JP2001294630A - Aqueous resin and method for producing the same - Google Patents
Aqueous resin and method for producing the sameInfo
- Publication number
- JP2001294630A JP2001294630A JP2000109193A JP2000109193A JP2001294630A JP 2001294630 A JP2001294630 A JP 2001294630A JP 2000109193 A JP2000109193 A JP 2000109193A JP 2000109193 A JP2000109193 A JP 2000109193A JP 2001294630 A JP2001294630 A JP 2001294630A
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- JP
- Japan
- Prior art keywords
- aqueous
- resin
- unsaturated monomer
- ethylene
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐溶剤性、耐アル
カリ性、耐食性に優れた皮膜を形成しうる水性樹脂の製
造方法およびそれから得られる水性樹脂に関する。The present invention relates to a method for producing an aqueous resin capable of forming a film having excellent solvent resistance, alkali resistance and corrosion resistance, and an aqueous resin obtained therefrom.
【０００２】[0002]
【従来の技術】塗料、防錆剤等の皮膜形成材料として使
用される水性樹脂は、従来から種々のものが知られてい
るが、特に金属塗布用としては、付着性、耐食性に優れ
た皮膜を得るために、エチレン−不飽和カルボン酸共重
合物の水分散体がよく使用される。そしてより高い耐食
性を得るために上記エチレン−不飽和カルボン酸共重合
物の水分散体にコロイダルシリカを添加、混合して用い
られることも多い。また、上記水分散体を用いるコーテ
ィング剤の貯蔵安定性や皮膜の上塗り塗料密着性などを
改善するために、他の樹脂をブレンドしたり複合したり
する場合もある。2. Description of the Related Art There have been known various aqueous resins used as film-forming materials such as paints and rust preventives. However, especially for coating a metal, a film having excellent adhesion and corrosion resistance is used. In order to obtain the above, an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer is often used. In order to obtain higher corrosion resistance, colloidal silica is often added to and mixed with the aqueous dispersion of the ethylene-unsaturated carboxylic acid copolymer. Further, in order to improve the storage stability of the coating agent using the above-mentioned aqueous dispersion and the adhesion of the top coat to the coating film, other resins may be blended or composited.
【０００３】たとえば、特開昭６０−２２８５１０号公
報にはエチレン−不飽和カルボン酸共重合体分散液中で
不飽和モノマーを乳化重合させて得られる水系樹脂の製
造方法が開示されている。また、特開昭６４−７３０８
３号公報にはエチレン−不飽和カルボン酸共重合体分散
液に不飽和モノマーを加えて乳化重合させ、重合後に後
架橋させて得られた水系樹脂にＳｉＯ2等のコロイドゾ
ルを加えた水性液でクロメート被覆めっき鋼板を処理す
る方法が記載されている。さらに、特開平１０−１７６
１１９号公報には、エチレン−不飽和カルボン酸共重合
体のアルカリ金属中和物（アイオノマー）の水分散液お
よび水性ポリエステル樹脂中で、不飽和モノマーを乳化
重合して得られる金属表面処理剤が開示されている。For example, JP-A-60-228510 discloses a method for producing an aqueous resin obtained by emulsion-polymerizing an unsaturated monomer in an ethylene-unsaturated carboxylic acid copolymer dispersion. Also, Japanese Unexamined Patent Publication No.
No. 3 discloses an aqueous solution in which an unsaturated monomer is added to an ethylene-unsaturated carboxylic acid copolymer dispersion, emulsion-polymerized, and post-crosslinking is performed after polymerization, and a water-based resin obtained by adding a colloidal sol such as SiO 2 to the aqueous resin. A method for treating a chromate-coated plated steel sheet is described. Further, JP-A-10-176
No. 119 discloses a metal surface treating agent obtained by emulsion polymerization of an unsaturated monomer in an aqueous dispersion of an alkali metal neutralized product of an ethylene-unsaturated carboxylic acid copolymer (ionomer) and an aqueous polyester resin. It has been disclosed.
【０００４】しかし、上記特開昭６０−２２８５１０号
公報の発明では、アンモニアや有機アミンによる中和物
の場合、これらの粘度が高いために不飽和モノマーの重
合時に分散安定性が損なわれることがあり、特開昭６４
−７３０８３号公報の発明では、乳化重合のあとにさら
に架橋させるため、特に架橋度を高めたい場合には、凝
集物が発生したり粘度が増して分散安定性が損なわれた
りする。さらに、特開平１０−１７６１１９号公報の発
明では水性ポリエステル樹脂の耐加水分解安定性が低い
ことがあり、また架橋反応性がないために形成された皮
膜の耐溶剤性も低いという問題点を有する。[0004] However, in the invention of Japanese Patent Application Laid-Open No. 60-228510, in the case of a neutralized product with ammonia or an organic amine, the dispersion stability may be impaired at the time of polymerization of the unsaturated monomer due to its high viscosity. Yes, JP
In the invention disclosed in Japanese Patent No. 73083, the crosslinking is further performed after the emulsion polymerization. Therefore, particularly when it is desired to increase the degree of crosslinking, agglomerates are generated or the viscosity is increased, and the dispersion stability is impaired. Furthermore, the invention of JP-A-10-176119 has the problem that the hydrolysis resistance of the aqueous polyester resin is sometimes low, and the solvent resistance of the formed film is low due to lack of crosslinking reactivity. .
【０００５】このように、エチレン−不飽和カルボン酸
共重合物の水分散体中での不飽和モノマーの乳化重合
は、エチレン−不飽和カルボン酸共重合体とアクリル樹
脂との複合には有効であるが、シード粒子となるエチレ
ン−不飽和カルボン酸共重合体の粘度が高いために高濃
度の条件で安定的に重合を進めることが困難であった。Thus, emulsion polymerization of an unsaturated monomer in an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer is effective for a composite of an ethylene-unsaturated carboxylic acid copolymer and an acrylic resin. However, since the viscosity of the ethylene-unsaturated carboxylic acid copolymer serving as seed particles is high, it has been difficult to stably proceed polymerization under high concentration conditions.
【０００６】[0006]
【発明が解決しようとする課題】したがって本発明の目
的は、シード粒子であるエチレン−不飽和カルボン酸共
重合体が高濃度であっても安定的に不飽和モノマーによ
る架橋を進めることができ、耐溶剤性、耐アルカリ性、
耐食性および上塗り密着性に優れた皮膜形成剤を製造す
ることができる水性樹脂の製造方法、およびこの方法か
ら得られる水性樹脂を提供することである。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to stably promote the crosslinking with unsaturated monomers even when the ethylene-unsaturated carboxylic acid copolymer as seed particles is at a high concentration, Solvent resistance, alkali resistance,
An object of the present invention is to provide a method for producing an aqueous resin capable of producing a film-forming agent excellent in corrosion resistance and top coat adhesion, and an aqueous resin obtained by this method.
【０００７】[0007]
【課題を解決するための手段】本発明の水性樹脂の製造
方法は、エチレン−不飽和カルボン酸共重合物の水分散
体をシード粒子とし、コロイダルシリカの共存下に、エ
ポキシ基含有不飽和モノマーおよび／または多官能性不
飽和モノマーを必須成分とする不飽和モノマー類を乳化
重合させるものである。上記シード粒子として、さら
に、水性ポリウレタン樹脂、水性ポリエステル樹脂およ
び水性アクリル樹脂から選ばれる水性樹脂が併用されて
いても良い。According to the process for producing an aqueous resin of the present invention, an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer is used as seed particles, and an epoxy group-containing unsaturated monomer is used in the presence of colloidal silica. And / or emulsion polymerization of unsaturated monomers containing a polyfunctional unsaturated monomer as an essential component. An aqueous resin selected from an aqueous polyurethane resin, an aqueous polyester resin, and an aqueous acrylic resin may be used in combination as the seed particles.
【０００８】また本発明の水性樹脂は、先の製造方法に
より得られるものであり、平均粒子径１０〜８０ｎｍで
あって良い。The aqueous resin of the present invention is obtained by the above-mentioned production method, and may have an average particle diameter of 10 to 80 nm.
【０００９】[0009]
【発明の実施の形態】以下、本発明について詳細に述べ
る。本発明の製造方法でシード粒子として使用するエチ
レン−不飽和カルボン酸共重合物は、エチレンと（メ
タ）アクリル酸等の不飽和カルボン酸とを高温高圧下で
ラジカル重合させて得られるコポリマーであり、不飽和
カルボン酸の共重合量が全体量の１５〜２０質量％を占
め、メルトインデックスが１００〜３０００のものが好
ましい。このようなエチレン−不飽和カルボン酸共重合
物としては、たとえばエチレン−アクリル酸共重合物が
商品名プリマコール５９８０、同５９９０としてダウケ
ミカル社から、ニュクレルＮ５１３０Ｈとして三井・デ
ュポンポリケミカル社から販売されている。これらエチ
レン−不飽和カルボン酸共重合物に含有されるカルボキ
シル基の一部または全量を、アンモニア等の水溶性アミ
ン、金属水酸化物および金属酸化物などを用いて中和す
ることによって水分散体を得ることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The ethylene-unsaturated carboxylic acid copolymer used as seed particles in the production method of the present invention is a copolymer obtained by radically polymerizing ethylene and an unsaturated carboxylic acid such as (meth) acrylic acid under high temperature and high pressure. Preferably, the copolymerization amount of the unsaturated carboxylic acid accounts for 15 to 20% by mass of the total amount and the melt index is 100 to 3000. As such an ethylene-unsaturated carboxylic acid copolymer, for example, an ethylene-acrylic acid copolymer is sold by Dow Chemical Company under the trade names Primacol 5980 and 5990, and by Mitsui / Dupont Polychemical Company under the name of Nucrel N5130H. ing. An aqueous dispersion is obtained by neutralizing a part or all of the carboxyl groups contained in these ethylene-unsaturated carboxylic acid copolymers with a water-soluble amine such as ammonia, a metal hydroxide and a metal oxide. Can be obtained.
【００１０】上記エチレン−不飽和カルボン酸共重合物
とともに、水性ポリウレタン樹脂、水性ポリエステル樹
脂および水性アクリル樹脂から選ばれる水性樹脂もシー
ド粒子として併用することができる。これら水性樹脂
は、１種類の使用でも良いし、２種類以上を併用しても
良い。An aqueous resin selected from an aqueous polyurethane resin, an aqueous polyester resin, and an aqueous acrylic resin can be used as seed particles together with the ethylene-unsaturated carboxylic acid copolymer. These aqueous resins may be used alone or in combination of two or more.
【００１１】水性ポリウレタン樹脂の例としては、ジイ
ソシアネートとジオールからノニオン基やアニオン基を
有する親水性ＮＣＯ基末端プレポリマーを合成し、これ
に水を加えて分散後、アミンで鎖延長して得られるもの
などを挙げることができる。また、水性ポリエステル樹
脂の例としては、ポリオールと二塩基酸との脱水縮合に
より得られるカルボキシル末端を有するポリエステルを
アミンで中和し水分散して得られるものなどを挙げるこ
とができる。水性アクリル樹脂の例としては、有機溶剤
中で不飽和カルボン酸を必須とする不飽和モノマー類を
ラジカル重合して得られるポリマーをアミンで中和し水
分散させたのち脱溶剤したもの、あるいは界面活性剤水
溶液中で不飽和モノマーを乳化重合させて得られるもの
などを挙げることができる。As an example of the aqueous polyurethane resin, a hydrophilic NCO-terminated prepolymer having a nonionic group or an anionic group is synthesized from diisocyanate and diol, added with water, dispersed, and then chain-extended with an amine. And the like. Examples of the aqueous polyester resin include those obtained by neutralizing a polyester having a carboxyl terminal obtained by dehydration condensation of a polyol and a dibasic acid with an amine and dispersing in water, and the like. Examples of the water-based acrylic resin include a polymer obtained by radical polymerization of an unsaturated monomer essentially including an unsaturated carboxylic acid in an organic solvent, which is neutralized with an amine, dispersed in water, and then desolventized, or an interface. Examples thereof include those obtained by emulsion polymerization of an unsaturated monomer in an aqueous activator solution.
【００１２】上記水性ポリウレタン樹脂、水性ポリエス
テル樹脂および水性アクリル樹脂から選ばれる粒子の固
形分添加量は、上記エチレン−不飽和カルボン酸共重合
物の固形分と同質量部か、またはそれ以下が好ましく、
この範囲を超えると金属への付着性や耐食性が低下する
原因となることがある。The solid content of the particles selected from the above-mentioned aqueous polyurethane resin, aqueous polyester resin and aqueous acrylic resin is preferably equal to or less than the mass of the solid content of the ethylene-unsaturated carboxylic acid copolymer. ,
Exceeding this range may cause a decrease in adhesion to metals and corrosion resistance.
【００１３】本発明の製造方法は、コロイダルシリカの
共存下に乳化重合を行うことに特徴がある。コロイダル
シリカは水性樹脂に比べると粘度が著しく低い。したが
ってこれを先のシード粒子と共存させておくと重合時に
粘度が下がって安定性が増す。この結果、樹脂濃度が比
較的高くても微小な水分散粒子を安定して得ることがで
きる。The production method of the present invention is characterized in that emulsion polymerization is carried out in the presence of colloidal silica. Colloidal silica has a significantly lower viscosity than aqueous resins. Therefore, if this is made to coexist with the above-mentioned seed particles, the viscosity is lowered during the polymerization and the stability is increased. As a result, fine water-dispersed particles can be stably obtained even when the resin concentration is relatively high.
【００１４】本発明の製造方法で使用するコロイダルシ
リカは、ｐＨ安定性が中性からアルカリ性の範囲で確保
でき、シード粒子との共存安定性の得られるものがよ
い。このような条件に合うコロイダルシリカの例とし
て、スノーテックスＮ、スノーテックスＣ（日産化学工
業社製）やカタロイドＳ−２０Ｌ、カタロイドＳＡ（触
媒化成工業社製）などが挙げられる。添加量はシード粒
子の樹脂固形分に対して１０〜１００質量部、さらに好
ましくは１５〜５０質量部の範囲である。この添加量が
１０質量部未満では形成された皮膜の硬度や耐食性が低
下し、１００質量部を超えると造膜性や耐水性が低下す
る場合がある。The colloidal silica used in the production method of the present invention preferably has a pH stability in a range from neutral to alkaline, and has good coexistence stability with seed particles. Examples of colloidal silica meeting such conditions include Snowtex N, Snowtex C (manufactured by Nissan Chemical Industries, Ltd.), Cataloid S-20L, and Cataroid SA (manufactured by Catalysis Kasei Kogyo). The addition amount is in the range of 10 to 100 parts by mass, more preferably 15 to 50 parts by mass, based on the resin solid content of the seed particles. If the addition amount is less than 10 parts by mass, the hardness and corrosion resistance of the formed film are reduced, and if it exceeds 100 parts by mass, the film-forming property and water resistance may be reduced.
【００１５】本発明の製造方法で乳化重合に用いられる
不飽和モノマー類はエポキシ基含有不飽和モノマーおよ
び／または多官能性不飽和モノマーを必須成分としてい
る。エポキシ基含有不飽和モノマーの例としては、グリ
シジル（メタ）アクリレートのような不飽和カルボン酸
のグリシジルエステルやアリルグリシジルエーテルなど
を挙げることができる。多官能性不飽和モノマーの例と
しては、エチレングリコールジメタクリレート、ネオペ
ンチルグリコールジメタクリレート、グリセリンジメタ
クリレート、ジビニルベンゼン、トリメチロールプロパ
ントリアクリレート、ペンタエリスリトールトリアクリ
レートなどを挙げることができる。The unsaturated monomers used for emulsion polymerization in the production method of the present invention contain an epoxy group-containing unsaturated monomer and / or a polyfunctional unsaturated monomer as essential components. Examples of the epoxy group-containing unsaturated monomer include glycidyl esters of unsaturated carboxylic acids such as glycidyl (meth) acrylate and allyl glycidyl ether. Examples of the polyfunctional unsaturated monomer include ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, glycerin dimethacrylate, divinylbenzene, trimethylolpropane triacrylate, and pentaerythritol triacrylate.
【００１６】また、エポキシ基含有不飽和モノマーおよ
び／または多官能性不飽和モノマー以外の他のラジカル
重合性不飽和モノマーも適宜併用することができる。こ
のようなラジカル重合性不飽和モノマーは特に限定され
るものではないが、疎水性のものが好ましく、たとえば
次のようなものが挙げられる。スチレン、α−メチルス
チレン、アクリロニトリル、酢酸ビニルなどのビニル化
合物類およびメチル（メタ）アクリレート、エチル（メ
タ）アクリレート、ブチル（メタ）アクリレート、２−
エチルヘキシル（メタ）アクリレートなどの（メタ）ア
クリル酸アルキルエステル類。また、上記疎水性モノマ
ー以外に、２−ヒドロキシエチル（メタ）アクリレー
ト、４−ヒドロキシブチル（メタ）アクリレートなどの
水酸基含有化合物類、アクリル酸、メタクリル酸、イタ
コン酸などのカルボキシル基含有化合物類および（メ
タ）アクリルアミド、Ｎ、Ｎ−ジメチルアクリルアミド
などのアミド化合物類といった親水性モノマー類も使用
することができる。In addition, other radically polymerizable unsaturated monomers other than the epoxy group-containing unsaturated monomer and / or the polyfunctional unsaturated monomer can be appropriately used in combination. Such a radical polymerizable unsaturated monomer is not particularly limited, but is preferably a hydrophobic one, and examples thereof include the following. Vinyl compounds such as styrene, α-methylstyrene, acrylonitrile, and vinyl acetate, and methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-
(Meth) acrylic acid alkyl esters such as ethylhexyl (meth) acrylate. In addition to the above-mentioned hydrophobic monomers, hydroxyl-containing compounds such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; carboxyl-containing compounds such as acrylic acid, methacrylic acid, and itaconic acid; and ( Hydrophilic monomers such as amide compounds such as (meth) acrylamide and N, N-dimethylacrylamide can also be used.
【００１７】不飽和モノマー類のトータルの固形分使用
量は、上記エチレン−不飽和カルボン酸共重合物の固形
分１００質量部に対して２０〜２００質量部が好まし
く、さらに好ましくは３０〜１２０質量部とするのが良
い。使用量が２０質量部未満では複合効果が認められ
ず、２００質量部を超えると粒子径が大きくなったり造
膜性が低下したりして付着性や耐食性を低下させる。The total solids content of the unsaturated monomers is preferably from 20 to 200 parts by mass, more preferably from 30 to 120 parts by mass, based on 100 parts by mass of the solid content of the ethylene-unsaturated carboxylic acid copolymer. Department is good. If the amount used is less than 20 parts by mass, no composite effect is observed, and if it exceeds 200 parts by mass, the particle size becomes large or the film-forming property is reduced, so that the adhesion and the corrosion resistance are reduced.
【００１８】本発明の水性樹脂の製造方法は以下のよう
にして行われる。エチレン−不飽和カルボン酸共重合物
の水分散体、コロイダルシリカ、および必要に応じて水
性ポリウレタン樹脂、水性ポリエステル樹脂および水性
アクリル樹脂から選ばれる水性樹脂から得られる混合物
を撹拌しながら適宜昇温し、ここへエポキシ基含有不飽
和モノマーおよび／または多官能性不飽和モノマーを必
須成分とする不飽和モノマー類を重合開始剤とともに添
加する。開始剤としては、乳化重合に使用される一般的
なものが使用でき、たとえば過硫酸アンモニウム、過硫
酸カリウムなどの過硫酸塩類、アゾビスシアノ吉草酸、
アゾビスイソブチロニトリルなどのアゾ化合物類を挙げ
ることができる。なお、不飽和モノマー類および重合開
始剤の添加は、一度に行わず連続的に滴下したり数回に
分けたりすることが、過剰反応を防止する面で好まし
い。反応は公知のシード乳化重合法に従って行うことが
でき、温度は３０〜９０℃、時間は３０分〜８時間、固
形分濃度は１５〜４５質量％で実施できる。The method for producing an aqueous resin of the present invention is carried out as follows. The mixture obtained from the aqueous dispersion of the ethylene-unsaturated carboxylic acid copolymer, colloidal silica, and the aqueous resin selected from the aqueous polyurethane resin, the aqueous polyester resin, and the aqueous acrylic resin, if necessary, is appropriately heated while stirring. Here, unsaturated monomers containing an epoxy group-containing unsaturated monomer and / or a polyfunctional unsaturated monomer as an essential component are added together with a polymerization initiator. As the initiator, those commonly used in emulsion polymerization can be used, for example, ammonium persulfate, persulfates such as potassium persulfate, azobiscyanovaleric acid,
Azo compounds such as azobisisobutyronitrile can be mentioned. The addition of the unsaturated monomer and the polymerization initiator is preferably performed not at once, but continuously, or divided into several portions, from the viewpoint of preventing an excessive reaction. The reaction can be carried out according to a known seed emulsion polymerization method, the temperature can be 30 to 90 ° C., the time can be 30 minutes to 8 hours, and the solid content concentration can be 15 to 45% by mass.
【００１９】コロイダルシリカの存在下で乳化重合を行
うと、粒子同士の凝集が起こりにくいので、得られる水
性樹脂の粒子径は、シード粒子の粒子径、シード樹脂の
質量比、コロイダルシリカの添加量と粒子径に依存し、
平均粒子径として１０〜８０ｎｍになる。この範囲の粒
子径では、造膜性が良好で、緻密な皮膜の形成が可能と
なるため各種の性能に優れたものとなる。When emulsion polymerization is carried out in the presence of colloidal silica, the particles hardly agglomerate. Therefore, the particle size of the resulting aqueous resin depends on the particle size of the seed particles, the mass ratio of the seed resin, and the amount of colloidal silica added. And particle size,
The average particle diameter becomes 10 to 80 nm. When the particle diameter is in this range, the film-forming properties are good and a dense film can be formed, so that various properties are excellent.
【００２０】上記不飽和モノマー類は、エポキシ基およ
び／または複数の不飽和結合、その他カルボキシル基等
の官能基を含有する。したがって乳化重合による架橋反
応は、シード粒子のカルボキシル基と不飽和モノマー類
との間、および／または不飽和モノマー類同士で進行す
る。さらに不飽和モノマー類同士の３次元架橋によって
シード粒子内に形成された重合体粒子は、シード粒子と
物理的に絡み合い、場合によっては化学的にも結合する
ため、本発明の樹脂により形成した皮膜は強靭なものと
なる。The unsaturated monomers contain an epoxy group and / or a plurality of unsaturated bonds, and other functional groups such as a carboxyl group. Therefore, the crosslinking reaction by emulsion polymerization proceeds between the carboxyl group of the seed particles and the unsaturated monomers, and / or between the unsaturated monomers. Further, the polymer particles formed in the seed particles by the three-dimensional crosslinking of the unsaturated monomers are physically entangled with the seed particles, and in some cases, are chemically bonded. Will be tough.
【００２１】[0021]
【実施例】次に、実施例および比較例を挙げて、本発明
をさらに具体的に説明する。Next, the present invention will be described more specifically with reference to examples and comparative examples.
【００２２】実施例１ 水性樹脂の合成 攪拌機、温度調節器、滴下漏斗、窒素導入管および冷却
器を備えたフラスコに、エチレン−アクリル酸共重合物
（プリマコール５９８０、ダウケミカル社製）をアンモ
ニア水で中和率８０％に調整した水分散液４００ｇ（固
形分２５質量％）、コロイダルシリカ（スノーテックス
Ｎ、日産化学工業製、固形分２０質量％）３００ｇと水
性ポリウレタン樹脂（アデカボンタイターＨＵＸ−３２
０、旭電化工業社製、固形分３２質量％）９３．８ｇを
加えて８３℃に昇温した。 Example 1 Synthesis of Aqueous Resin An ethylene-acrylic acid copolymer (Primacol 5980, manufactured by Dow Chemical Co.) was added to ammonia in a flask equipped with a stirrer, temperature controller, dropping funnel, nitrogen inlet tube and condenser. 400 g (solid content: 25% by mass) of an aqueous dispersion adjusted to a neutralization ratio of 80% with water, 300 g of colloidal silica (Snowtex N, manufactured by Nissan Chemical Industries, solid content: 20% by mass), and an aqueous polyurethane resin (Adecabon Titer HUX) −32
0, manufactured by Asahi Denka Kogyo Co., Ltd., solid content: 32% by mass) and heated to 83 ° C.
【００２３】続いて、窒素雰囲気下に、グリシジルメタ
クリレート３５ｇ、スチレン２１ｇおよびメチルメタク
リレート１４ｇから得られるモノマー混合物の１０分の
１量を添加し１０分間撹拌した後、アゾビスシアノ吉草
酸１ｇをＮ，Ｎ−ジメチルアミノエタノール０．６部で
中和し脱イオン水６０ｇに溶解させた重合開始剤水溶液
の４分の１量を投入して重合を開始させた。この重合開
始剤の投入後１０分経過してから、残りのモノマー混合
物と開始剤水溶液をそれぞれ６０分間および７０分間に
わたって均等に滴下した。滴下終了後には、そのままの
温度で１２０分間エージングを行い反応を完結させた。
冷却後金網で濾過し固形分２８質量％、平均粒子径４０
ｎｍの水性樹脂分散体を得た。Subsequently, under a nitrogen atmosphere, 1/10 of the monomer mixture obtained from 35 g of glycidyl methacrylate, 21 g of styrene and 14 g of methyl methacrylate was added and stirred for 10 minutes, and 1 g of azobiscyanovaleric acid was added to N, N- A quarter amount of a polymerization initiator aqueous solution neutralized with 0.6 part of dimethylaminoethanol and dissolved in 60 g of deionized water was charged to initiate polymerization. Ten minutes after the addition of the polymerization initiator, the remaining monomer mixture and the aqueous initiator solution were dropped uniformly over 60 minutes and 70 minutes, respectively. After the completion of the dropwise addition, aging was continued for 120 minutes at the same temperature to complete the reaction.
After cooling, the mixture was filtered through a wire mesh, solid content was 28% by mass, and average particle size was 40
nm aqueous resin dispersion was obtained.
【００２４】皮膜形成 脱脂、洗浄した板厚０．５ｍｍの溶融５５質量％アルミ
ニウム−亜鉛合金めっき鋼板（市販品）の表面に、先に
得られた水性樹脂分散体を、乾燥膜厚が１．５ｇ／ｍ2
になるようバーコーターで塗布し、電気乾燥炉で２６０
℃、８秒間乾燥させた。なお、この時の被塗物到達温度
は８０℃であった。これを冷却したものを試験板とし、
耐溶剤性、耐食性、耐アルカリ性および上塗り塗料密着
性を下記の方法によって評価し、その結果を表１に記載
した。The film-forming degreasing, melting 55 wt% aluminum washed thickness 0.5 mm - on the surface of the zinc alloy coated steel sheet (commercially available), the aqueous resin dispersion obtained above, a dry film thickness of 1. 5 g / m 2
Apply with a bar coater so that it becomes 260
C. and dried for 8 seconds. At this time, the temperature at which the object was reached was 80 ° C. The cooled one is used as a test plate,
The solvent resistance, corrosion resistance, alkali resistance and adhesion of the topcoat paint were evaluated by the following methods, and the results are shown in Table 1.
【００２５】評価方法 ＜平均粒子径＞得られた水性樹脂の一部を脱イオン水で
希釈し、動的光散乱測定機（ＥＬＳ−８００、大塚電子
社製）により測定した。 Evaluation Method <Average Particle Diameter> A part of the obtained aqueous resin was diluted with deionized water and measured with a dynamic light scattering analyzer (ELS-800, manufactured by Otsuka Electronics Co., Ltd.).
【００２６】＜重合安定性＞水性樹脂の重合後の状態を
下記の基準で評価した。 ○：濾過可能で凝集物なし △：濾過困難および／または凝集物発生量が２質量％以
上 ×：濾過不能および／または凝集物発生量が５質量％以
上<Polymerization Stability> The state of the aqueous resin after polymerization was evaluated according to the following criteria. ：: Filterable and no aggregates Δ: Difficult to filter and / or the amount of aggregates generated is 2% by mass or more ×: Unfilterable and / or the amount of aggregates generated is 5% by mass or more
【００２７】＜耐溶剤性＞試験板をラビング・テスター
にセットし、キシレンを含浸させたガーゼを０．５ｋｇ
ｆ／ｃｍ2で押し当てて１０回往復させた後、試験板表
面の皮膜の状態を目視で観察した。 ○：ほとんど傷がつかない △：少し傷がつく ×：全面に傷がつく<Solvent resistance> The test plate was set on a rubbing tester, and 0.5 kg of gauze impregnated with xylene was used.
After pressing and reciprocating 10 times at f / cm 2 , the state of the film on the surface of the test plate was visually observed. ：: scarcely scarred △: slightly scratched ×: scratched all over
【００２８】＜耐アルカリ性＞試験板を１％ＮａＯＨ水
溶液に３０分間浸漬した後、表面外観を目視で測定し
た。 ○：ほとんど黒変なし △：少し黒変する ×：全面黒変<Alkali Resistance> After the test plate was immersed in a 1% aqueous NaOH solution for 30 minutes, the surface appearance was visually measured. ：: almost no blackening △: slightly blackening ×: blackening of the entire surface
【００２９】＜耐食性＞試験板をＪＩＳＺ２３７１に基
づき塩水噴霧試験機にかけ７２時間後の錆発生面積を測
定し、下記基準で評価し、表１に示す結果を得た。 ○：１０％未満 △：１０％以上〜５０％未満 ×：５０％以上<Corrosion Resistance> The test plate was subjected to a salt spray tester based on JISZ2371 to measure the rust generation area after 72 hours, and evaluated according to the following criteria. The results shown in Table 1 were obtained. ：: less than 10% △: 10% or more to less than 50% ×: 50% or more
【００３０】＜上塗り密着性＞試験板にメラミンアルキ
ド樹脂塗料（オルガセレクト２００、日本ペイント社
製）を乾燥膜厚が３０μｍとなるようにバーコーターで
塗装し、１１０℃で２０分間熱風乾燥炉を用いて焼き付
けて塗装板を作成した。この塗装板の塗膜に、カッター
ナイフを用いて１ｍｍ間隔の碁盤目を１００個作り、そ
こへ粘着テープを貼り付けて垂直に剥離した。そして塗
膜の残存した碁盤目の数を測定し、下記の基準で評価し
た。 ：残存数１００個 △： 〃 ９９〜５１個 ×： 〃 ５０個以下<Adhesion of Topcoat> A melamine alkyd resin paint (Olga Select 200, manufactured by Nippon Paint Co., Ltd.) was applied on a test plate with a bar coater so as to have a dry film thickness of 30 μm. And baked to make a painted plate. Using a cutter knife, 100 grids at 1 mm intervals were formed on the coating film of the painted plate, and an adhesive tape was stuck thereon and peeled vertically. Then, the number of grids where the coating film remained was measured and evaluated according to the following criteria. : 100 remaining number △: ９９ 99 to 51 ×: ５０ 50 or less
【００３１】実施例２〜４ 表１に示す処方に変更した以外は実施例１と同じ装置、
手順で反応を行い水性樹脂分散体を得た。また、実施例
１と同様にして試験板の作製および評価を行った。得ら
れた結果を表１に記載する。 Examples 2 to 4 The same apparatus as in Example 1 except that the formulations shown in Table 1 were changed.
The reaction was performed according to the procedure to obtain an aqueous resin dispersion. Further, a test plate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the obtained results.
【００３２】比較例１ 表１に示す処方に変更した以外は実施例１と同じ装置、
手順で反応を行い水性樹脂分散体を得た。これにスノー
テックスＮを３００質量部後添加して塗布液とし、これ
を実施例１と同様にして試験板の作製および評価を行っ
た。得られた結果を表１に記載する。 Comparative Example 1 The same apparatus as in Example 1 except that the formulation was changed to the formulation shown in Table 1,
The reaction was performed according to the procedure to obtain an aqueous resin dispersion. To this was added 300 parts by mass of Snowtex N to prepare a coating solution, which was then prepared and evaluated in the same manner as in Example 1. Table 1 shows the obtained results.
【００３３】比較例２〜４ 表１に示す処方に変更した以外は実施例１と同じ装置、
手順で反応を行い水性樹脂分散体を得た。また、実施例
１と同様にして試験板の作製および評価を行った。得ら
れた結果を表１に記載する。 Comparative Examples 2 to 4 The same apparatus as in Example 1 except that the formulations shown in Table 1 were changed.
The reaction was performed according to the procedure to obtain an aqueous resin dispersion. Further, a test plate was prepared and evaluated in the same manner as in Example 1. Table 1 shows the obtained results.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表１の内容から明らかなように、本実施例
で製造した水性樹脂は、平均粒子径が４０〜５２ｎｍの
重合安定性の高いものであった。また形成した皮膜は、
耐溶剤性、耐アルカリ性、耐食性および上塗り密着性に
優れていた。As is clear from the contents of Table 1, the aqueous resin produced in this example had an average particle diameter of 40 to 52 nm and high polymerization stability. The formed film is
It had excellent solvent resistance, alkali resistance, corrosion resistance, and overcoat adhesion.
【００３６】[0036]
【発明の効果】本発明の水性樹脂は、シード重合法を採
用することにより、乳化剤を使用することなく安定的に
乳化重合できる。これに加えて、コロイダルシリカを反
応系に共存させたため、反応液の粘度が下がり重合安定
性が向上して微小粒子の合成が可能である。The aqueous resin of the present invention can be stably emulsion-polymerized by using a seed polymerization method without using an emulsifier. In addition to this, colloidal silica is allowed to coexist in the reaction system, so that the viscosity of the reaction solution is reduced, the polymerization stability is improved, and fine particles can be synthesized.
【００３７】また、エチレン−不飽和カルボン酸共重合
物とエポキシ基含有不飽和モノマーおよび／または多官
能性不飽和モノマーとを複合して重合させるため、各樹
脂の相溶性向上による上塗り塗料密着性の確保、樹脂の
平均酸価低下による塗膜の耐アルカリ性向上、架橋によ
る分子量の増大から耐食性、耐溶剤性、および耐アルカ
リ性の向上をはかることができる。In addition, since the ethylene-unsaturated carboxylic acid copolymer and the epoxy group-containing unsaturated monomer and / or the polyfunctional unsaturated monomer are polymerized in a complex manner, the adhesion of the topcoat paint is improved by improving the compatibility of each resin. , The alkali resistance of the coating film is improved by lowering the average acid value of the resin, and the corrosion resistance, solvent resistance, and alkali resistance are improved by increasing the molecular weight by crosslinking.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 123/08 Ｃ０９Ｄ 123/08 133/02 133/02 151/00 151/00 163/10 163/10 Ｆターム(参考） 4J011 AA05 AA08 KA11 KB08 KB13 KB19 KB22 KB29 4J026 AA12 AA43 AA45 AB02 AB07 AC17 AC23 BA05 BA07 BA16 BA20 BA25 BA27 BA28 BA30 BA31 BA34 BA38 BB02 DB04 DB12 DB14 DB25 DB28 DB30 4J038 CB061 CB062 CC011 CC021 CC081 CE051 CF021 CG031 CG032 CG061 CG141 CG161 CG171 CH031 CH051 CH061 CH071 CH121 CH171 DD041 DD042 DD241 DD242 DG051 DG052 DG061 DG062 DG261 DG262 HA156 HA446 KA08 LA02 MA08 MA10 NA03 NA04 NA12 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) C09D 123/08 C09D 123/08 133/02 133/02 151/00 151/00 163/10 163/10 F Terms (reference) 4J011 AA05 AA08 KA11 KB08 KB13 KB19 KB22 KB29 4J026 AA12 AA43 AA45 AB02 AB07 AC17 AC23 BA05 BA07 BA16 BA20 BA25 BA27 BA28 BA30 BA31 BA34 BA38 BB02 DB04 DB12 DB14 DB25 DB28 DB30 4J01 CB061 CB061 CB061 CB061 CG06 CG141 CG161 CG171 CH031 CH051 CH061 CH071 CH121 CH171 DD041 DD042 DD241 DD242 DG051 DG052 DG061 DG062 DG261 DG262 HA156 HA446 KA08 LA02 MA08 MA10 NA03 NA04 NA12
Claims (4)
分散体をシード粒子とし、コロイダルシリカの共存下
に、エポキシ基含有不飽和モノマーおよび／または多官
能性不飽和モノマーを必須成分とする不飽和モノマー類
を乳化重合させることを特徴とする水性樹脂の製造方
法。1. An aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer is used as seed particles, and an epoxy group-containing unsaturated monomer and / or a polyfunctional unsaturated monomer is an essential component in the presence of colloidal silica. A method for producing an aqueous resin, comprising subjecting an unsaturated monomer to emulsion polymerization.
ウレタン樹脂、水性ポリエステル樹脂および水性アクリ
ル樹脂から選ばれる水性樹脂を併用することを特徴とす
る請求項１に記載の水性樹脂の製造方法。2. The method for producing an aqueous resin according to claim 1, wherein an aqueous resin selected from an aqueous polyurethane resin, an aqueous polyester resin and an aqueous acrylic resin is further used as the seed particles.
得られる水性樹脂。3. An aqueous resin obtained by the method according to claim 1.
３記載の水性樹脂。4. The aqueous resin according to claim 3, having an average particle size of 10 to 80 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000109193A JP2001294630A (en) | 2000-04-11 | 2000-04-11 | Aqueous resin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000109193A JP2001294630A (en) | 2000-04-11 | 2000-04-11 | Aqueous resin and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JP2001294630A true JP2001294630A (en) | 2001-10-23 |
Family
ID=18621915
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002256209A (en) * | 2001-03-02 | 2002-09-11 | Nippon Paint Co Ltd | Aqueous coating composition |
| JP2008506831A (en) * | 2004-09-15 | 2008-03-06 | エルジー・ケム・リミテッド | Film or building exterior material using self-cleaning coating composition and method for producing the same |
| JP2008239637A (en) * | 2007-03-23 | 2008-10-09 | Sekisui Plastics Co Ltd | Method for producing polymer particle |
| US8241742B2 (en) * | 2006-06-15 | 2012-08-14 | Nippon Steel Corporation | Coated steel sheet comprising a composite coat containing compounded resin particles |
| US8349446B2 (en) * | 2006-06-15 | 2013-01-08 | Nippon Paint Co., Ltd. | Coated steel sheet |
| WO2013100836A1 (en) * | 2011-12-29 | 2013-07-04 | Perstorp Ab | Alkyd resin composition comprising silica |
| JP2015048389A (en) * | 2013-08-30 | 2015-03-16 | 東邦化学工業株式会社 | Aqueous floor polishing agent composition |
| JP2018104620A (en) * | 2016-12-28 | 2018-07-05 | 三菱ケミカル株式会社 | Aqueous resin dispersion |
| WO2019112039A1 (en) * | 2017-12-07 | 2019-06-13 | 三菱ケミカル株式会社 | Aqueous resin dispersion, method for producing aqueous resin dispersion, aqueous coating material, and adhesive |
-
2000
- 2000-04-11 JP JP2000109193A patent/JP2001294630A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002256209A (en) * | 2001-03-02 | 2002-09-11 | Nippon Paint Co Ltd | Aqueous coating composition |
| JP2008506831A (en) * | 2004-09-15 | 2008-03-06 | エルジー・ケム・リミテッド | Film or building exterior material using self-cleaning coating composition and method for producing the same |
| JP4712802B2 (en) * | 2004-09-15 | 2011-06-29 | エルジー・ケム・リミテッド | Film or building exterior material using self-cleaning coating composition and method for producing the same |
| TWI408255B (en) * | 2006-06-15 | 2013-09-11 | Nippon Steel & Sumitomo Metal Corp | Coated steel plate |
| US8241742B2 (en) * | 2006-06-15 | 2012-08-14 | Nippon Steel Corporation | Coated steel sheet comprising a composite coat containing compounded resin particles |
| US8349446B2 (en) * | 2006-06-15 | 2013-01-08 | Nippon Paint Co., Ltd. | Coated steel sheet |
| TWI397609B (en) * | 2006-06-15 | 2013-06-01 | Nippon Paint Co Ltd | Coated steel plate |
| KR101278773B1 (en) | 2006-06-15 | 2013-06-25 | 신닛테츠스미킨 카부시키카이샤 | Coated steel sheet |
| KR101298801B1 (en) * | 2006-06-15 | 2013-08-22 | 신닛테츠스미킨 카부시키카이샤 | Coated steel sheet |
| JP2008239637A (en) * | 2007-03-23 | 2008-10-09 | Sekisui Plastics Co Ltd | Method for producing polymer particle |
| WO2013100836A1 (en) * | 2011-12-29 | 2013-07-04 | Perstorp Ab | Alkyd resin composition comprising silica |
| JP2015048389A (en) * | 2013-08-30 | 2015-03-16 | 東邦化学工業株式会社 | Aqueous floor polishing agent composition |
| JP2018104620A (en) * | 2016-12-28 | 2018-07-05 | 三菱ケミカル株式会社 | Aqueous resin dispersion |
| WO2019112039A1 (en) * | 2017-12-07 | 2019-06-13 | 三菱ケミカル株式会社 | Aqueous resin dispersion, method for producing aqueous resin dispersion, aqueous coating material, and adhesive |
| CN111433272A (en) * | 2017-12-07 | 2020-07-17 | 三菱化学株式会社 | Aqueous resin dispersion, method for producing aqueous resin dispersion, aqueous coating material, and adhesive |
| JPWO2019112039A1 (en) * | 2017-12-07 | 2020-12-10 | 三菱ケミカル株式会社 | Water-based resin dispersion, manufacturing method of water-based resin dispersion, water-based paint, adhesive |
| US11421101B2 (en) | 2017-12-07 | 2022-08-23 | Mitsubishi Chemical Corporation | Aqueous resin dispersion, method for producing aqueous resin dispersion, aqueous coating material, and adhesive |
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