〜′２
００℃で反応させることにより容易に得られ、この場合
不活性溶剤を使用してもかまわない。In acrylic emulsions, it is necessary for the average molecular weight of the copolymer to be quite large, for example from 100,000 to 600,000, in terms of coating performance.If the average molecular weight is small, drying properties, water resistance, etc. considered inferior. However, due to the unique structural composition of the acrylic copolymer according to the present invention, the polymer itself becomes three-dimensional and polymerized through oxidative polymerization after coating, so the emulsion itself does not need to have a high molecular weight and has a number average molecular weight. If it is about 5,000, the effect can be sufficiently achieved. In addition, because it is difficult to produce a copolymer with a very high molecular weight, the number average molecular weight of the copolymer is 500.
．． It can be designed in a range of up to 000. However, since the number average molecular weight of the emulsion resin also depends on coexisting substances such as emulsifiers, the above is not absolute, and it should be understood that some variation is allowed. Oxidative polymerization type aqueous emulsion according to the present invention
One of the components constituting the copolymer of acrylic emulsion)
One is drying oil fatty acid and/or semi-drying oil fatty acid and α
It is a fatty acid-modified monomer obtained by the reaction of β, β-ethylene saturated acid with aziridinyl alkyl ester. Such monomers include, for example, aziridinyl alkyl esters of α, β, β-ethylene saturated acids for drying oil fatty acids and/or semi-drying oil fatty acids in the presence of polymerization inhibitors.
It can be easily obtained by reacting at 00°C, and in this case an inert solvent may be used.

乾性油脂肪酸または半乾性油脂肪酸としては例えばキリ
油脂肪酸、脱水ヒマシ油脂肪酸、アマニ油脂肪酸、ザフ
ラワー油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ケシ油
脂肪酸、トール油脂肪酸、ぬか油脂肪酸、トウモロコシ
油脂肪酸、ヒマワリ油脂肪酸等通常の任意の型のものが
用いられる。Drying oil fatty acids or semi-drying oil fatty acids include, for example, tung oil fatty acids, dehydrated castor oil fatty acids, linseed oil fatty acids, safflower oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy oil fatty acids, tall oil fatty acids, rice bran oil fatty acids, corn oil fatty acids. Any conventional type of fatty acid, sunflower oil fatty acid, etc. can be used.

またα、β、β−エチレン飽和酸のアジリジニルアルキ
ルエステルの代表例はアジリジニルメチル−、アジリジ
ニルエチル−、アジリジニルプロピル−およびアジリジ
ニルブチル−アクリレートあるいはメタクリレートなど
である。共重合体の別の成分は、前記脂肪酸変性単量体
と共重合可能な他のα、β、β−エチレン飽和単量体で
ある。が１３− かる単量体としてはアクリル酸、メタクリル酸、および
それらのヒドロキシアルキルエステル、アルキルエステ
ル類；アクリルアミドおよびメタクリルアミドなどの不
飽和アミド化合物：スチレン、ビニルトルエン、α−メ
チルスチレンなどのスチレン系七ツマー；アクリロニト
リル、メタクリレートリル等の不飽和ニトリル；酢酸ビ
ニル等があげられ、それらの１種または２種以上を組合
わせて使用する。Typical examples of aziridinyl alkyl esters of α, β, β-ethylene saturated acids include aziridinyl methyl, aziridinyl ethyl, aziridinyl propyl, and aziridinyl butyl acrylate or methacrylate. Another component of the copolymer is another α,β,β-ethylene saturated monomer copolymerizable with the fatty acid modified monomer. Examples of such monomers include acrylic acid, methacrylic acid, and their hydroxyalkyl esters and alkyl esters; unsaturated amide compounds such as acrylamide and methacrylamide; styrenic compounds such as styrene, vinyltoluene, and α-methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylate trile; and vinyl acetate; one type or a combination of two or more of them may be used.

本発明のアクリル共重合体はしかしながら前記の脂肪酸
変性単量体２〜６０重量部と共重合可能なα、β−エチ
レン性不性用飽和単量体９８〜４０重量部構成されてい
ることを必須とする。脂肪酸部分には酸化硬化に関与す
る不飽和結合が含まれているが、この脂肪酸変性単量体
の割合が２％未満では酸化重合（自然酸化あるいは金属
ドライヤーの混入で促進）してもポリマーの架橋が少く
塗膜の性能向上がみられず、また６０％をこえると酸化
重合がすすみすぎて七〇くなり共に望ましくない。脂肪
酸変性単量体の割合は全七ツマ−中１４− ４〜４０重量％Ｃあることが特に９了ましい。However, it should be noted that the acrylic copolymer of the present invention is composed of 2 to 60 parts by weight of the fatty acid-modified monomer and 98 to 40 parts by weight of an α,β-ethylenic non-saturated monomer that can be copolymerized. Required. The fatty acid moiety contains unsaturated bonds that are involved in oxidative curing, but if the proportion of the fatty acid modified monomer is less than 2%, even if oxidative polymerization (promoted by natural oxidation or by the addition of a metal dryer) occurs, the polymer will not form. Since there is little crosslinking, no improvement in the performance of the coating film can be seen, and if it exceeds 60%, oxidative polymerization will proceed too much and it will reach 70%, both of which are undesirable. It is particularly preferable that the proportion of the fatty acid-modified monomer is 14-4 to 40% by weight C based on the total weight of the monomer.

本発明のエマルションは上記共重合体が水中に分散され
てなるものであって、樹脂分子内に酸化重合に関巧する
乾性油脂肪酸および／または半乾性ｈ１１脂肪酸部分が
組みこまれているため、塗装後自然醇化により、あるい
はより好ましくは金属ドライＡ７−の存イＥＴ”促進さ
れる酸化で共重合体自身がヨ次元的に架橋硬化され耐食
性、耐水性に特にすぐれた強じ／Ｖな塗膜が形成される
。The emulsion of the present invention is made by dispersing the above-mentioned copolymer in water, and since the drying oil fatty acid and/or semi-drying H11 fatty acid moiety involved in oxidative polymerization is incorporated into the resin molecule, After painting, the copolymer itself is cross-linked and hardened in a horizontal manner by natural thickening or, more preferably, by oxidation promoted by the presence of Metal Dry A7, resulting in a strong/V coating with particularly excellent corrosion resistance and water resistance. A film is formed.

また、乾性油脂肪酸および／にたは半乾性油脂肪酸とα
、β−エチレン性不性用飽和酸ジリジニルアルキル１ス
テルど反応の結果、脂肪酸変性用吊体に第２級のアミン
基が形成されるが、これが耐水性、耐アルカリ性等に悪
影響を及ぼすおそれがあるときには、アミン基と反応覆
る化合物（たトエハイワシ）ノネー１〜化合物）を加え
てアミノ基をつぶすことｅ、さらに耐水１ｆＪ１耐アル
カリ性は良好となる。In addition, drying oil fatty acids and/or semi-drying oil fatty acids and α
As a result of the β-ethylenically unsaturated saturated acid diridinyl alkyl 1-stere reaction, secondary amine groups are formed on the fatty acid modification suspension, but this has a negative effect on water resistance, alkali resistance, etc. If there is a risk, add a compound that reacts with the amine group (compounds) to crush the amino group, and further improve the water resistance 1fJ1 alkali resistance.

本発明のエマルションには所望により顔わ１、親水性溶
剤、可ソ性、着色剤等を加えたり、変性アミノ樹脂、−
［ポキシ樹脂、ポリエステル樹脂、アクリル樹脂等の広
範囲の水溶性もしくは水分散性樹脂をエマルションの特
性をそこなわぬ範囲内において配合Ｊることも可能であ
る。これらの組成物は常法にｊ、り塗料化され、浸漬法
、へケ塗り、スプレー塗り、ロール塗り等の方法により
塗装することが可能であり、各種素材に適用されるが、
特に水性であり且つ耐食性に優れた皮膜を与えるところ
から、金属月利のプライマーとして有用である。If desired, the emulsion of the present invention may contain additives such as 1, hydrophilic solvent, solubilizer, coloring agent, modified amino resin, -
[It is also possible to blend a wide range of water-soluble or water-dispersible resins such as poxy resins, polyester resins, and acrylic resins within a range that does not impair the properties of the emulsion. These compositions can be made into paints by conventional methods and applied to various materials by methods such as dipping, brushing, spraying, and roll coating.
It is especially useful as a primer for metals because it is water-based and provides a film with excellent corrosion resistance.

上記酸化重合型水性エマルションは、既に述べた乾性油
脂肪酸および／または半乾性油脂肪酸とα、β−エヂレ
ン性不飽和酸のアジリジニルアルキルエステルとの反応
で得られる脂肪酸変性単量体２〜６０重量部と、共重合
可能な他のα、β−］−チレン性不飽和単量体９８〜４
０重量部とを、水性媒体中、界面活性剤および／または
高分子保護コ［１イドの存在下に乳化重合させることに
より好都合に製造せられる。界面活性剤としては通常乳
化重合に使用せられる任意の公知のものが用いられるが
、例えばアルキルベンゼンスルボンＭＩＭ。The above-mentioned oxidative polymerization type aqueous emulsion contains fatty acid-modified monomers 2 to 2 obtained by the reaction of the above-mentioned drying oil fatty acid and/or semi-drying oil fatty acid with an aziridinyl alkyl ester of an α,β-edylenically unsaturated acid. 60 parts by weight and 98 to 4 other copolymerizable α,β-]-thyrenically unsaturated monomers
It is conveniently prepared by emulsion polymerization of 0 parts by weight in an aqueous medium in the presence of a surfactant and/or a polymeric protective co-hydrogen. As the surfactant, any known surfactant commonly used in emulsion polymerization can be used, such as alkylbenzenesulfone MIM.

脂肪酸石（プん、アルキル硫酸エステル等の陰イオン性
活性剤および／あるいはポリオキシエヂレンアルキル工
−デル、ポリオキシエチレン脂肪酸エステル、ソルビタ
ン脂肪酸エステル等の非イオン性活性剤が好都合に用い
られる。また乳化安定剤として、水溶性アルキド樹脂、
水溶性アクリル樹脂、マレイン化ポリブタジェン、マレ
イン化イソプレン等水溶性の高分子保護コロイドを使用
することもできる。Anionic activators such as fatty acid stones, alkyl sulfate esters and/or nonionic activators such as polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, sorbitan fatty acid esters are advantageously used. In addition, as an emulsion stabilizer, water-soluble alkyd resin,
Water-soluble polymeric protective colloids such as water-soluble acrylic resins, maleated polybutadiene, and maleated isoprene can also be used.

乳化重合は従来公知の方法で行うことができる。Emulsion polymerization can be performed by a conventionally known method.

重合温度は２０〜１００’Ｃで行われるが４０〜８０℃
で重合Ｊるのが好ましい。重合触媒としては水溶性の過
酸化物、過硫酸カリ、過硫酸アンモニウム等のラジカル
遊離触媒が用いられ、特に好ましいものは過硫酸アンモ
ニウム−メタ重亜硫酸ソーダ等のレドックス系触媒であ
る。またメルカプタン、四塩化炭素、四臭化炭素、イソ
プロパツール等の分子量調整剤を使用することもできる
。Polymerization temperature is 20-100'C, but 40-80'C
Preferably, the polymerization is carried out at As the polymerization catalyst, radical-releasing catalysts such as water-soluble peroxide, potassium persulfate, and ammonium persulfate are used, and particularly preferred are redox catalysts such as ammonium persulfate-sodium metabisulfite. Further, molecular weight modifiers such as mercaptan, carbon tetrachloride, carbon tetrabromide, and isopropanol can also be used.

本発明にかかる水性エマルションは樹脂成分が＝１７− 塗装後三次元化され強じんな塗膜を作るため、このよう
に界面活性剤などを使用してもその欠点が大幅に改善さ
れ、何らさまたげとならない。しかしながら乳化重合に
際し、かかる外部乳化剤、分散剤の使用量を可及的に減
少し、あるいは使用せぬことがより好ましいことは当然
である。これは脂肪酸変性単量体と共重合ゼしむべきα
、β−エチレン性不性用飽和単量体部分にそれ自体乳化
剤機能を有する単量体を選択使用することにより好都合
にその目的を達成することができる。乳化剤機能をもつ
単量体として特公昭５５−４１６８４号には一般式 ％式％ （式中Ｒ１は水素、低級アルキル、ハロゲン、フェニル
基；Ｒ２はエチレン、プロピレン基；Ｒ３は水素、低級
アルキル基、ｎは４〜２５の正数）で表わされる非イオ
ン性重合型単量体が、特公昭４、９−４６２９１号には
一般式 ＲＩ ■ ＣＨ２ＣＯＯ（ＡＯ）ｎ　　ＣＨ２Ｃ＝ＣＨｚ（式中Ｒ
１は水素またはメチル基；Ｒ２は飽和または不飽和の炭
化水素または置換炭化水素基、またはオキシアルキレン
基を含む有機基；Ａは炭素数２〜４のアルキレンまたは
置換アルキレン基；Ｍは水素、アルカリ金属、アルカリ
土類金属、アンモニウムまたは有機アミン：ｍはＭの原
子価またはイオン価；ｎはＯまたは正数） で示される陰イオン性重合型単量体が、さらによた米国
特許第４．０４９．６０８号には一般式（式中Ｒ１は水
素またはメチル基；Ｒ２は飽和よたは不飽和の炭化水素
または置換炭化水素基、またはオキシアルキレン基を含
む有機基：Ａ′は炭素数１〜２０の飽和または不飽和の
炭化水素また置換炭化水素基；Ｂは炭素数１〜６の飽和
炭化水素基；Ｍは水素、アルカリ金属、アルカリ土類金
属、アンモニウムまたは有機アミン；ｍはＭの原子価ま
たはイオン価） で示される陰イオン性重合型単量体が夫々示されている
。The aqueous emulsion according to the present invention has a resin component of = 17- after being applied to form a three-dimensional coating, which creates a strong coating film, so even if a surfactant is used, the drawbacks can be greatly improved, and there will be no hindrance. Not. However, it is natural that during emulsion polymerization, it is more preferable to reduce the amount of such external emulsifiers and dispersants used, or to eliminate their use. This is α that should be copolymerized with the fatty acid modified monomer.
This objective can be conveniently achieved by selectively using a monomer which itself has an emulsifier function in the β-ethylenically unsaturated saturated monomer portion. As a monomer with an emulsifier function, Japanese Patent Publication No. 55-41684 describes the general formula % (in the formula, R1 is hydrogen, lower alkyl, halogen, phenyl group; R2 is ethylene, propylene group; R3 is hydrogen, lower alkyl group). , n is a positive number from 4 to 25), and in Japanese Patent Publication No. 4,9-46291, there is a nonionic polymerizable monomer represented by the general formula RI ■ CH2COO(AO)n CH2C=CHz (in the formula R
1 is hydrogen or a methyl group; R2 is a saturated or unsaturated hydrocarbon or substituted hydrocarbon group, or an organic group containing an oxyalkylene group; A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group; M is hydrogen or alkali The anionic polymerizable monomer represented by the following formula is further described in US Pat. No. 049.608 contains the general formula (wherein R1 is hydrogen or a methyl group; R2 is a saturated or unsaturated hydrocarbon group or a substituted hydrocarbon group, or an organic group containing an oxyalkylene group; A' is a carbon number 1 ~20 saturated or unsaturated hydrocarbon or substituted hydrocarbon group; B is a saturated hydrocarbon group having 1 to 6 carbon atoms; M is hydrogen, alkali metal, alkaline earth metal, ammonium or organic amine; m is M Anionic polymerizable monomers with atomic or ionic valences are shown.

本発明者らはこれら乳化剤機能を有する重合性の単量体
がいづれも本発明においＣ前記のα、β−■ヂレン竹不
飽和単量体の一部として用いることかでき、しかもこの
場合には界面活性剤あるいは高分子保護コロイドの不存
在下に、脂肪酸変性単量体とエチレン性不飽和単量体の
乳化重合が実施でき、本発明の酸化重合型水性エマルシ
ョンを与えうろことを知った。但し、前記の非イオン性
重合型単量体の場合、α、β−エチレン性不性用飽和単
量体成分〜２０重量部を、また陰イオン性重合型＋４１
　ｆｄ体の場合には０．５〜１０重量部をかかる乳化剤
機能を有する単量体で置換することができ、それら下限
値未満では充分な内部乳化剤機能を期待し得ず、また上
限値をこえるとかえって塗膜の耐水性等に悪影響を及ぼ
すことをも見出した。勿論これら単量体と共に所望によ
り他の界面活性剤、分散安定剤を用いてもかまわない。The present inventors have found that any of these polymerizable monomers having an emulsifier function can be used as a part of the above-mentioned α,β-dylene bamboo unsaturated monomer C in the present invention, and that in this case, discovered that emulsion polymerization of fatty acid-modified monomers and ethylenically unsaturated monomers can be carried out in the absence of surfactants or polymeric protective colloids, yielding the oxidatively polymerized aqueous emulsion of the present invention. . However, in the case of the above-mentioned nonionic polymerizable monomer, ~20 parts by weight of the α,β-ethylenic non-saturated monomer component and anionic polymerizable monomer +41 parts by weight are added.
In the case of the fd form, 0.5 to 10 parts by weight can be substituted with a monomer having such an emulsifier function; below these lower limits, sufficient internal emulsifier function cannot be expected, and above the upper limit. On the contrary, it was found that it had an adverse effect on the water resistance of the coating film. Of course, other surfactants and dispersion stabilizers may be used together with these monomers, if desired.

従って本発明はまた前記の脂肪酸変性単量体２〜６０重
量部と、上記一般式で示される非イオン性重合型単量体
２〜２０重量部およびその他のα。Therefore, the present invention also includes 2 to 60 parts by weight of the aforementioned fatty acid-modified monomer, 2 to 20 parts by weight of the nonionic polymerizable monomer represented by the above general formula, and other α.

β−エチレン性不飽和単量体９６〜２０重量部を構成単
量体成分として含む共重合体、あるいは脂肪酸変性単（
イ）体２〜６０重量部と、上記の陰イオン性重合型単量
体０．５〜１０重量部およびその他のα、β、β−エチ
レン飽和単量体９７，５〜３０重量部を構成単量体成分
として含む共重合体の水性エマルションをも、好ましい
実施態様として含み、これらの製造法、すなわち内部乳
化剤機能を有する上記単量体の所定間をα、β−エチレ
ン性不性用飽和単量体部として選択使用し、界面活性剤
あるいは高分子保護コロイドの不存在下に＝２１− 乳化重合手法で酸化重合型水性エマルションを製造する
方法をも包含するものである。乳化重合法自体は公知の
方法に準じ実施せられる。上記いづれの方法を用いる場
合でも乳化重合により製造された上記共重合体の数平均
分子量は約５，０００〜５００．０００である。A copolymer containing 96 to 20 parts by weight of β-ethylenically unsaturated monomer as a constituent monomer component, or a fatty acid modified monomer (
b) Consists of 2 to 60 parts by weight of the monomer, 0.5 to 10 parts by weight of the above-mentioned anionic polymerizable monomer, and 97.5 to 30 parts by weight of other α, β, β-ethylene saturated monomers. Preferred embodiments also include aqueous emulsions of copolymers containing as monomer components, the method of preparing them, i.e. saturated α,β-ethylenically unsaturated monomers having internal emulsifier function. It also includes a method of producing an oxidative polymerization type aqueous emulsion by emulsion polymerization in the absence of a surfactant or polymeric protective colloid by selectively using it as a monomer part. The emulsion polymerization method itself is carried out according to a known method. No matter which method is used, the copolymer produced by emulsion polymerization has a number average molecular weight of about 5,000 to 500,000.

本発明にかかるエマルションは塗装後、酸化重合により
樹脂自体の三次元化で耐水性、耐溶剤性、耐薬品性、耐
食性に優れ、硬度の大なる皮膜を与え、特に耐食性の点
で従来の溶剤型アルキド樹脂塗料に匹敵する効果を示す
点に於て極めて特徴のあるものである。After painting, the emulsion of the present invention makes the resin itself three-dimensional through oxidative polymerization, giving a film with excellent water resistance, solvent resistance, chemical resistance, and corrosion resistance, and high hardness. It is extremely unique in that it exhibits effects comparable to type alkyd resin paints.

以下実施例ならびに比較例により本発明を説明する。例
文中「部」および「％」は「重量部」および［重量％−
１を各々意味する。The present invention will be explained below with reference to Examples and Comparative Examples. "Parts" and "%" in the example sentences are "parts by weight" and [% by weight -
Each means 1.

実施例１ ｌ−（ａ） あまに油脂肪酸　　　　　　　　２３７部メタクリル酸
アジリジニルエチル １３０部 ２２− ハイドロキノン　　　　　　　　０．４部を反応容器に
入れ、攪拌しながら１１０〜１２０℃の温度Ｃ反応を行
った。アジリジニル基とカルボキシル基の付加反応は、
残存カルボキシル基の量を測定しながら追跡した。反応
が完了するまで約３時間かかった。Example 1 l-(a) 237 parts of linseed oil fatty acid, 130 parts of aziridinylethyl methacrylate, and 0.4 parts of 22-hydroquinone were placed in a reaction vessel, and a temperature C reaction of 110 to 120°C was carried out with stirring. The addition reaction between aziridinyl group and carboxyl group is
The amount of remaining carboxyl groups was tracked while being measured. The reaction took approximately 3 hours to complete.

１−（ｂ） 攪拌器、冷？Ｊｌ器、温度制御装置、窒素導入管を備え
た１リツ１ヘル］ルベンに、１；（イオン水３７０部、
ラウリル硫酸す１〜リウム（花王石鹸社製：エマールＯ
）４．．２部とポリオキシエチレンノニルフェニル十−
デル（花王石鹸社製：エマルゲン９３５）１４部を仕込
み、攪拌下で温度を８０°Ｃに９？渇した。別に用意し
た過硫酸カリウム１．４部を脱イオン水６０部に溶解し
たもののうち２０部を１リツｉ〜ルコルベンに仕込み、
約１０分間ののら、１−（ａ）の付加反応物５２．５部
、スチレン５６部、メタクリル酸メチル１２８部、アク
リル酸ｎ−ブチル１０９部、アクリル酸４．５部の混合
物を３時間かかつて滴下した。反応は窒素流入下で８０
″Ｃに保ちながら行った。過硫酸カリウムの残りは単量
体混合物の滴下と同時に３時間３０分で終了づるｊ、う
に滴下した。単量体混合物の滴下終了後、波調を８０’
Ｃに保ち２時間経過して終了とした。この方法により、
不揮発分４３．５％、粘度３５０　Ｃｐ、のエマルショ
ンを得た。樹脂の数平均分子量は約１５０．０００であ
った。1-(b) Is the stirrer cold? 1; (370 parts of ionized water,
So-lium lauryl sulfate (manufactured by Kao Soap Co., Ltd.: Emar O
)4. ．． 2 parts and polyoxyethylene nonylphenyl
Add 14 parts of Emulgen 935 (manufactured by Kao Soap Co., Ltd.) and raise the temperature to 80°C with stirring. I'm thirsty. Prepared separately, 1.4 parts of potassium persulfate was dissolved in 60 parts of deionized water, and 20 parts of it was added to 1 liter of water.
After about 10 minutes, a mixture of 52.5 parts of the addition reaction product 1-(a), 56 parts of styrene, 128 parts of methyl methacrylate, 109 parts of n-butyl acrylate, and 4.5 parts of acrylic acid was heated for 3 hours. It once dripped. The reaction was carried out at 80°C under nitrogen flow.
The remaining potassium persulfate was added dropwise at the same time as the monomer mixture, which was completed after 3 hours and 30 minutes. After the monomer mixture was added, the wave tone was adjusted to 80°C.
The test was kept at C and finished after 2 hours. With this method,
An emulsion with a non-volatile content of 43.5% and a viscosity of 350 Cp was obtained. The number average molecular weight of the resin was approximately 150,000.

実施例２ 攪拌器、冷却器、温度制御装置、窒素導入管を備えた１
リツｉ〜ルコルベンに、脱イオン水２２０部、ドデシル
ベンゼンスルフオン酸ナトリウム（花王石鹸社製：ネオ
ペレツクスＮｏ、６）１．０部、ポリオキシエチレンノ
ニルフェニルエーテル（花王石鹸ネ］製：エマルゲン９
３１）２．７部を什込み、攪拌下で温度を５０°Ｃに胃
渇した。別に、過硫酸アンモニウム１．７５部を脱イオ
ン水８０部に溶解したものと、亜硫酸水素ナトリウム１
゜７５部を脱イオン水８０部に溶解したものを用意した
。一方、脱イオン水１４０部に前記の界面活性剤すなわ
ちドデシルベンゼンスルフオン酸ナトリウムの２．５部
とポリオキシエチレンノニルフェニルエーテル１０．６
部を溶解したものを攪拌し４丁がら１−（ａ）の付加反
応物１４０部、スチレン２８部、メタクリル酸メチル８
７．５部、アクリル酸２−エヂルヘキシル７０部、アク
リル酸ヒドロキシエチル１６部、メタクリル１８．５部
の混合物をゆっくりと添加し、約５分後に反応単量体の
プレエマルションをえた。１リツ１ヘルコルベン中の乳
剤水溶液が５０℃であることを確かめたのら、先に用意
した過硫酸アンモニウムの水溶液と亜硫酸水素ナトリウ
ムの水溶液を３時間３０分で終了Ｊるように別個に滴下
した。開始剤の滴下をはじめて約１５分後窒素流入下で
先に用意したプレエマルションを３時間かかつて滴下し
た。Example 2 1 equipped with a stirrer, cooler, temperature control device, and nitrogen introduction pipe
In addition, 220 parts of deionized water, 1.0 part of sodium dodecylbenzenesulfonate (Neoperex No. 6, manufactured by Kao Soap Co., Ltd.), Emulgen 9, polyoxyethylene nonylphenyl ether (manufactured by Kao Soap Co., Ltd.)
31) Add 2.7 parts and bring the temperature to 50°C while stirring. Separately, 1.75 parts of ammonium persulfate dissolved in 80 parts of deionized water and 1 part of sodium bisulfite were prepared.
A solution of 75 parts of the solution was prepared in 80 parts of deionized water. Meanwhile, in 140 parts of deionized water, 2.5 parts of the above surfactant, namely sodium dodecylbenzene sulfonate, and 10.6 parts of polyoxyethylene nonylphenyl ether.
140 parts of the addition reaction product of 1-(a), 28 parts of styrene, and 8 parts of methyl methacrylate were dissolved.
A mixture of 7.5 parts of acrylic acid, 70 parts of 2-edylhexyl acrylate, 16 parts of hydroxyethyl acrylate, and 18.5 parts of methacryl was slowly added, and after about 5 minutes, a pre-emulsion of the reaction monomer was obtained. After confirming that the aqueous emulsion solution in 1 liter Herkolben was at 50°C, the previously prepared aqueous solution of ammonium persulfate and aqueous solution of sodium bisulfite were separately added dropwise so as to complete in 3 hours and 30 minutes. Approximately 15 minutes after the initiator was added dropwise, the previously prepared pre-emulsion was added dropwise for 3 hours under nitrogen flow.

反応開始剤の水溶液が滴下終了後、温度を６０℃に１時
間保ち、反応を終了した。この方法により、不揮発分４
０．６％、粘度１６０Ｃ１１，のエマルションを１９だ
。樹脂の数平均分子量は約１２０，０００であった。After the aqueous solution of the reaction initiator was added dropwise, the temperature was maintained at 60° C. for 1 hour to complete the reaction. By this method, the non-volatile content of 4
An emulsion of 0.6% and a viscosity of 160C11 is 19. The number average molecular weight of the resin was approximately 120,000.

実施例３ ２５− ３−（ａ＞ ザフラワー油脂肪酸　　　　　　２３６部メタクリル酸
アジリジニルエチル １４３部 ハイドロキノン　　　　　　　　０．４部エチルセ［］
ソルブ　　　　　　　　８９部を反応容器に入れ、攪拌
しながら１００〜１１０°Ｃの濡面で反応を行った。ア
ジリジニル基とカルボキシル基のイ」加反応は、残存カ
ルボキシル基の量を測定しながら追跡した。反応が完了
するまで約４時間かかった。このものを８０℃に保ち、
攪拌しながら減圧下で脱溶剤した。Example 3 25-3-(a> Safflower oil fatty acid 236 parts Aziridinylethyl methacrylate 143 parts Hydroquinone 0.4 part Ethylcetate []
89 parts of SOLV was placed in a reaction vessel, and the reaction was carried out on a wet surface at 100 to 110°C while stirring. The addition reaction between the aziridinyl group and the carboxyl group was monitored while measuring the amount of the remaining carboxyl group. The reaction took approximately 4 hours to complete. Keep this thing at 80℃,
The solvent was removed under reduced pressure while stirring.

３−（ｂ） 攪拌器、冷却器、温度制御装置、窒素導入管を備えた１
リツトル］ルベンに、脱イオン水４．　Ｏ０部、３−　
（ａ　）の付加反応物３部、メトキシポリ］ニチレング
リ］−ルモノメタクリレートＨ３ （ＣＨ２＝ＣＣｏｏ　（ＣＨ２Ｃｔ−ｈ　Ｏ）　２３０
Ｈ３、ＮＫエステルＭ−２３Ｇ　　新中村化学社製）６
部、スチレ２６一 ン１５部、メタクリル酸エチル１８部、アクリル酸２−
エチルヘキシル１６．８部、アクリル酸１゜２部、過硫
酸アンモニウム０．６部を仕込み、窒素気流下で８０°
Ｃに臂濡した。品温後、過硫酸アンモニウム０．９部を
脱イオン水５０部に溶かした液と、別に用意した３−（
ａ）の付加反応物１２部、メトキシポリエチレングリコ
ールモノメタクリレ−１２４部、スチレン６０部、メタ
クリル酸エチル７２部、アクリル９２−ｘデルヘキシル
６７．２部、アクリル酸４．８部を混合した浩を別々に
３時間にわたって滴下した。反応ｉ都度は８０℃に保っ
た。滴下終了後さらに２時間８０℃に保ち、反応を終了
した。このＩｉ法で不揮発分３９゜５％、粘度１５０ｃ
ｐのエマルシヨンをえた。樹脂の数平均分子量は約１５
０．０ＯＯＦあった。3-(b) 1 equipped with a stirrer, cooler, temperature control device, and nitrogen inlet pipe
[Little] Reuben, deionized water 4. O part, 3-
3 parts of the addition reaction product of (a), methoxypoly]nitylenegly]-ru monomethacrylate H3 (CH2=CCoo (CH2Ct-hO) 230
H3, NK Ester M-23G (manufactured by Shin-Nakamura Chemical Co., Ltd.) 6
parts, 26 parts of styrene, 15 parts of ethyl methacrylate, 2-2 parts of acrylic acid.
16.8 parts of ethylhexyl, 1.2 parts of acrylic acid, and 0.6 parts of ammonium persulfate were added and heated to 80° under a nitrogen stream.
C got my arm wet. After reaching temperature, add a solution prepared by dissolving 0.9 parts of ammonium persulfate in 50 parts of deionized water and 3-(
A mixture of 12 parts of the addition reaction product of a), 124 parts of methoxypolyethylene glycol monomethacrylate, 60 parts of styrene, 72 parts of ethyl methacrylate, 67.2 parts of acrylic 92-x derhexyl, and 4.8 parts of acrylic acid was prepared. They were added dropwise over a period of 3 hours. The temperature was maintained at 80°C during each reaction. After the dropwise addition was completed, the temperature was maintained at 80° C. for another 2 hours to complete the reaction. With this Ii method, the non-volatile content is 39.5% and the viscosity is 150c.
I got an emulsion of p. The number average molecular weight of the resin is approximately 15
There was 0.0OOF.

実施例４ トール油脂肪酸　　　　　　　　２３５部メタクリル酸
アジリジニルメチル １１９部 ハイドロキノン　　　　　　　　０．４部テトラＪデル
アンモニウムブロマイド ０．２部 を反応容器に入れ、攪拌しながら８０〜９０℃の温度Ｃ
反応を行った。アジリジニル基とカルボキシル基の付加
反応は残存カルボキシル基の量を測定しながら追跡した
。反応が完了するまで約４゜５時間かかった。Example 4 Tall oil fatty acid 235 parts Aziridinyl methyl methacrylate 119 parts Hydroquinone 0.4 part Tetra J delammonium bromide 0.2 part was placed in a reaction vessel and heated to a temperature of 80 to 90°C while stirring.
The reaction was carried out. The addition reaction between the aziridinyl group and the carboxyl group was monitored while measuring the amount of remaining carboxyl group. It took approximately 4.5 hours for the reaction to complete.

４、−（１’ｌ） 攪拌器、冷ｉＡ器、温麻制御装置、窒素導入管を備えた
１リツ１〜ルコルベンにｎ９；イオン水３５０部、４−
（ａ）の付加反応物２２．５部、メトキシポリエヂレン
グリコールモノメタクリレートＨｈ （ＣＨ２＝ＣＣｏｏ　（ＣＩ−＋２　ＣＨ２０）　２３
　ＣＨ３、ＮＫエステルＭ−９Ｇ　　新中村化学社製）
１５部、メタクリル酸メチル２７部、メタクリル酸ｎ−
ブチル５゜３部、アクリル％ｎ−ブチル９部を仕込み、
窒素気流下で攪拌した。アゾビスシアノ吉草酸６部をジ
メチルエタノールアミン５．７部を含む脱イオン水１０
０部に溶解し、この水溶液の８０％をコルベンに仕込み
、８０’Ｃに胃温した。８０’Ｃに達したのＪう、４−
（ａ）の付加反応物６７．５部、メトキシポリエチレン
グリコール３０部、メタクリル酸メチル８１部、メタク
リル酸ｎ−ブチル１５゜７部、アクリル酸ｎ−ブチル２
７部を混合した液を１時間３０分で滴下した。滴下終了
後アゾビスシアノ青草散水溶液の残りを仕込み、８０”
Ｃｒざらに２時間保ち、反応を終了した。この方法で不
揮発分３９．２％、粘度２０（Ｍｌ）のエマルションを
えた。樹脂の数平均分子量は約６０，０００であ時間か
かった。4, - (1'l) 1 litre, equipped with a stirrer, cold iA device, heating control device, and nitrogen inlet pipe n9; 350 parts of ionized water, 4-
22.5 parts of addition reaction product of (a), methoxypolyethylene glycol monomethacrylate Hh (CH2=CCoo (CI-+2 CH20) 23
CH3, NK ester M-9G manufactured by Shin-Nakamura Chemical Co., Ltd.)
15 parts, methyl methacrylate 27 parts, methacrylic acid n-
Add 5.3 parts of butyl and 9 parts of acrylic% n-butyl.
The mixture was stirred under a nitrogen stream. 10 parts of deionized water containing 6 parts of azobiscyanovaleric acid and 5.7 parts of dimethylethanolamine
0 parts, and 80% of this aqueous solution was charged into a Kolben and heated to 80'C. It reached 80'C, 4-
67.5 parts of the addition reaction product of (a), 30 parts of methoxypolyethylene glycol, 81 parts of methyl methacrylate, 15.7 parts of n-butyl methacrylate, 2 parts of n-butyl acrylate
A mixture of 7 parts was added dropwise over 1 hour and 30 minutes. After the dripping is complete, add the rest of the azobiscyano green grass watering solution to 80"
The reaction was completed by keeping it in a Cr atmosphere for 2 hours. In this way, an emulsion with a nonvolatile content of 39.2% and a viscosity of 20 (Ml) was obtained. The number average molecular weight of the resin was about 60,000 and it took a long time.

実施例５ ５−（ａ） 大豆油脂肪酸　　　　　　　　１４２部脱水ひまし油脂
肪酸　　　　　　９５部メタクリル酸アジリジニルエチ
ル １３０部 ハイドロキノン　　　　　　　０．３部を反応容器に入
れ、攪拌しながら１３０〜１４０℃の温度で反応を行っ
た。アジリジニル基とカル２９− ホキシル基の（１加反応は残存カルボキシル基の量を測
定しながら追跡した。反応が完了するまで約１時間かか
った。Example 5 5-(a) 142 parts of soybean oil fatty acid 95 parts of dehydrated castor oil fatty acid 130 parts of aziridinylethyl methacrylate 0.3 part of hydroquinone was placed in a reaction vessel and the reaction was carried out at a temperature of 130 to 140°C with stirring. Ta. The monoaddition reaction between the aziridinyl group and the carboxyl group was monitored while measuring the amount of residual carboxyl group. It took about 1 hour for the reaction to complete.

５−　（ｂ　） 攪拌器、冷却器、温度制御装買、窒素導入管を備えた１
リツ１〜ルコルベンに、脱イオン水４００部、１−（ａ
）の付加反応物１２部、 ＣＨ２Ｃ０ＯＲ ＣＨＣ００ＣＨ２ＣＨ＝ＣＨ２ ■ ０３Ｎａ エレミノールＪＳ−２（三洋化成工業社製　ＲはＣｌ２
ｌ−ｌｚａとＣＩ３１−１２７の混合物）２２．５部（
有効成分９部）、スチレン９．６部、メタクリル酸メチ
ル１８部、アクリル酸ｎ−ブチル１５部、アクリル酸２
．４部、過硫酸カリウム０．３部、亜硫酸水素ナトリウ
ム１．５部を仕込み、窒素気流下で６０℃に品温した。5-(b) 1 equipped with a stirrer, cooler, temperature control equipment, and nitrogen inlet pipe
400 parts of deionized water, 1-(a
), 12 parts of addition reaction product, CH2C0OR CHC00CH2CH=CH2
mixture of l-lza and CI31-127) 22.5 parts (
9 parts of active ingredient), 9.6 parts of styrene, 18 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 2 parts of acrylic acid
．． 4 parts of potassium persulfate, 0.3 parts of potassium persulfate, and 1.5 parts of sodium bisulfite were added, and the temperature was raised to 60°C under a nitrogen stream.

昇温後、過硫酸カリウム１．２部を脱イオ“ン水５０部
に溶かした液と、別に用意した１−（ａ）の付加反応物
４８部、スチレン３８゜４部、メタクリル酸メチル７２
部、アクリル酸ｎ−３０− ブチル６０部、アクリル酸９．６部を混合した液を別々
に２時間３０分にわたって滴下した。反応温度は６０　
’Ｃに保った。滴下終了後さらに２時間６０℃に保ち終
了した。この方法で不揮発分３８゜７％、粘度１００ｃ
ｐのエマルションをえた。樹脂の数平均分子量は約２０
０，０００であった。After raising the temperature, a solution of 1.2 parts of potassium persulfate dissolved in 50 parts of deionized water, 48 parts of the addition reaction product of 1-(a) prepared separately, 4 parts of 38° styrene, and 72 parts of methyl methacrylate were added.
A mixture of 60 parts of n-30-butyl acrylate and 9.6 parts of acrylic acid was separately added dropwise over 2 hours and 30 minutes. The reaction temperature is 60
'Kept at C. After the dropwise addition was completed, the temperature was maintained at 60° C. for another 2 hours. With this method, the non-volatile content is 38.7% and the viscosity is 100c.
I got an emulsion of p. The number average molecular weight of the resin is approximately 20
It was 0,000.

実施例６ 攪拌器、冷ＪＪＩ器、温度制御装置、窒素導入管を備え
た１リツトルコルベンに、脱イオン水２２０部、■レミ
ノールＪＳ−５（三洋化成工業着製）：Ｃｌ−１２−〇
〇〇〇＋５Ｈ３ｙ ＣＨＣ００ＣＨｚＣ１−４＝ＣＨｚ ０３　Ｎａ ２．２部、およびエマルゲン９５０（非イオン系界面活
性剤：花工石鹸社製）２．１部を仕込み、窒素気流上で
攪拌しながらで温度を５０℃に昇温した。別に、過硫酸
アンモニウム１．７５部を脱イオン水８０部に溶解した
ものと、曲硫酸水素すｌ−リウム１．７５部を脱イオン
水８０部に溶解したものを用意した。一方、脱イオン水
１４０部に前記■レミノールＪＳ−５を８．８部とエマ
ルゲン９５０を８．４部溶解したものを攪拌しながら、
実施例５−　（ａ　）の付加反応物１４０部、スチレン
２８部、メタクリル酸メチル８５．５部、アクリル酸２
−エヂルヘキシル７０部、アクリル酸ヒドロキシエチル
１６部、メタクリルｌ’１ｌｌｏ、５部の混合物をゆっ
くりと添加し、約５分後に反応単量体のプレエマルショ
ンをえた。１リツトルコルベン中の乳剤水溶液が５０℃
であることを確かめたのち、先に用意した過硫酸アンモ
ニウムの水溶液と亜硫酸水素す１〜リウムの水溶液を３
時間３０分で終了するように別個に滴下した。開始剤の
滴下をはじめて約１５分後窒素流入下で先に用意したプ
レエマルションを３時間かかって滴下した。Example 6 220 parts of deionized water was added to a 1-liter colben equipped with a stirrer, a cold JJI device, a temperature control device, and a nitrogen inlet pipe, ■Leminol JS-5 (manufactured by Sanyo Chemical Industries, Ltd.): Cl-12-〇〇 〇〇+5H3y CHC00CHzC1-4=CHz 03 2.2 parts of Na and 2.1 parts of Emulgen 950 (nonionic surfactant: manufactured by Hanako Soap Co., Ltd.) were charged, and the temperature was raised to 50°C while stirring in a nitrogen stream. The temperature was raised to ℃. Separately, 1.75 parts of ammonium persulfate dissolved in 80 parts of deionized water and 1.75 parts of sulfurium hydrogen sulfate dissolved in 80 parts of deionized water were prepared. On the other hand, while stirring, 8.8 parts of Reminol JS-5 and 8.4 parts of Emulgen 950 were dissolved in 140 parts of deionized water.
Example 5 - 140 parts of addition reactant of (a), 28 parts of styrene, 85.5 parts of methyl methacrylate, 2 parts of acrylic acid
- A mixture of 70 parts of edylhexyl, 16 parts of hydroxyethyl acrylate, and 5 parts of methacrylic l'1llo was slowly added, and after about 5 minutes a pre-emulsion of the reacted monomers was obtained. The emulsion aqueous solution in 1 liter of alcohol is at 50°C.
After confirming that the aqueous solution of ammonium persulfate prepared earlier and the aqueous solution of 1 to 3 lithium hydrogen sulfite are
The dropwise addition was completed in 30 minutes. Approximately 15 minutes after the initiator was added dropwise, the previously prepared pre-emulsion was added dropwise over a period of 3 hours under nitrogen flow.

反応開始剤の水溶液が滴下終了後、温度を６０℃に１時
間保ち、反応を終了した。この方法により、不揮発分４
０．２％、粘度２５０ｃｐのエマルションを得た。樹脂
の数平均分子量は約１２０，０００であった。After the aqueous solution of the reaction initiator was added dropwise, the temperature was maintained at 60° C. for 1 hour to complete the reaction. By this method, the non-volatile content of 4
An emulsion of 0.2% and a viscosity of 250 cp was obtained. The number average molecular weight of the resin was approximately 120,000.

比較例１ 実施例１′ｃｌ−（ａ）の付加反応物の代わりにメタク
リル酸ｎ−ブチルを用いるほかは実施例１と全く同じ方
法で不揮発４３．６％、粘度３００ｃｐのエマルション
をえた。樹脂の数平均分子量は約１３０．０００であっ
た。Comparative Example 1 An emulsion with a non-volatility of 43.6% and a viscosity of 300 cp was obtained in exactly the same manner as in Example 1, except that n-butyl methacrylate was used instead of the addition reaction product of Example 1'cl-(a). The number average molecular weight of the resin was approximately 130,000.

比較例２ 実施例３で３−　（ａ　）の付加反応物の代わりにアク
リル酸ｎ−ブチルを用いるほかは実施例３と全く同じ方
法で不揮発分４０．８％、粘度１３０ｃｐのエマルショ
ンをえた。樹脂の数平均分子量は約１００．０００であ
った。Comparative Example 2 An emulsion with a nonvolatile content of 40.8% and a viscosity of 130 cp was obtained in exactly the same manner as in Example 3, except that n-butyl acrylate was used instead of the addition reaction product of 3-(a). The number average molecular weight of the resin was approximately 100,000.

比較例３ 実施例６で５−（ａ）の付加反応物の代わりにメタクリ
ル酸イソブチルを用いるほがは実施例６と全く同じ方法
で不揮発分３９．９％、粘度２゜Ｏｃｐのエマルション
をえた。樹脂の数平均分子けは１４０．０００であった
。Comparative Example 3 An emulsion with a nonvolatile content of 39.9% and a viscosity of 2°Ocp was obtained in exactly the same manner as in Example 6, except that isobutyl methacrylate was used instead of the addition reaction product of 5-(a). . The number average molecular weight of the resin was 140.000.

上記各実施例および比較例のエマルションにドライヤー
としてナフテン酸コバルト水溶液（ディックネート３１
１１．大日本インキ化学社製）を３３− 不揮発分の１％の割合で加えガラス板に４　　ｍｉｌの
ドクターブレードで塗布したもの、および磨鋼板に１　
Ｂ２あたり１００（］の塗付量になるように刷毛塗りし
たのち、室温で３時間乾燥後の撥水性および７日間乾燥
後の塗膜性能をしらべそれぞれ下記第１表の如ぎ結果を
得た。A cobalt naphthenate aqueous solution (Dicknate 31
11. (manufactured by Dainippon Ink Chemical Co., Ltd.) was added at a rate of 1% of non-volatile content and applied to a glass plate with a 4 mil doctor blade, and 1% to a polished steel plate.
After applying with a brush to a coating amount of 100 () per B2, the water repellency after drying at room temperature for 3 hours and the coating film performance after drying for 7 days were examined, and the results shown in Table 1 below were obtained. .

（以下余白〉 ３４− 第１表 尚試験ならびに評価は次の通りに行った。(Margin below) 34- Table 1 The tests and evaluations were conducted as follows.

（注１）耐温水性 ／ＩＯ℃の渇水中に２週間浸漬し、塗膜に発生する異常
を観察し、 ◎　異常なし ○　小さなフクレが少し存在する 口　小さなフクレが存在し、つやが少しひ（プている △　フクレが多い、またはつやがひけている×　フクレ
が多く、つやもひ（ブている（注２）耐ツルトスプレー
性 ５％塩水を４０℃で１２０時間スプレーした後のサビ発
生の状態を観察し ◎　サビの発生なし ○　点サビが少し発生 口　糸サビがところどころ発生 Δ　サビが多い ×　サビ多く、塗膜剥離あり （注３）鉛筆硬度 ６Ｂ〜９日硬度記号の三菱ユニ鉛筆を用い、塗膜をひつ
かきキズの生成する硬度の一段下の硬度記号で表示 （注４）キシロールスポラ１〜 塗膜上にキシレンを１滴落し、キシレン揮発後の塗膜状
態を観察、チヂミは硬化しているが、硬化不良を示す ◎　異常なし Ｏ殆んど異常なし 口　少しチヂミあり ×　溶解 （注５）剥離強電 塗膜上に水を１滴落し、塗膜の水をはじく状態を観察 ◎　よく撥水し、異常なし ○　異常なし △　溶解傾向 ×　溶解 （注６）撥水性 アドヒジョンテスター（エルコメータ？ｔ）を使用 ３７− ◎〉○〉Δ〉× ３８−(Note 1) Warm water resistance/Immersed in drought water at IO℃ for 2 weeks and observed any abnormalities that occur on the paint film. (Poor △ Lots of blistering or loss of luster × Lots of blistering and lack of luster (Note 2) Rust formation after spraying with 5% salt water at 40℃ for 120 hours Observe the condition of ◎ No rust ○ A few spots of rust Thread rust occurs here and there Δ A lot of rust 1 drop of xylene on the paint film and observe the state of the paint film after xylene volatilizes. is cured, but indicates poor curing ◎ No abnormalities O Almost no abnormalities A little sagging × Dissolved (Note 5) Drop a drop of water on the peeling strong electric coating film and check the state of the coating film to repel water. Observation ◎ Water repellent well, no abnormalities ○ No abnormalities △ Dissolution tendency

Claims (1)

【特許請求の範囲】 （１）乾性油脂肪酸および／または半乾性油脂肪酸にα
、β−エチレン性不性用飽和酸ジリジニルアルキルエス
テルを反応させて得られる脂肪酸変性単量体２〜６０重
量部ならびに、これと共重合可能なα、β−エヂレン性
不飽和単量体９８〜４０重量部を構成！Ｊｉ量体成分と
して含む平均分子量約５，０００〜５００，０００共重
合体が水媒体中に分散され−（なる酸化重合型水性エマ
ルション。 （２）共重合可能なα、β−エヂレン性不飽和単噴体成
分の２〜２０重量部が、α、β−エチレン性不性用飽和
基−テル結合を有する非イオン性重合型単量体である特
許請求の範囲第１項記載のエマルション。 （３）非イオン性重合型単量体が、式 ０式％ （式中Ｒ１は水素、低級アルキル、ハロゲンまたはフェ
ニル基で、Ｒｚはエチレンまたはプロピレン％’Ｑ、Ｒ
３は水素または低級アルキル基であり、０は４〜２５の
正数） で表わされる化合物である特許請求の範囲第２項記載の
エマルション。 （４）共重合可能なα、β、β−エチレン飽和単量体成
分の０．５〜１０重量部が、α、β−エチレン性不性用
飽和基ルホン酸あるいはスルホネート基を有する陰イオ
ン性重合型中吊体である特許請求の範囲第１項記載のエ
マルション。 〈５）陰イオン性重合型単量体が、下記式のいづれかに
より表わされる化合物 Ｃト１□ＣＯＯＲ２ ＣＨ２ＣＯＯ（ＡＯ）ｎ　ＣＨ２Ｃ＝ＣＨｈ１ ２ （式中Ｒ１は水素またはメチル基；Ｒ２は置換基を有し
ていてもかまわない飽和または不飽和炭化水素またはオ
キシアルキレン基を含む右ｍＷ　：　Ａは炭素数２〜４
のアルキレン基または置換アルキレン基：Ｍは水素、ア
ルカリ金属、アルカリ土類金属、アンモニウム、または
有機アミン；ｍはＭの原子価またはイオン価；ｎはＯま
たは正数：Ａ′は炭素数１〜２０の飽和または不飽和の
炭化水素または”ｆｌ　１ｆＪ！基を有する炭化水素；
１３は炭素数１〜６の飽和炭化水素を夫々表わ（） である特許請求の範囲第４項記載の１マルシヨン。 （６）乾性油脂ｌｈ酸たまは半乾性油脂肪酸がキリ油脂
肪酸、脱水ヒマシ油脂肪酸、アマニ油脂肪酸、リーフラ
ワー油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ケシ油脂
肪酸、ｌ・−ル油脂肪酸、ぬか油脂肪酸、トウモロコシ
油脂肪酸、またはヒマワリ油脂肪酸である１Ｓｆ訂請求
の範囲第１項〜第５項のいづれかに記載のエマルション
。 （７）α、β−エチレン性不性用飽和酸ジリジニルアル
キルエステルがアジリジニルメチルアクリレート、アジ
リジニルエチルアクリレート、アジリジニルプロピルア
クリレート、アジリジニルブチルアクリレートあるいは
それらの対応メタクリレートである特許請求の範囲第１
項〜第６項のいづれかに記載のエマルション。 （８）共重合可能なα、β−エチレン性不性用飽和単量
体クリル酸およびメタクリル酸、それらのアルギルエス
テル、ヒドロキシアルキルエステルま１＝はアミド類、
スチレンおよびスチレン誘導体、およびアクリロニトリ
ル、メタクリレートリルからなる群にり選ばれる１種ま
たは２種以上の単量体である特許請求の範囲第１項〜第
７項のいづれかに記載の■マル、ジョン。 （９） （Ａ＞乾性油脂肪酸および／または半乾性油脂肪酸にα
、β−エヂレン性不性用飽和酸ジリジニルアルキルエス
テルを反応させて得られる脂肪酸変性単量体２〜６０重
量部と （Ｂ）共重合可能なα、β−エチレン性不飽和中量体９
８〜４０重間部とを水性媒体中で乳化重合せしめること
を特徴とする酸化重合型水性エマルションの製造法。 （１０）乳化重合を界面活性剤および／または高分子保
護コロイドの存在下もしくは不存在下に実施する特許請
求の範囲第９項記載の方法。 （１１）共重合可能なα、β−丁チレン性不飽和単量体
成分として２〜２０重量部の式 ％式％： （式中Ｒ１は水素、低級アルキル、ハロゲンまたはフェ
ニルＭ：Ｒ２はエチレンまたはプロピレン５− 基；Ｒ３は水素または低級アルキル基：ｎは４〜２５の
正数） で表わされる単量体と、９６〜２０重量部のその他の共
重合可能なα、β−エチレン性不飽和単吊体を用いる特
許請求の範囲第９項または第１０項記載の方法。 （１２）共重合可能なα、β−エチレン性不性用飽和単
量体成分て、０．５〜１０重最部の式％式％ （式中Ｒ１は水素またはメチル基；Ｒ２は置換基６− を有していてもかまわない飽和または不飽和炭化水素ま
たはオキシアルキレン基を含む有機基；Ａは炭素数２〜
４のアルキレン基または置換アルキレン基；Ｍは水素、
アルカリ金属、アルカリ土類金属、アンモニウムまたは
有機アミン；ＩｌｌはＭの原子価またはイオン価；ｎは
Ｏまたは正数；Ａ′は炭素数１〜２０の飽和または不飽
和の炭化水素または置換炭化水素；Ｂは炭素数１〜６の
飽和炭化水素） のいづれかで表わされる単量体と、上記以外の共重合可
能なα、β−エチレン性不飽和単邑体９７゜５〜３０重
量部を用いる特許請求の範囲第９項または第１０項記載
の方法。 （１３）乾性油脂肪酸または半乾性油脂肪酸がキリ油脂
肪酸、脱水ヒマシ油脂肪酸、アマニ油脂肪酸、ザフラワ
ー油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ケシ油脂肪
酸、トール油脂肪酸、ぬか油脂肪酸、トウモロコシ油脂
肪酸、またはヒマワリ油脂肋耐である特許請求の範囲第
９項〜第１２項のいづれかに記載の方法。 （１４）α、β−エチレン性不性用飽和酸ジリジニルア
ルキルエステルがアジリジニルメチルアクリレート、ア
ジリジニルエチルアクリレート、アジリジニルプロピル
アクリレート、アジリジニルエチルアクリレ−１〜ある
いはそれらの対応メタクリレ−１〜である特許請求の範
囲第９項〜第１３項のいづれかに記載の方法。 （１５）共重合可能なα、β−エチレン性不飽和単量体
がアクリル酸およびメタクリル酸、それらのアルキルエ
ステル、ヒドロキシアルキルエステルまたはアミド類、
スチレンおよびスチレン誘導体、およびアクリロニトリ
ル、メタクリロニトリルからなるＭ　Ｊ：り選ばれる１
種または２種以上の中量体である特許請求の範囲第９項
〜第１４項のいづれかに記載の方法。[Claims] (1) α in drying oil fatty acid and/or semi-drying oil fatty acid
, 2 to 60 parts by weight of a fatty acid modified monomer obtained by reacting β-ethylenically unsaturated saturated acid diridinyl alkyl ester, and an α,β-ethylenically unsaturated monomer copolymerizable therewith. Consists of 98 to 40 parts by weight! A copolymer having an average molecular weight of about 5,000 to 500,000 contained as a Ji polymer component is dispersed in an aqueous medium to form an oxidative polymerization type aqueous emulsion. The emulsion according to claim 1, wherein 2 to 20 parts by weight of the monomer component is a nonionic polymerizable monomer having an α,β-ethylenically unsaturated group-ter bond. 3) The nonionic polymerizable monomer has the formula 0% (wherein R1 is hydrogen, lower alkyl, halogen or phenyl group, and Rz is ethylene or propylene%'Q, R
The emulsion according to claim 2, wherein 3 is hydrogen or a lower alkyl group, and 0 is a positive number from 4 to 25. (4) Anionic in which 0.5 to 10 parts by weight of the copolymerizable α, β, β-ethylene saturated monomer component has a sulfonic acid or sulfonate group, an α, β-ethylenically unsaturated saturated group. The emulsion according to claim 1, which is a polymeric suspended body. <5) The anionic polymerizable monomer is a compound represented by one of the following formulas: Right mW that may contain a saturated or unsaturated hydrocarbon or oxyalkylene group: A has 2 to 4 carbon atoms
alkylene group or substituted alkylene group: M is hydrogen, alkali metal, alkaline earth metal, ammonium, or organic amine; m is the valence or ionic valence of M; n is O or a positive number; A' is a carbon number of 1 to 20 saturated or unsaturated hydrocarbons or hydrocarbons having the "fl 1fJ!"group;
13 represents a saturated hydrocarbon having 1 to 6 carbon atoms, respectively (). 1 Mulsion according to claim 4. (6) Drying fat lh acid or semi-drying oil fatty acid is tung oil fatty acid, dehydrated castor oil fatty acid, linseed oil fatty acid, leafflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, l-l oil fatty acid, The emulsion according to any one of claims 1 to 5, which is a bran oil fatty acid, a corn oil fatty acid, or a sunflower oil fatty acid. (7) The α,β-ethylenic saturated acid diridinyl alkyl ester is aziridinyl methyl acrylate, aziridinyl ethyl acrylate, aziridinyl propyl acrylate, aziridinyl butyl acrylate, or their corresponding methacrylates. Claim 1
The emulsion according to any one of Items 6 to 6. (8) Copolymerizable α, β-ethylenically unsaturated monomers acrylic acid and methacrylic acid, their argylesters, hydroxyalkyl esters or amides;
1. The compound according to any one of claims 1 to 7, which is one or more monomers selected from the group consisting of styrene and styrene derivatives, acrylonitrile, and methacrylate trile. (9) (A>α for drying oil fatty acids and/or semi-drying oil fatty acids)
, 2 to 60 parts by weight of a fatty acid modified monomer obtained by reacting β-ethylenically unsaturated saturated acid diridinyl alkyl ester, and (B) a copolymerizable α,β-ethylenically unsaturated intermediate 9
1. A method for producing an oxidative polymerization type aqueous emulsion, which comprises emulsion polymerizing 8 to 40 polymer parts in an aqueous medium. (10) The method according to claim 9, wherein the emulsion polymerization is carried out in the presence or absence of a surfactant and/or a polymeric protective colloid. (11) 2 to 20 parts by weight of the copolymerizable α,β-tyrenically unsaturated monomer component: (wherein R1 is hydrogen, lower alkyl, halogen, or phenyl M; R2 is ethylene or propylene 5- group; R3 is hydrogen or a lower alkyl group; n is a positive number from 4 to 25) and 96 to 20 parts by weight of other copolymerizable α,β-ethylenic monomers. 11. The method according to claim 9 or 10, using a saturated single-hung body. (12) The copolymerizable α,β-ethylenically unsaturated monomer component has a formula% of 0.5 to 10% (in the formula, R1 is hydrogen or a methyl group; R2 is a substituent 6- A is an organic group containing a saturated or unsaturated hydrocarbon or oxyalkylene group; A has 2 to 2 carbon atoms;
4 alkylene group or substituted alkylene group; M is hydrogen,
Alkali metal, alkaline earth metal, ammonium or organic amine; Ill is the valence or ionic valence of M; n is O or a positive number; A' is a saturated or unsaturated hydrocarbon or substituted hydrocarbon having 1 to 20 carbon atoms ;B is a saturated hydrocarbon having 1 to 6 carbon atoms) and 97.5 to 30 parts by weight of a copolymerizable α,β-ethylenically unsaturated monomer other than the above. A method according to claim 9 or 10. (13) Drying oil fatty acids or semi-drying oil fatty acids include tung oil fatty acids, dehydrated castor oil fatty acids, linseed oil fatty acids, safflower oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy oil fatty acids, tall oil fatty acids, rice bran oil fatty acids, and corn oil fatty acids. 13. The method according to any one of claims 9 to 12, which is an oil fatty acid or a sunflower oil fatty acid. (14) The α,β-ethylenically unsaturated saturated acid diridinyl alkyl ester is aziridinyl methyl acrylate, aziridinylethyl acrylate, aziridinylpropyl acrylate, aziridinylethyl acrylate-1 or their like. 14. The method according to any one of claims 9 to 13, wherein the corresponding methacrylates are 1 to 1. (15) The copolymerizable α, β-ethylenically unsaturated monomer is acrylic acid and methacrylic acid, their alkyl esters, hydroxyalkyl esters or amides,
M J: 1 selected from styrene and styrene derivatives, acrylonitrile, methacrylonitrile
The method according to any one of claims 9 to 14, which is a species or two or more intermediates.