JP2005089716A - Aqueous coating composition and method for producing the same - Google Patents
Aqueous coating composition and method for producing the same Download PDFInfo
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本発明は、有機溶剤の不存在下に共重合してなる、ＣＯＯＨ基を有する特定のアクリル系共重合体を一種の高分子乳化剤として用いて、エチレン性不飽和モノマーを種々の方法で水の存在下にラジカル重合してなるポリマーエマルジョンを含有する水性塗料組成物に関する。詳しくは、衛生性、耐レトルト性、加工性、密着性に優れる塗膜を形成し得る水性塗料組成物であって、有機溶剤を留去する必要がないので、生産性、経済性に優れる水性塗料組成物に関する。さらに詳しくは飲料や食品を収容する缶の内面被覆に好適に用いられる水性塗料組成物及びにそれを用いて缶内面を被覆してなる被覆缶に関する。 The present invention uses a specific acrylic copolymer having a COOH group, which is copolymerized in the absence of an organic solvent, as a kind of polymer emulsifier, and an ethylenically unsaturated monomer in various ways. The present invention relates to an aqueous coating composition containing a polymer emulsion formed by radical polymerization in the presence thereof. Specifically, it is an aqueous coating composition that can form a coating film excellent in hygiene, retort resistance, workability, and adhesion, and it is not necessary to distill off the organic solvent. The present invention relates to a coating composition. More specifically, the present invention relates to an aqueous coating composition suitably used for coating an inner surface of a can containing a beverage or food, and a coated can formed by using the aqueous coating composition.
ビスフェノールＡ（以下ＢＰＡと略す）とエピクロルヒドリンとを原料として合成されるＢＰＡ型エポキシ樹脂は、耐煮沸性、加工性、密着性に優れた塗膜を形成する機能を有することから、缶内外面被覆用塗料に好適に用いられている。
缶内面被覆用水性塗料には、従来から、ＢＰＡ型エポキシ樹脂をアクリル樹脂で変性し、カルボキシル基などを分子中に導入した水分散型アクリル変性エポキシ樹脂が主にして使用されている。
The BPA type epoxy resin synthesized from bisphenol A (hereinafter abbreviated as BPA) and epichlorohydrin has the function of forming a coating film excellent in boiling resistance, workability, and adhesion. It is suitably used for paints.
Conventionally, water-dispersed acrylic modified epoxy resins in which a BPA type epoxy resin is modified with an acrylic resin and a carboxyl group or the like is introduced into the molecule are mainly used for water-based coatings for can inner surface coating.
ＢＰＡ型エポキシ樹脂以外で、ＢＰＡ型エポキシ樹脂と同等の加工性、密着性を持つ樹脂として、乳化重合により合成したエマルジョン型アクリル樹脂がある。乳化重合で合成したエマルジョン型アクリル樹脂は、一般に非常に高分子量になることが知られており、樹脂が高分子量になることで、加工性、密着性が得られると考えられる。
しかし、一般に乳化重合には界面活性剤が用いられるので、硬化塗膜中に界面活性剤が含まれることとなる。この界面活性剤が硬化塗膜の耐レトルト性悪化の原因となるので、現状では、乳化重合により合成したエマルジョン型アクリル樹脂を缶内面被覆用塗料に使用するには至っていない。
As a resin other than the BPA type epoxy resin and having processability and adhesion similar to those of the BPA type epoxy resin, there is an emulsion type acrylic resin synthesized by emulsion polymerization. Emulsion-type acrylic resins synthesized by emulsion polymerization are generally known to have a very high molecular weight, and it is considered that processability and adhesion can be obtained when the resin has a high molecular weight.
However, since a surfactant is generally used for emulsion polymerization, the surfactant is contained in the cured coating film. Since this surfactant causes deterioration of the retort resistance of the cured coating film, at present, an emulsion type acrylic resin synthesized by emulsion polymerization has not been used for a paint for coating inner surfaces of cans.
耐レトルト性悪化の原因である界面活性剤を用いずに、その代わりにカルボキシル基をもつアクリル系共重合体を塩基性化合物で中和させて水に溶解ないし分散させ、その水溶液ないし水性分散体を用いる方法が、提案された（特許文献１：特開２００２−１５５２３４号公報参照）。即ち、特許文献１には、上記水溶液ないし水性分散体の存在下に、エチレン性不飽和単量体の水性分散体を重合してなる、ソープフリー型アクリル樹脂エマルジョンが缶用水性塗料組成物に用い得る旨記載されている。特許文献１に記載される缶用水性塗料組成物は、加工性、密着性、耐レトルト性に優れる塗膜を形成し得る。 Instead of using a surfactant that causes a deterioration in retort resistance, instead of neutralizing an acrylic copolymer having a carboxyl group with a basic compound and dissolving or dispersing it in water, an aqueous solution or dispersion thereof Has been proposed (see Patent Document 1: Japanese Patent Laid-Open No. 2002-155234). That is, Patent Document 1 discloses a soap-free acrylic resin emulsion obtained by polymerizing an aqueous dispersion of an ethylenically unsaturated monomer in the presence of the above aqueous solution or aqueous dispersion as an aqueous coating composition for cans. It is described that it can be used. The water-based paint composition for cans described in Patent Document 1 can form a coating film excellent in processability, adhesion, and retort resistance.
ところで、一般に乳化重合は溶剤の存在しない状態で行うことが多く、溶剤が存在しても、系全体中の溶剤の割合があまり多くないほうが好ましい。溶剤の割合が多い場合、重合の転化率が十分に得られない場合や、重合物から形成される塗膜の物性が悪化する場合がある。
従って、溶液重合によって得たアクリル系共重合体を高分子乳化剤として乳化重合の際に用いるためには、アクリル系共重合体重合時の溶剤を留去しておく必要がある。溶剤留去は、生産性低下の原因ともなり、コストを上昇させる原因ともなる。
By the way, in general, emulsion polymerization is often performed in the absence of a solvent, and even if a solvent is present, it is preferable that the proportion of the solvent in the entire system is not so large. When the ratio of the solvent is large, the polymerization conversion rate may not be sufficiently obtained, or the physical properties of the coating film formed from the polymer may be deteriorated.
Therefore, in order to use an acrylic copolymer obtained by solution polymerization as a polymer emulsifier in emulsion polymerization, it is necessary to distill off the solvent during the polymerization of the acrylic copolymer. Solvent evaporation also causes a decrease in productivity and a cost increase.
有機溶剤を使用せずに、溶剤留去工程を省ければ、生産性及び経済性向上を図ることができる。
しかし、特許文献１に開示される高分子乳化剤は、カルボキシル基以外にも塗膜形成時の硬化に寄与する架橋性官能基を有する。従って、有機溶剤を使用せずに、高分子乳化剤を得ようとすると、重合時にゲル化が起こり、合成できない。
However, the polymer emulsifier disclosed in Patent Document 1 has a crosslinkable functional group that contributes to curing during coating film formation in addition to the carboxyl group. Therefore, when an attempt is made to obtain a polymer emulsifier without using an organic solvent, gelation occurs at the time of polymerization and synthesis cannot be performed.
本発明の課題は、溶剤留去工程を経ることなく、ＢＰＡ由来の構成成分を全く用いず、焼付け後の硬化塗膜の耐煮沸性を悪化させる界面活性剤を実質的に用いずに、加工性、密着性に優れる塗膜を形成し得る、生産性、経済性に優れる缶内面被覆用水性塗料組成物及びそれを用いて缶内面を被覆してなる被覆缶を提供することである。 The object of the present invention is to pass through a solvent distillation step, use no BPA-derived components, and substantially use a surfactant that deteriorates the boiling resistance of a cured coating film after baking. An aqueous coating composition for can inner surface coating that can form a coating film having excellent properties and adhesion, and an excellent productivity and economy, and a coated can formed by coating the can inner surface using the same.
本発明者は、鋭意検討した結果、界面活性剤を用いずに、架橋性官能基としてカルボキシル基のみを有するアクリル系共重合体を高分子乳化剤として、これを塩基性化合物で中和することにより水に溶解ないし分散させ、この高分子乳化剤を用いてアクリルモノマーを乳化し、乳化重合を行うことにより得られるポリマーエマルジョンとフェノール樹脂とを含有する水性塗料組成物が生産性、経済性に優れると共に、加工性、密着性、耐レトルト性に優れる塗膜を形成し得ることを見出し、本発明を完成するに至った。 As a result of diligent study, the present inventor has neutralized this with a basic compound, using an acrylic copolymer having only a carboxyl group as a crosslinkable functional group as a polymer emulsifier without using a surfactant. An aqueous coating composition containing a polymer emulsion obtained by dissolving or dispersing in water, emulsifying an acrylic monomer using this polymer emulsifier, and performing emulsion polymerization and a phenol resin is excellent in productivity and economy. The inventors have found that a coating film excellent in processability, adhesion, and retort resistance can be formed, and have completed the present invention.
即ち、第１の発明は、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルは含有しない被乳化成分（Ａ）、ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｂ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｂ２）を含有しないエチレン性不飽和モノマー（ｂ）を有機溶剤の不存在下に共重合してなるアクリル系共重合体（Ｂ）、塩基性化合物（Ｃ）及び水（Ｄ）を含有するモノマーエマルジョン（１）を、
水（Ｇ）の存在下に、
ラジカル重合してなるポリマーエマルジョン（３）、及びフェノール樹脂（６）
を含有することを特徴とする水性塗料組成物に関する。
That is, the first invention contains an ethylenically unsaturated monomer (A1) that contains an ethylenically unsaturated monomer (A1) and does not contain polyester, an ethylenically unsaturated monomer (b1) having a COOH group, and other than COOH groups An acrylic copolymer (B) obtained by copolymerizing an ethylenically unsaturated monomer (b) not containing an ethylenically unsaturated monomer (b2) having a crosslinkable functional group in the absence of an organic solvent, Monomer emulsion (1) containing compound (C) and water (D)
In the presence of water (G)
Polymer emulsion (3) obtained by radical polymerization, and phenol resin (6)
It is related with the water-based coating composition characterized by containing.
また、第２の発明は、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルは含有しない被乳化成分（Ａ）、ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｂ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｂ２）を含有しないエチレン性不飽和モノマー（ｂ）を有機溶剤の不存在下に共重合してなるアクリル系共重合体（Ｂ）、塩基性化合物（Ｃ）及び水（Ｄ）を含有するモノマーエマルジョン（１）を、
ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を有機溶剤の不存在下に共重合してなるアクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）を含有してなるポリマー水溶液ないしエマルジョン（２）の存在下に、
ラジカル重合してなるポリマーエマルジョン（４）、及びフェノール樹脂（６）
を含有することを特徴とする水性塗料組成物に関する。
Moreover, 2nd invention contains the ethylenically unsaturated monomer (b1) which contains the to-be-emulsified component (A) which contains an ethylenically unsaturated monomer (A1), and does not contain polyester, COOH group, Other than COOH group An acrylic copolymer (B) obtained by copolymerizing an ethylenically unsaturated monomer (b) not containing an ethylenically unsaturated monomer (b2) having a crosslinkable functional group in the absence of an organic solvent, Monomer emulsion (1) containing compound (C) and water (D)
An ethylenically unsaturated monomer (e) containing an ethylenically unsaturated monomer (e1) having a COOH group and not containing an ethylenically unsaturated monomer (e2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. In the presence of an aqueous polymer solution or emulsion (2) containing an acrylic copolymer (E), a basic compound (F) and water (G) copolymerized in the presence,
Polymer emulsion (4) obtained by radical polymerization and phenol resin (6)
It is related with the water-based coating composition characterized by containing.
さらに、第３の発明は、エチレン性不飽和モノマー（Ａ１）を、
ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を有機溶剤の不存在下に共重合してなるアクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）を含有してなるポリマー水溶液ないしエマルジョン（２）の存在下に、
ラジカル重合してなるポリマーエマルジョン（４）、及びフェノール樹脂（６）
を含有することを特徴とする水性塗料組成物、
に関する。
Furthermore, the third invention provides an ethylenically unsaturated monomer (A1),
An ethylenically unsaturated monomer (e) containing an ethylenically unsaturated monomer (e1) having a COOH group and not containing an ethylenically unsaturated monomer (e2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. In the presence of an aqueous polymer solution or emulsion (2) containing an acrylic copolymer (E), a basic compound (F) and water (G) copolymerized in the presence,
Polymer emulsion (4) obtained by radical polymerization and phenol resin (6)
A water-based coating composition comprising:
About.
また、本発明は、エチレン性不飽和モノマー（Ａ１）が、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマーを少なくとも１種含有することを特徴とする上記発明のいずれかに記載の水性塗料組成物に関する。 In the present invention, the ethylenically unsaturated monomer (A1) is at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. The present invention relates to the aqueous coating composition according to any one of the above inventions, characterized by containing a seed.
さらに、本発明は、エチレン性不飽和モノマー（Ａ１）が、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマーを含有せず、かつ、エチレン性不飽和モノマー（ｂ）及び（ｅ）が、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマーを含有しないことを特徴とする上記発明のいずれかに記載の水性塗料組成物に関する。 Further, in the present invention, the ethylenically unsaturated monomer (A1) contains an amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. And the ethylenically unsaturated monomers (b) and (e) are amide monomers selected from the group consisting of N-alkoxyalkyl (meth) acrylamides, N-hydroxyalkyl (meth) acrylamides and (meth) acrylamides. The aqueous coating composition according to any one of the above inventions, which is not contained.
また、本発明は、缶内面被覆用であることを特徴とする上記発明のいずれかに記載の水性塗料組成物に関する。 The present invention also relates to the aqueous coating composition according to any one of the above inventions, characterized in that it is for can inner surface coating.
また、本発明は、上記発明のいずれかに記載の水性塗料組成物で、缶内面を被覆してなることを特徴とする被覆缶に関する。 The present invention also relates to a coated can characterized in that the inner surface of the can is coated with the aqueous coating composition according to any one of the above inventions.
また、本発明は、ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｂ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｂ２）を含有しないエチレン性不飽和モノマー（ｂ）を有機溶剤の不存在下に共重合し、アクリル系共重合体（Ｂ）を得、該アクリル系共重合体（Ｂ）を塩基性化合物（Ｃ）の存在下に水に溶解ないし分散せしめ、アクリル系共重合体（Ｂ）の水溶液ないし水性分散体を得、
該アクリル系共重合体（Ｂ）の水溶液ないし水性分散体の存在下に、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルは含有しない被乳化成分（Ａ）を、水に分散し、モノマーエマルジョン（１）を得、
該モノマーエマルジョン（１）を水に滴下し、上記モノマー（Ａ１）を重合してなるポリマーエマルジョン（３）とフェノール樹脂（６）とを混合することを特徴とする水性塗料組成物の製造方法に関する。
Moreover, this invention contains the ethylenically unsaturated monomer (b1) which contains the ethylenically unsaturated monomer (b1) which has a COOH group, and does not contain the ethylenically unsaturated monomer (b2) which has crosslinkable functional groups other than a COOH group. ) In the absence of an organic solvent to obtain an acrylic copolymer (B), and the acrylic copolymer (B) is dissolved or dispersed in water in the presence of a basic compound (C). Obtaining an aqueous solution or dispersion of the acrylic copolymer (B),
In the presence of an aqueous solution or dispersion of the acrylic copolymer (B), the emulsified component (A) containing the ethylenically unsaturated monomer (A1) and not the polyester is dispersed in water, and the monomer is dispersed. Emulsion (1) was obtained
The present invention relates to a method for producing an aqueous coating composition, which comprises dropping the monomer emulsion (1) into water and mixing a polymer emulsion (3) obtained by polymerizing the monomer (A1) and a phenol resin (6). .
また、本発明は、ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｂ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｂ２）を含有しないエチレン性不飽和モノマー（ｂ）を有機溶剤の不存在下に共重合し、アクリル系共重合体（Ｂ）を得、該アクリル系共重合体（Ｂ）を塩基性化合物（Ｃ）の存在下に水に溶解ないし分散せしめ、アクリル系共重合体（Ｂ）の水溶液ないし水性分散体を得、
該アクリル系共重合体（Ｂ）の水溶液ないし水性分散体の存在下に、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルは含有しない被乳化成分（Ａ）を、水に分散し、モノマーエマルジョン（１）を得、
ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を有機溶剤の不存在下に共重合し、アクリル系共重合体（Ｅ）を得、該アクリル系共重合体（Ｅ）を塩基性化合物（Ｆ）の存在下に水に溶解ないし分散せしめ、アクリル系共重合体（Ｅ）の水溶液ないし水性分散体を得、
前記モノマーエマルジョン（１）を、前記アクリル系共重合体（Ｅ）の水溶液ないし水性分散体に滴下し、モノマー（Ａ１）を重合してなるポリマーエマルジョン（４）とフェノール樹脂（６）とを混合することを特徴とする水性塗料組成物の製造方法に関する。
Moreover, this invention contains the ethylenically unsaturated monomer (b1) which contains the ethylenically unsaturated monomer (b1) which has a COOH group, and does not contain the ethylenically unsaturated monomer (b2) which has crosslinkable functional groups other than a COOH group. ) In the absence of an organic solvent to obtain an acrylic copolymer (B), and the acrylic copolymer (B) is dissolved or dispersed in water in the presence of a basic compound (C). Obtaining an aqueous solution or dispersion of the acrylic copolymer (B),
In the presence of an aqueous solution or dispersion of the acrylic copolymer (B), the emulsified component (A) containing the ethylenically unsaturated monomer (A1) and not the polyester is dispersed in water, and the monomer is dispersed. Emulsion (1) was obtained
An ethylenically unsaturated monomer (e) containing an ethylenically unsaturated monomer (e1) having a COOH group and not containing an ethylenically unsaturated monomer (e2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. Acrylic copolymer (E) is obtained by copolymerization in the presence, and the acrylic copolymer (E) is dissolved or dispersed in water in the presence of the basic compound (F). Obtaining an aqueous solution or dispersion of (E),
The monomer emulsion (1) is dropped into an aqueous solution or dispersion of the acrylic copolymer (E), and the polymer emulsion (4) obtained by polymerizing the monomer (A1) and the phenol resin (6) are mixed. The present invention relates to a method for producing a water-based coating composition.
また、本発明は、ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を有機溶剤の不存在下に共重合し、アクリル系共重合体（Ｅ）を得、該アクリル系共重合体（Ｅ）を塩基性化合物（Ｆ）の存在下に水に溶解ないし分散せしめ、アクリル系共重合体（Ｅ）の水溶液ないし水性分散体を得、
エチレン性不飽和モノマー（Ａ１）を、前記アクリル系共重合体（Ｅ）の水溶液ないし水性分散体に滴下し、モノマー（Ａ１）を重合してなるポリマーエマルジョン（５）とフェノール樹脂（６）とを混合することを特徴とする水性塗料組成物の製造方法に関する。
Moreover, this invention contains the ethylenically unsaturated monomer (e1) which contains the ethylenically unsaturated monomer (e1) which has COOH group, and does not contain the ethylenically unsaturated monomer (e2) which has crosslinkable functional groups other than a COOH group. ) In the absence of an organic solvent to obtain an acrylic copolymer (E), and the acrylic copolymer (E) is dissolved or dispersed in water in the presence of a basic compound (F). Obtaining an aqueous solution or dispersion of the acrylic copolymer (E),
An ethylenically unsaturated monomer (A1) is dropped into an aqueous solution or dispersion of the acrylic copolymer (E), and the polymer emulsion (5) obtained by polymerizing the monomer (A1), the phenol resin (6), It is related with the manufacturing method of the water-based coating composition characterized by mixing.
本発明より、ＢＰＡ由来の構成成分を全く用いず、加工性、密着性、耐レトルト性に優れる塗膜を形成し得る缶内面被覆用水性塗料組成物を生産性よく、経済性よく提供することができる。 From the present invention, it is possible to provide an aqueous coating composition for coating the inner surface of a can with good productivity and economical efficiency that can form a coating film excellent in processability, adhesion, and retort resistance without using any BPA-derived components. Can do.
まず、被乳化成分（Ａ）について説明する。
第１、第２の発明における被乳化成分（Ａ）は、後述するアクリル系共重合体（Ｂ）を塩基性化合物（Ｃ）で中和させて水（Ｄ）に溶解ないし分散させたものによって、乳化される成分である。即ち、被乳化成分（Ａ）とアクリル系共重合体（Ｂ）と塩基性化合物（Ｃ）と水（Ｄ）とがモノマーエマルジョン（１）を形成し、このモノマーエマルジョン（１）を水（Ｇ）の存在下にラジカル重合することにより、本発明の水性塗料組成物の主成分たるポリマーエマルジョン（３）が得られる。あるいは、上記モノマーエマルジョン（１）を、後述するアクリル系共重合体（Ｅ）と塩基性化合物（Ｆ）と水と水（Ｇ）とを含有してなるポリマー水溶液ないしポリマーエマルジョンの存在下にラジカル重合することにより、本発明の水性塗料組成物の主成分たるポリマーエマルジョン（４）が得られる。
First, the emulsified component (A) will be described.
The emulsified component (A) in the first and second inventions is obtained by neutralizing an acrylic copolymer (B) described later with a basic compound (C) and dissolving or dispersing in water (D). The component to be emulsified. That is, the emulsified component (A), the acrylic copolymer (B), the basic compound (C), and water (D) form a monomer emulsion (1), and this monomer emulsion (1) is converted into water (G The polymer emulsion (3) as the main component of the aqueous coating composition of the present invention is obtained by radical polymerization in the presence of Alternatively, the monomer emulsion (1) may be radicalized in the presence of an aqueous polymer emulsion or polymer emulsion containing an acrylic copolymer (E), a basic compound (F), water and water (G) described later. By polymerizing, a polymer emulsion (4) as the main component of the aqueous coating composition of the present invention is obtained.
また、第３の発明に記載するようにモノマーエマルジョン（１）でなく、エチレン性不飽和モノマー（Ａ１）のみを、後述するアクリル系共重合体（Ｅ）と塩基性化合物（Ｆ）と水（Ｇ）とを含有してなるポリマー水溶液ないしポリマーエマルジョンの存在下にラジカル重合することによって、主成分たるポリマーエマルジョン（５）を得ることもできる。 Further, as described in the third invention, not the monomer emulsion (1) but only the ethylenically unsaturated monomer (A1), an acrylic copolymer (E), a basic compound (F) and water (described later) The polymer emulsion (5) as a main component can also be obtained by radical polymerization in the presence of an aqueous polymer solution or polymer emulsion containing G).
第１、第２の発明における被乳化成分（Ａ）は、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルを含有しない。
そこで、第１〜第３の発明におけるエチレン性不飽和モノマー（Ａ１）について説明する。
エチレン性不飽和モノマー（Ａ１）には、通常の乳化重合を行う際、乳化される成分であるエチレン性不飽和モノマーと同等のものを用いることができる。
エチレン性不飽和モノマー（Ａ１）の例としては、
単官能モノマーとしては、（メタ）アクリル酸、（無水）イタコン酸、（無水）マレイン酸等のカルボキシル基を有するエチレン性不飽和モノマー、
メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート、
ヒドロキシメチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（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、ヒドロキシペンチル（メタ）アクリレート、ヒドロキシヘキシル（メタ）アクリレート等の水酸基を有するエチレン性不飽和モノマー、
スチレン、メチルスチレン等の芳香族系モノマー、
Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎーヒドロキシエチル（メタ）アクリルアミド、Ｎ−ヒドロキシブチル（メタ）アクリルアミド等のＮ−ヒドロキシアルキル（メタ）アクリルアミド、
Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−エトキシメチル（メタ）アクリルアミド、Ｎ−（ｎ−，イソ）ブトキシメチル（メタ）アクリルアミド、Ｎ−メトキシエチル（メタ）アクリルアミド、Ｎ−エトキシエチル（メタ）アクリルアミド、Ｎ−（ｎ−、イソ）ブトキシエチル（メタ）アクリルアミド等のＮ−アルコキシアルキル（メタ）アクリルアミド、
（メタ）アクリルアミド、
グリシジルメタクリレート等が挙げられる。
また、２官能モノマーとしては、エチレングリコールジメタクリレート、ジビニルベンゼン等が挙げられる。
エチレン性不飽和モノマー（Ａ１）としては、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれる少なくとも１種のアミド系モノマー、2官能モノマー及びＣＯＯＨ基を有するエチレン性不飽和モノマーを含有することが好ましい。
The emulsified component (A) in the first and second inventions contains an ethylenically unsaturated monomer (A1) and does not contain polyester.
Therefore, the ethylenically unsaturated monomer (A1) in the first to third inventions will be described.
As the ethylenically unsaturated monomer (A1), the same ethylenically unsaturated monomer as a component to be emulsified can be used when performing normal emulsion polymerization.
Examples of the ethylenically unsaturated monomer (A1) include
Monofunctional monomers include ethylenically unsaturated monomers having a carboxyl group such as (meth) acrylic acid, (anhydrous) itaconic acid, (anhydrous) maleic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl ( Alkyl (meth) acrylates such as (meth) acrylate and ethylhexyl (meth) acrylate,
Hydroxyl groups such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxyhexyl (meth) acrylate An ethylenically unsaturated monomer having
Aromatic monomers such as styrene and methylstyrene,
N-hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide,
N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (n-, iso) butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-alkoxyalkyl (meth) acrylamides such as N- (n-, iso) butoxyethyl (meth) acrylamide,
(Meth) acrylamide,
Examples thereof include glycidyl methacrylate.
Examples of the bifunctional monomer include ethylene glycol dimethacrylate and divinylbenzene.
As the ethylenically unsaturated monomer (A1), at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide, a bifunctional monomer And an ethylenically unsaturated monomer having a COOH group.
エチレン性不飽和モノマー（Ａ１）が、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマーを少なくとも１種含有することによって、被乳化成分（Ａ）をラジカル重合してなるポリマーに架橋性官能基を導入することができる。架橋性官能基を導入することによって、塗膜の硬化性、またその他の物性がより向上するので好ましい。
また、エチレン性不飽和モノマー（Ａ１）が2官能モノマーを少なくとも１種含有することによって、被乳化成分（Ａ）をラジカル重合してなるポリマーに架橋構造を導入することができる。架橋構造を導入することによって、その後形成される塗膜の耐溶剤性、またその他の物性がより向上するので好ましい。2官能モノマーを使用する場合、その使用量は、エチレン性不飽和モノマー（Ａ１）１００重量％中に５〜３０重量％であることが好ましい。
When the ethylenically unsaturated monomer (A1) contains at least one amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide, A crosslinkable functional group can be introduced into a polymer obtained by radical polymerization of the emulsified component (A). It is preferable to introduce a crosslinkable functional group since the curability of the coating film and other physical properties are further improved.
Further, when the ethylenically unsaturated monomer (A1) contains at least one bifunctional monomer, a crosslinked structure can be introduced into a polymer obtained by radical polymerization of the emulsified component (A). By introducing a crosslinked structure, the solvent resistance and other physical properties of the coating film formed thereafter are further improved, which is preferable. When using a bifunctional monomer, it is preferable that the usage-amount is 5 to 30 weight% in 100 weight% of ethylenically unsaturated monomer (A1).
また、エチレン性不飽和モノマー（Ａ１）として、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマーを含有しないエチレン性不飽和モノマー（Ａ１）を用い、かつ後述するＣＯＯＨ基を有するアクリル系共重合体（Ｂ）、ＣＯＯＨ基を有するアクリル系共重合体（Ｅ）としても上記のようなアミド系モノマーに由来する架橋性官能基を含有しないものを用いればアマイドフリーのポリマーエマルジョンを得ることもできる。
その際、エチレン性不飽和モノマー（Ａ１）に2官能モノマーを含有させると、アマイドフリーでかつ塗膜の耐溶剤性、またその他の物性をより向上させ得るポリマーエマルジョンを得ることもできる。
Further, the ethylenically unsaturated monomer (A1) does not contain an amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. A crosslinkable functional group derived from the amide monomer as described above, using the monomer (A1) and the acrylic copolymer (B) having a COOH group, which will be described later, and the acrylic copolymer (E) having a COOH group. If one containing no group is used, an amide-free polymer emulsion can be obtained.
In that case, when a bifunctional monomer is contained in the ethylenically unsaturated monomer (A1), a polymer emulsion that is amide-free and can further improve the solvent resistance of the coating film and other physical properties can be obtained.
ＣＯＯＨ基を有するエチレン性不飽和モノマーは、エチレン性不飽和モノマー（Ａ１）１００重量％中に、多くとも２０重量％以下であることが好ましく、０〜５重量％であることがより好ましい。ＣＯＯＨ基を有するエチレン性不飽和モノマーは、親水性が高いために乳化されにくく、これが多すぎる場合には、重合時のブツの原因となり易いからである。 The ethylenically unsaturated monomer having a COOH group is preferably at most 20% by weight and more preferably 0 to 5% by weight in 100% by weight of the ethylenically unsaturated monomer (A1). This is because an ethylenically unsaturated monomer having a COOH group is difficult to be emulsified due to its high hydrophilicity, and if it is too much, it is likely to cause blisters during polymerization.
エチレン性不飽和モノマー（Ａ１）は、該モノマー（Ａ１）から形成され得る重合体のガラス転移温度が３０〜１００℃となるようなものを用いることが好ましく、重合体のガラス転移温度が４０〜８０℃となるようなものを用いることがより好ましい。ガラス転移温度が３０℃未満の重合体を形成し得るようなエチレン性不飽和モノマー（Ａ１）を用いて形成されるポリマーエマルジョンを飲料缶等の内面被覆に使用すると、内容物の香りや味を吸着してしまい易い。他方、ガラス転移温度が１００℃を超える重合体を形成し得るようなエチレン性不飽和モノマー（Ａ１）を用いて形成される複合樹脂エマルジョンの場合は、塗膜の加工性が劣る傾向にある。
尚、エチレン性不飽和モノマー（Ａ１）から形成され得る重合体のガラス転移温度は、各モノマーからそれぞれ形成され得る各ホモポリマーのガラス転移温度と、重合に供されるエチレン性不飽和モノマー（Ａ１）の組成比とから常法に従って計算によって求められる。
As the ethylenically unsaturated monomer (A1), a polymer that can be formed from the monomer (A1) preferably has a glass transition temperature of 30 to 100 ° C., and the glass transition temperature of the polymer is 40 to 40 ° C. It is more preferable to use one that is 80 ° C. When a polymer emulsion formed using an ethylenically unsaturated monomer (A1) capable of forming a polymer having a glass transition temperature of less than 30 ° C. is used for inner coating of a beverage can or the like, the scent and taste of the contents are reduced. Easy to adsorb. On the other hand, in the case of a composite resin emulsion formed using an ethylenically unsaturated monomer (A1) that can form a polymer having a glass transition temperature exceeding 100 ° C., the processability of the coating film tends to be inferior.
The glass transition temperature of the polymer that can be formed from the ethylenically unsaturated monomer (A1) is the same as the glass transition temperature of each homopolymer that can be formed from each monomer, and the ethylenically unsaturated monomer (A1) that is subjected to polymerization. ) By the calculation according to the conventional method.
次に、アクリル系共重合体（Ｂ）について説明する。
アクリル系共重合体（Ｂ）は、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステル含有しない被乳化成分（Ａ）を乳化する、高分子乳化剤としての役割を担う。
一般に、高分子乳化剤は、疎水性成分を水媒体中で乳化する役割をもち、そのために、親水性部分と疎水性部分とを有することが必須である。
アクリル系共重合体（Ｂ）は、親水性部分としてＣＯＯＨ基を有している。ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）は、ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｂ１）を必須成分として含有するエチレン性不飽和モノマー（ｂ）を共重合してなるものである。ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｂ１）は、共重合に供されるモノマー１００重量％中少なくとも１０重量％以上含まれることが好ましく、２０〜５０重量％含まれることがより好ましい。
また、ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）は、疎水性部分を有することが好ましい。そこで、芳香環を有するエチレン性不飽和モノマーもしくは炭素原子数６以上のアルキル鎖を有するエチレン性不飽和モノマーを共重合成分に有することが好ましい。
Next, the acrylic copolymer (B) will be described.
The acrylic copolymer (B) serves as a polymer emulsifier that contains the ethylenically unsaturated monomer (A1) and emulsifies the emulsified component (A) not containing polyester.
In general, a polymer emulsifier has a role of emulsifying a hydrophobic component in an aqueous medium, and therefore it is essential to have a hydrophilic portion and a hydrophobic portion.
The acrylic copolymer (B) has a COOH group as a hydrophilic portion. The acrylic copolymer (B) having a COOH group is obtained by copolymerizing an ethylenically unsaturated monomer (b) containing an ethylenically unsaturated monomer (b1) having a COOH group as an essential component. The ethylenically unsaturated monomer (b1) having a COOH group is preferably contained in an amount of at least 10% by weight, more preferably 20 to 50% by weight, based on 100% by weight of the monomer used for copolymerization.
Moreover, it is preferable that the acrylic copolymer (B) having a COOH group has a hydrophobic portion. Therefore, it is preferable to have an ethylenically unsaturated monomer having an aromatic ring or an ethylenically unsaturated monomer having an alkyl chain having 6 or more carbon atoms in the copolymer component.
ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）の形成に供されるエチレン性不飽和モノマー（ｂ）は、ＣＯＯＨ基以外の架橋反応性官能基を有するエチレン性不飽和モノマー（ｂ２）は含有しない。ＣＯＯＨ基以外の架橋反応性官能基を有するエチレン性不飽和モノマー（ｂ２）を含有しないことによって、ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）を有機溶剤の不存在下に重合、即ち塊状重合によって得ることができる。
塊状重合は一般に高温で重合するため、その重合温度でＣＯＯＨ基以外に架橋反応し得る官能基をもつエチレン性不飽和モノマー（ｂ２）を用いれば、重合時ゲル化が起こり、合成できない。
The ethylenically unsaturated monomer (b) used for the formation of the acrylic copolymer (B) having a COOH group does not contain the ethylenically unsaturated monomer (b2) having a crosslinking reactive functional group other than the COOH group. . By not containing an ethylenically unsaturated monomer (b2) having a crosslinkable functional group other than a COOH group, the acrylic copolymer (B) having a COOH group is polymerized in the absence of an organic solvent, that is, bulk polymerization. Can be obtained by:
Bulk polymerization is generally carried out at a high temperature. Therefore, if an ethylenically unsaturated monomer (b2) having a functional group capable of undergoing a crosslinking reaction in addition to the COOH group is used at the polymerization temperature, gelation occurs at the time of polymerization and synthesis cannot be performed.
ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）の共重合成分であるＣＯＯＨ基を有するエチレン性不飽和モノマー（ｂ１）としては、（メタ）アクリル酸、（無水）イタコン酸、（無水）マレイン酸が挙げられる。
ＣＯＯＨ基以外の架橋反応性官能基を有するエチレン性不飽和モノマー（ｂ２）としては、上記エチレン性不飽和モノマー（Ａ１）の場合と同様ものが例示できる。
例えば、ＣＯＯＨ基以外の架橋反応性官能基を有するエチレン性不飽和モノマー（ｂ２）としては、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマー、グリシジルメタクリレート、カレンズＭＯＩ（昭和電工製）が例示できる。
Examples of the ethylenically unsaturated monomer (b1) having a COOH group that is a copolymer component of the acrylic copolymer (B) having a COOH group include (meth) acrylic acid, (anhydrous) itaconic acid, and (anhydrous) maleic acid. Is mentioned.
Examples of the ethylenically unsaturated monomer (b2) having a crosslinking reactive functional group other than the COOH group include the same as those in the case of the ethylenically unsaturated monomer (A1).
For example, the ethylenically unsaturated monomer (b2) having a crosslinking reactive functional group other than the COOH group is selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. Examples include selected amide monomers, glycidyl methacrylate, and Karenz MOI (manufactured by Showa Denko).
ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）は、数平均分子量２０００〜６００００であることが好ましく、数平均分子量５０００〜２００００であることがより好ましい。数平均分子量が２０００よりも小さいと、乳化力が低下する傾向にあり、重合時のブツや沈降物の原因となり易い。数平均分子量が６００００よりも大きい場合も同様である。
ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）の酸価は、２０〜４００（mgＫＯＨ／g）であることが好ましく、１００〜３００（mgＫＯＨ／g）であることがより好ましい。酸価が２０（mgＫＯＨ／g）よりも小さいと、乳化力が低下する傾向にあり、重合時のブツや沈降物の原因となり易い。酸価が４００（mgＫＯＨ／g）よりも大きい場合も同様である。
ＣＯＯＨ基を有するアクリル系共重合体（Ｂ）のガラス転移温度は、３０〜１００℃であることが好ましく、４０〜８０℃であることがより好ましい。ガラス転移温度が３０℃未満だと、缶の中に収容される飲料物の香りや味が変わり易い。一方、ガラス転移温度が、１００℃を超えると塗膜の加工性が低下する傾向にある。
The acrylic copolymer (B) having a COOH group preferably has a number average molecular weight of 2000 to 60000, and more preferably a number average molecular weight of 5000 to 20000. When the number average molecular weight is less than 2,000, the emulsifying power tends to decrease, which tends to cause blisters and sediment during polymerization. The same applies when the number average molecular weight is larger than 60000.
The acid value of the acrylic copolymer (B) having a COOH group is preferably 20 to 400 (mgKOH / g), and more preferably 100 to 300 (mgKOH / g). When the acid value is less than 20 (mgKOH / g), the emulsifying power tends to be lowered, and it tends to cause lumps and sediment during polymerization. The same applies when the acid value is greater than 400 (mg KOH / g).
The glass transition temperature of the acrylic copolymer (B) having a COOH group is preferably 30 to 100 ° C, and more preferably 40 to 80 ° C. If the glass transition temperature is less than 30 ° C., the scent and taste of the beverage contained in the can is easily changed. On the other hand, when the glass transition temperature exceeds 100 ° C., the processability of the coating film tends to decrease.
次にモノマーエマルジョン（１）について説明する。
モノマーエマルジョン（１）は、上記したようにエチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルを含有しない被乳化成分（Ａ）、アクリル系共重合体（Ｂ）、塩基性化合物（Ｃ）及び水（Ｄ）を含有する。（Ａ）〜（Ｄ）を一気に混合することもできるが、アクリル系共重合体（Ｂ）をあらかじめ塩基性化合物（Ｃ）で中和させて、水（Ｄ）に溶解ないし分散させておき、この中和水溶液ないし分散体で被乳化成分（Ａ）を乳化することが好ましい。（Ａ）〜（Ｄ）は、通常の方法で攪拌するにより、乳化することもできるし、高速で攪拌したり、シェアをかけたりすることにより、乳化しても良い。
また、 塩基性化合物（Ｃ）の量は、アクリル系共重合体（Ｂ）中のＣＯＯＨ基の全部ではなく一部を中和し得ることが好ましい。具体的には、塩基性化合物（Ｃ）は、アクリル系共重合体（Ｂ）中のＣＯＯＨ基１００モル％に対して、３０〜７０モル％であることが好ましく、４０〜６０モル％であることがより好ましい。
Next, the monomer emulsion (1) will be described.
As described above, the monomer emulsion (1) contains the ethylenically unsaturated monomer (A1) and does not contain polyester, the emulsified component (A), the acrylic copolymer (B), the basic compound (C) and Contains water (D). (A) to (D) can be mixed at once, but the acrylic copolymer (B) is previously neutralized with the basic compound (C) and dissolved or dispersed in water (D). The emulsified component (A) is preferably emulsified with this neutralized aqueous solution or dispersion. (A)-(D) can also be emulsified by stirring by a normal method, and may be emulsified by stirring at high speed or applying a shear.
Moreover, it is preferable that the quantity of a basic compound (C) can neutralize one part instead of all the COOH groups in an acryl-type copolymer (B). Specifically, the basic compound (C) is preferably 30 to 70 mol%, and 40 to 60 mol% with respect to 100 mol% of the COOH groups in the acrylic copolymer (B). It is more preferable.
本発明で用いられる塩基性化合物（Ｃ）としては、ジメチルアミノエタノールのようなアミン化合物、アンモニア、アルカリ金属の水酸化物等が挙げられる。 Examples of the basic compound (C) used in the present invention include amine compounds such as dimethylaminoethanol, ammonia, alkali metal hydroxides, and the like.
次に、アクリル系共重合体（Ｅ）について説明する。
アクリル系共重合体（Ｅ）は、アクリル系共重合体（Ｂ）と同様に被乳化成分（Ａ）に対し、乳化剤成分として機能するものである。アクリル系共重合体（Ｂ）は、モノマーエマルジョン（１）の形成時、及び重合中並びに重合後のポリマーエマルジョンにとって、乳化剤成分として機能するものであり、本発明において必須の成分である。一方、アクリル系共重合体（Ｅ）は、主として重合中並びに重合後のポリマーエマルジョンにとって、乳化剤成分として機能するものであり、このアクリル系共重合体（Ｅ）を補助的に併用することによって、ポリマーエマルジョンの乳化、分散状態をより安定に保つことができる。アクリル系共重合体（Ｅ）を用いる場合、アクリル系共重合体（Ｂ）と同様にＣＯＯＨ基の一部を塩基性化合物で中和したものを用いることが好ましい。
Next, the acrylic copolymer (E) will be described.
The acrylic copolymer (E) functions as an emulsifier component with respect to the emulsified component (A), similarly to the acrylic copolymer (B). The acrylic copolymer (B) functions as an emulsifier component during the formation of the monomer emulsion (1), and during and after the polymerization, and is an essential component in the present invention. On the other hand, the acrylic copolymer (E) functions mainly as an emulsifier component for the polymer emulsion during polymerization and after polymerization. By using this acrylic copolymer (E) in an auxiliary manner, The emulsification and dispersion state of the polymer emulsion can be kept more stable. When the acrylic copolymer (E) is used, it is preferable to use a material obtained by neutralizing a part of the COOH group with a basic compound in the same manner as the acrylic copolymer (B).
アクリル系共重合体（Ｅ）を塊状重合で得るためには、アクリル系共重合体（Ｂ）の場合と同様にＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を共重合に供する。アクリル系共重合体（Ｅ）の好適な数平均分子量、酸価、ガラス転移温度は、アクリル系共重合体（Ｂ）の場合と同様である。 In order to obtain the acrylic copolymer (E) by bulk polymerization, as in the case of the acrylic copolymer (B), it contains an ethylenically unsaturated monomer (e1) having a COOH group, and crosslinks other than the COOH group. The ethylenically unsaturated monomer (e) not containing the ethylenically unsaturated monomer (e2) having a functional functional group is subjected to copolymerization. The suitable number average molecular weight, acid value, and glass transition temperature of the acrylic copolymer (E) are the same as those of the acrylic copolymer (B).
第１の発明の場合、被乳化成分（Ａ）１００重量部に対して、アクリル系共重合体（Ｂ）は、５〜３００重量部であることが好ましく、１０〜２００重量部であることがより好ましく、２０〜１００重量部であることがさらに好ましい。
また、被乳化成分（Ａ）１００重量部に対して、水（Ｄ）は、５０〜５００重量部であることが好ましく、１００〜３００重量部であることがより好ましい。
被乳化成分（Ａ）１００重量部に比して、乳化剤成分たるアクリル系共重合体（Ｂ）とアクリル系共重合体（Ｅ）との合計が５重量部より少ない場合、被乳化成分（Ａ）や重合後のポリマーが乳化されにくくなり易い。また、被乳化成分（Ａ）１００重量部に対して、乳化剤成分たるアクリル系共重合体（Ｂ）とアクリル系共重合体（Ｅ）との合計が３００重量部より多い場合、焼き付け硬化後の塗膜の加工性の向上があまり期待できない。被乳化成分（Ａ）は、ラジカル重合によって、非常に高分子量になる成分であり、これが硬化塗膜の加工性の向上に寄与することとなる。従って、乳化剤成分たるＣＯＯＨ基含有成分（Ｂ）とＣＯＯＨ基含有成分（Ｅ）との合計が３００重量部よりも多くなると、相対的に被乳化成分（Ａ）が少なくなり、その結果硬化塗膜の加工性の向上があまり期待できなくなる。
In the case of the first invention, the acrylic copolymer (B) is preferably 5 to 300 parts by weight and more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the emulsified component (A). More preferred is 20 to 100 parts by weight.
Moreover, it is preferable that it is 50-500 weight part with respect to 100 weight part of to-be-emulsified components (A), and it is more preferable that it is 100-300 weight part.
When the total of the acrylic copolymer (B) and acrylic copolymer (E) as emulsifier components is less than 5 parts by weight compared to 100 parts by weight of the emulsified component (A), the emulsified component (A ) And the polymer after polymerization are less likely to be emulsified. Moreover, when the sum total of the acrylic copolymer (B) and acrylic copolymer (E) which are emulsifier components is more than 300 parts by weight with respect to 100 parts by weight of the emulsified component (A), We cannot expect much improvement in the processability of the coating film. The component to be emulsified (A) is a component having a very high molecular weight by radical polymerization, and this contributes to the improvement of the workability of the cured coating film. Therefore, when the total of the COOH group-containing component (B) and the COOH group-containing component (E) as the emulsifier component is more than 300 parts by weight, the emulsified component (A) is relatively reduced, and as a result, the cured coating film The improvement of workability cannot be expected.
アクリル系共重合体（Ｂ）とアクリル系共重合体（Ｅ）とを用いる第２の発明の場合は、被乳化成分（Ａ）１００重量部に対して、アクリル系共重合体（Ｂ）は好ましい範囲が２つあり、２０〜１００重量部と、１〜５重量部である。
被乳化成分（Ａ）１００重量部に対して、アクリル系共重合体（Ｂ）が２０〜１００重量部のときは、被乳化成分（Ａ）１００重量部に対して、水（Ｄ）は、５０〜５００重量部であることが好ましく、また、被乳化成分（Ａ）１００重量部に対して、アクリル系共重合体（Ｂ）とアクリル系共重合体（Ｅ）との合計は、２０〜３００重量部であることが好ましく、３０〜２００重量部であることがさらに好ましい。
また、被乳化成分（Ａ）１００重量部に対して、アクリル系共重合体（Ｂ）が１〜５重量部のときは、被乳化成分（Ａ）１００重量部に対して、水（Ｄ）は、２〜２０重量部であることが好ましく、また、被乳化成分（Ａ）１００重量部に対して、アクリル系共重合体（Ｂ）とアクリル系共重合体（Ｅ）との合計は、５〜３００重量部であることが好ましく、１０〜２００重量部であることがより好ましく、２０〜１００重量部であることがさらに好ましい。
被乳化成分（Ａ）１００重量部に比して、乳化剤成分たるアクリル系共重合体（Ｂ）とアクリル系共重合体（Ｅ）との合計が５重量部より少ない場合、被乳化成分（Ａ）や重合後のポリマーが乳化されにくくなり易い。また、被乳化成分（Ａ）１００重量部に対して、乳化剤成分たるアクリル系共重合体（Ｂ）とアクリル系共重合体（Ｅ）との合計が３００重量部より多い場合、焼き付け硬化後の塗膜の加工性の向上があまり期待できない。被乳化成分（Ａ）は、ラジカル重合によって、非常に高分子量になる成分であり、これが硬化塗膜の加工性の向上に寄与することとなる。従って、乳化剤成分たるＣＯＯＨ基含有成分（Ｂ）とＣＯＯＨ基含有成分（Ｅ）との合計が３００重量部よりも多くなると、相対的に被乳化成分（Ａ）が少なくなり、その結果硬化塗膜の加工性の向上があまり期待できなくなる。
In the case of the second invention using the acrylic copolymer (B) and the acrylic copolymer (E), the acrylic copolymer (B) is used with respect to 100 parts by weight of the emulsified component (A). There are two preferred ranges, 20-100 parts by weight and 1-5 parts by weight.
When the acrylic copolymer (B) is 20 to 100 parts by weight with respect to 100 parts by weight of the emulsified component (A), water (D) is 100 parts by weight of the emulsified component (A). The total amount of the acrylic copolymer (B) and the acrylic copolymer (E) is preferably 20 to 100 parts by weight based on 100 parts by weight of the emulsified component (A). The amount is preferably 300 parts by weight, and more preferably 30 to 200 parts by weight.
Further, when the acrylic copolymer (B) is 1 to 5 parts by weight with respect to 100 parts by weight of the emulsified component (A), water (D) with respect to 100 parts by weight of the emulsified component (A). Is preferably 2 to 20 parts by weight, and the total of the acrylic copolymer (B) and the acrylic copolymer (E) with respect to 100 parts by weight of the emulsified component (A) is: The amount is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, and still more preferably 20 to 100 parts by weight.
When the total of the acrylic copolymer (B) and acrylic copolymer (E) as emulsifier components is less than 5 parts by weight compared to 100 parts by weight of the emulsified component (A), the emulsified component (A ) And the polymer after polymerization are less likely to be emulsified. Moreover, when the sum total of the acrylic copolymer (B) and acrylic copolymer (E) which are emulsifier components is more than 300 parts by weight with respect to 100 parts by weight of the emulsified component (A), We cannot expect much improvement in the processability of the coating film. The component to be emulsified (A) is a component having a very high molecular weight by radical polymerization, and this contributes to the improvement of the workability of the cured coating film. Therefore, when the total of the COOH group-containing component (B) and the COOH group-containing component (E) as the emulsifier component is more than 300 parts by weight, the emulsified component (A) is relatively reduced, and as a result, the cured coating film The improvement of workability cannot be expected.
アクリル系共重合体（Ｂ）は用いずにアクリル系共重合体（Ｅ）のみを用いる第３の発明の場合、被乳化成分（Ａ）１００重量部に対してアクリル系共重合体（Ｅ）は、５〜３００重量部であることが好ましく、１０〜２００重量部であることがより好ましく、２０〜１００重量部であることがさらに好ましい。
また、被乳化成分（Ａ）１００重量部に対して、水（Ｄ）は、５０〜５００重量部であることが好ましく、１００〜３００重量部であることがより好ましい。
被乳化成分（Ａ）１００重量部に比して、乳化剤成分たるアクリル系共重合体（Ｅ）が５重量部より少ない場合、被乳化成分（Ａ）や重合後のポリマーが乳化されにくくなり易い。また、被乳化成分（Ａ）１００重量部に対して、乳化剤成分たるアクリル系共重合体（Ｅ）が３００重量部より多い場合、焼き付け硬化後の塗膜の加工性の向上があまり期待できない。被乳化成分（Ａ）は、ラジカル重合によって、非常に高分子量になる成分であり、これが硬化塗膜の加工性の向上に寄与することとなる。従って、乳化剤成分たるＣＯＯＨ基含有成分（Ｅ）が３００重量部よりも多くなると、相対的に被乳化成分（Ａ）が少なくなり、その結果硬化塗膜の加工性の向上があまり期待できなくなる。
In the case of the third invention in which only the acrylic copolymer (E) is used without using the acrylic copolymer (B), the acrylic copolymer (E) with respect to 100 parts by weight of the emulsified component (A). Is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, and still more preferably 20 to 100 parts by weight.
Moreover, it is preferable that it is 50-500 weight part with respect to 100 weight part of to-be-emulsified components (A), and it is more preferable that it is 100-300 weight part.
When the amount of the acrylic copolymer (E) as an emulsifier component is less than 5 parts by weight compared to 100 parts by weight of the component to be emulsified (A), the emulsified component (A) and the polymer after polymerization tend to be difficult to be emulsified. . Moreover, when there are more than 300 weight part of acrylic copolymers (E) which are emulsifier components with respect to 100 weight part of emulsified components (A), the improvement of the workability of the coating film after baking hardening cannot be expected so much. The component to be emulsified (A) is a component having a very high molecular weight by radical polymerization, and this contributes to the improvement of the workability of the cured coating film. Therefore, when the amount of the COOH group-containing component (E) as an emulsifier component is more than 300 parts by weight, the emulsified component (A) is relatively decreased, and as a result, the improvement in workability of the cured coating film cannot be expected.
次にポリマーエマルジョン（３）、（４）について説明する。
ポリマーエマルジョン（３）は、モノマーエマルジョン（１）を、水（Ｇ）の存在下に、ポリマーエマルジョン（４）は、アクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）の存在下に、それぞれラジカル重合してなるものである。
例えば、水（Ｇ）、またはアクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）を入れた反応容器に、モノマーエマルジョン（１）を添加することによって得ることができる。重合開始剤は、反応容器内に入れておいてもよいし、モノマーエマルジョン（１）内に入れておいてもよいし、あるいはモノマーエマルジョン（１）とは別に反応容器内に添加してもよい。
用いられる重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等が挙げられる。
Next, the polymer emulsions (3) and (4) will be described.
The polymer emulsion (3) is a monomer emulsion (1) in the presence of water (G), and the polymer emulsion (4) is an acrylic copolymer (E), a basic compound (F) and water (G). In the presence of each, radical polymerization is performed.
For example, it can be obtained by adding the monomer emulsion (1) to a reaction vessel containing water (G) or an acrylic copolymer (E), a basic compound (F) and water (G). The polymerization initiator may be put in the reaction vessel, may be put in the monomer emulsion (1), or may be added to the reaction vessel separately from the monomer emulsion (1). .
Examples of the polymerization initiator used include potassium persulfate and ammonium persulfate.
次にポリマーエマルジョン（５）について説明する。
ポリマーエマルジョン（５）は、モノマー（Ａ１）を、アクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）の存在下にラジカル重合してなるものである。
例えば、アクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）を入れた反応容器に、モノマー（Ａ１）を添加することによって得ることができる。重合開始剤は、反応容器内に入れておいてもよいし、モノマー（Ａ１）内に入れておいてもよいし、あるいはモノマー（Ａ１）とは別に反応容器内に添加してもよい。
用いられる重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等が挙げられる。
Next, the polymer emulsion (5) will be described.
The polymer emulsion (5) is obtained by radical polymerization of the monomer (A1) in the presence of an acrylic copolymer (E), a basic compound (F) and water (G).
For example, it can be obtained by adding the monomer (A1) to a reaction vessel containing an acrylic copolymer (E), a basic compound (F) and water (G). The polymerization initiator may be put in the reaction vessel, may be put in the monomer (A1), or may be added to the reaction vessel separately from the monomer (A1).
Examples of the polymerization initiator used include potassium persulfate and ammonium persulfate.
ポリマーエマルジョン（３）〜（５）は、被乳化成分（Ａ）から構成される樹脂成分とアクリル系共重合体（Ｂ）、（Ｅ）とが不均一な構造の複合樹脂組成物を形成しつつ、全体としては安定した分散状態を呈するものと考えられる。即ち、被乳化成分（Ａ）から構成される樹脂成分の多い部分と、アクリル系共重合体（Ｂ）、（Ｅ）の多い部分とが局所的に存在するものと考察される。
ポリマーエマルジョン（３）〜（５）の分散粒子の不均一な構造故に、焼付け後の硬化塗膜も完全に均一な構造にはなりにくいと考えられ、被乳化成分（Ａ）に由来する樹脂成分の多い部分と、アクリル系共重合体（Ｂ）、（Ｅ）の多い部分とが局所的に存在すると考えられる。
The polymer emulsions (3) to (5) form a composite resin composition in which the resin component composed of the emulsified component (A) and the acrylic copolymers (B) and (E) are non-uniform. However, as a whole, it is considered to exhibit a stable dispersion state. That is, it is considered that a portion having a large amount of the resin component composed of the emulsified component (A) and a portion having a large amount of the acrylic copolymers (B) and (E) exist locally.
Due to the non-uniform structure of the dispersed particles of the polymer emulsions (3) to (5), it is considered that the cured coating film after baking is unlikely to have a completely uniform structure, and the resin component derived from the emulsified component (A) It is considered that a portion having a large amount and a portion having a large amount of the acrylic copolymer (B) or (E) exist locally.
被乳化成分（Ａ）のうち、エチレン性不飽和モノマー（Ａ１）が、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマーを含有する場合には、被乳化成分（Ａ）に由来する樹脂成分の多い部分を硬化、架橋させることができる。 Of the emulsified component (A), the ethylenically unsaturated monomer (A1) is an amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. When it contains, the part with many resin components originating in an emulsified component (A) can be hardened and bridge | crosslinked.
次に、本発明の水性塗料組成物について説明する。
本発明の水性塗料組成物は、上記ポリマーエマルジョン（３）〜（５）の少なくとも１種とフェノール樹脂（６）とを含有するものである。
フェノール樹脂（６）は、自己架橋反応する他、ポリマーエマルジョン（３）〜（５）を構成する高分子乳化剤であるアクリル系共重合体（Ｂ）や（Ｅ）中のＣＯＯＨ基、そして被乳化成分（Ａ）がＣＯＯＨ基を有する場合にはこのＣＯＯＨ基と反応、硬化し、硬化塗膜を形成する。
また、上記したように被乳化成分（Ａ）のうち、エチレン性不飽和モノマー（Ａ１）が、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれる少なくとも１種のアミド系モノマーを含有する場合には、これらアミド系モノマーに由来する官能基が自己架橋したり、フェノール樹脂（６）とも架橋反応したりする。なお、これらアミド系モノマーを使用せず、アクリル系共重合体（Ｂ）や（Ｅ）がアミド系モノマーを共重合組成に含まなければ、アマイドフリーの水性塗料組成物を得ることもできる。
Next, the aqueous coating composition of the present invention will be described.
The aqueous coating composition of the present invention contains at least one of the polymer emulsions (3) to (5) and a phenol resin (6).
In addition to the self-crosslinking reaction, the phenolic resin (6) is an acrylic copolymer (B), which is a polymer emulsifier constituting the polymer emulsions (3) to (5), COOH groups in (E), and emulsified When component (A) has a COOH group, it reacts with this COOH group and cures to form a cured coating film.
Moreover, as mentioned above, among the emulsified components (A), the ethylenically unsaturated monomer (A1) is composed of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. In the case of containing at least one amide monomer selected from the above, the functional group derived from these amide monomers self-crosslinks or crosslinks with the phenol resin (6). If these amide monomers are not used and the acrylic copolymer (B) or (E) does not contain an amide monomer in the copolymer composition, an amide-free aqueous coating composition can be obtained.
本発明において用いられるフェノール樹脂としては、メタクレゾール骨格のもの、パラクレゾール骨格のもの等が挙げられ、メタクレゾール骨格のものが好ましい。
フェノール樹脂を用いる場合には、複合樹脂１００重量部に対して、フェノール樹脂は１〜２０重量部であることが好ましく、２〜１０重量部であることがより好ましい。
Examples of the phenol resin used in the present invention include those having a metacresol skeleton and those having a paracresol skeleton, and those having a metacresol skeleton are preferable.
When using a phenol resin, it is preferable that it is 1-20 weight part with respect to 100 weight part of composite resins, and it is more preferable that it is 2-10 weight part.
以下に合成例、比較合成例、実施例、比較例により本発明を説明する。例中、部とは重量部、％とは重量％をそれぞれ表す。 The present invention will be described below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.
［合成例１］アクリル系共重合体（Ｂ−１）の合成
耐圧反応容器にモノマー４００ｇを入れて、密閉した状態で、２５０℃で加熱攪拌しながら、４０分間重合し、数平均分子量１００００、ガラス転移音素約３８℃、酸価２５５（mgＫＯＨ／g）の固形のアクリル系共重合体（Ｂ−１）を得た。なお、モノマー組成は、スチレン４０％、エチルアクリレート２２％、メタクリル酸３８％とした。
その後、ジメチルアミノエタノールを１５７．３ｇ加え、その後水を加えて、アクリル系共重合体（Ｂ−１）の固形分２５％の水溶液を得た。
[Synthesis Example 1] Synthesis of Acrylic Copolymer (B-1) In a pressure-resistant reaction vessel, 400 g of a monomer was put, and in a sealed state, polymerized for 40 minutes while heating and stirring at 250 ° C., and the number average molecular weight was 10,000. A solid acrylic copolymer (B-1) having a glass transition phoneme of about 38 ° C. and an acid value of 255 (mg KOH / g) was obtained. The monomer composition was 40% styrene, 22% ethyl acrylate, and 38% methacrylic acid.
Thereafter, 157.3 g of dimethylaminoethanol was added, and then water was added to obtain an aqueous solution of an acrylic copolymer (B-1) having a solid content of 25%.
［合成例２］アクリル系共重合体（Ｂ−２）の合成
モノマー組成を、スチレン２７％、エチルアクリレート１５％、２−ヒドロキシエチルアクリレート２０％、メタクリル酸３８％とした以外は、上記合成例１と同様にして、数平均分子量１００００、ガラス転移温度約５６℃、酸価２５５（mgＫＯＨ／g）の固形のアクリル系共重合体（Ｂ−２）を得た。次いで、同様にして、ジメチルアミノエタノール及び水を加え、アクリル系共重合体（Ｂ−２）の固形分２５％の水溶液を得た。
[Synthesis Example 2] Synthesis of acrylic copolymer (B-2) The above synthesis example except that the monomer composition was 27% styrene, 15% ethyl acrylate, 20% 2-hydroxyethyl acrylate, and 38% methacrylic acid. In the same manner as in Example 1, a solid acrylic copolymer (B-2) having a number average molecular weight of 10,000, a glass transition temperature of about 56 ° C., and an acid value of 255 (mgKOH / g) was obtained. Subsequently, dimethylaminoethanol and water were added in the same manner to obtain an aqueous solution of an acrylic copolymer (B-2) having a solid content of 25%.
［合成例３］アクリル系共重合体（Ｂ−３）の合成
耐圧反応容器に圧力釜に１５０℃で加熱攪拌しながら、窒素雰囲気下に、モノマー４００ｇを入れて合成を行った。モノマー組成は、スチレン２７％、エチルアクリレート１５％、Ｎ−ｎ−ブトキシメチルアクリルアミド２０％、メタクリル酸３８％とした。しかし、反応途中でゲル化した。
[Synthesis Example 3] Synthesis of Acrylic Copolymer (B-3) Synthesis was performed by adding 400 g of the monomer in a nitrogen atmosphere while stirring in a pressure vessel at 150 ° C. in a pressure vessel. The monomer composition was 27% styrene, 15% ethyl acrylate, 20% Nn-butoxymethylacrylamide, and 38% methacrylic acid. However, it gelled during the reaction.
［実施例１］ポリマーエマルジョン（ＰＥ−１）の合成
スチレン７６．３ｇ、エチルアクリレート３０ｇ、Ｎ−ｎ−ブトキシメチルアクリルアミド１８．８ｇ、［合成例１］で得た固形分２５％のアクリル系共重合体（Ｂ−１）水溶液を１０ｇを加えて、通常の方法で攪拌して、モノマーエマルジョン（Ｍ−１）を得た。尚、上記モノマーから求められる共重合体のガラス転移温度は、５５℃である。
反応容器に、固形分２５％アクリル系共重合体（Ｂ−１）水溶液２４０ｇと水２５０ｇを仕込み、８０℃で加熱攪拌しながら、窒素雰囲気下に、モノマーエマルジョン（Ｍ−１）と過硫酸カリウム０．５ｇの混合物を２時間かけて滴下した。滴下終了後１時間ごとに２回、さらに過硫酸カリウムを０．０５ｇずつ加え、固形分３０％のポリマーエマルジョン（ＰＥ−１）を得た。
このポリマーエマルジョン（ＰＥ−１）２０ｇに、フェノール樹脂として昭和高分子製ショウノールＣＫＳ−３８９４（固形分５０％溶液）１．２ｇ、ブチルジグリコール２ｇ、ブタノール１ｇと水８．８ｇの混合物を加えて水性塗料組成物を得た。
[Example 1] Synthesis of polymer emulsion (PE-1) 76.3 g of styrene, 30 g of ethyl acrylate, 18.8 g of Nn-butoxymethylacrylamide, and an acrylic copolymer having a solid content of 25% obtained in [Synthesis Example 1] 10 g of the polymer (B-1) aqueous solution was added and stirred by a usual method to obtain a monomer emulsion (M-1). In addition, the glass transition temperature of the copolymer calculated | required from the said monomer is 55 degreeC.
A reactor vessel was charged with 240 g of an aqueous 25% solid copolymer (B-1) solution and 250 g of water, and heated under stirring at 80 ° C. under a nitrogen atmosphere, and the monomer emulsion (M-1) and potassium persulfate. 0.5 g of the mixture was added dropwise over 2 hours. 0.05 g of potassium persulfate was further added twice every hour after the completion of the dropwise addition to obtain a polymer emulsion (PE-1) having a solid content of 30%.
To 20 g of this polymer emulsion (PE-1) was added 1.2 g of Shounol CKS-3894 (50% solid content solution), 2 g of butyl diglycol, 1 g of butanol and 8.8 g of water as a phenol resin. Thus, an aqueous coating composition was obtained.
［実施例２］ポリマーエマルジョン（ＰＥ−２）の合成
スチレン８５ｇ、エチルアクリレート４０ｇ、［合成例１］で得た固形分２５％のアクリル系共重合体（Ｂ−１）水溶液を１０ｇを加えて、通常の方法で攪拌して、モノマーエマルジョン（Ｍ−１）を得た。尚、上記モノマーから求められる共重合体のガラス転移温度は、５０℃である。
反応容器に、固形分２５％アクリル系共重合体（Ｂ−１）水溶液２４０ｇと水２５０ｇを仕込み、８０℃で加熱攪拌しながら、窒素雰囲気下に、モノマーエマルジョン（Ｍ−１）と過硫酸カリウム０．５ｇの混合物を２時間かけて滴下した。滴下終了後１時間ごとに２回、さらに過硫酸カリウムを０．０５ｇずつ加え、固形分３０％のポリマーエマルジョン（ＰＥ−２）を得た。
このポリマーエマルジョン（ＰＥ−１）２０ｇに、フェノール樹脂として昭和高分子製ショウノールＣＫＳ−３８９４（固形分５０％溶液）１．２ｇ、ブチルジグリコール２ｇ、ブタノール１ｇと水８．８ｇの混合物を加えて水性塗料組成物を得た。
[Example 2] Synthesis of polymer emulsion (PE-2) 85 g of styrene, 40 g of ethyl acrylate, 10 g of an aqueous solution of an acrylic copolymer (B-1) having a solid content of 25% obtained in [Synthesis Example 1] were added. The monomer emulsion (M-1) was obtained by stirring by a usual method. In addition, the glass transition temperature of the copolymer calculated | required from the said monomer is 50 degreeC.
A reactor vessel was charged with 240 g of an aqueous 25% solid copolymer (B-1) solution and 250 g of water, and heated under stirring at 80 ° C. under a nitrogen atmosphere, and the monomer emulsion (M-1) and potassium persulfate. 0.5 g of the mixture was added dropwise over 2 hours. 0.05 g of potassium persulfate was further added twice every hour after completion of the dropwise addition to obtain a polymer emulsion (PE-2) having a solid content of 30%.
To 20 g of this polymer emulsion (PE-1) was added 1.2 g of Shounol CKS-3894 (50% solid content solution), 2 g of butyl diglycol, 1 g of butanol and 8.8 g of water as a phenol resin. Thus, an aqueous coating composition was obtained.
［実施例３］ポリマーエマルジョン（ＰＥ−３）の合成
反応容器に、固形分２５％アクリル系共重合体（Ｂ−１）水溶液２５０ｇと水２５０ｇを仕込み、８０℃で加熱攪拌しながら、窒素雰囲気下に、スチレン７６．３ｇ、エチルアクリレート３０ｇ、Ｎ−ｎ−ブトキシメチルアクリルアミド１８．８ｇと過硫酸カリウム０．５ｇを、別々に２時間かけて滴下した。尚、上記モノマーから求められる共重合体のガラス転移温度は、５５℃である。
滴下終了後１時間ごとに２回、さらに過硫酸カリウムを０．０５ｇずつ加え、固形分３０％のポリマーエマルジョン（ＰＥ−３）を得た。
このポリマーエマルジョン（ＰＥ−３）２０ｇに、フェノール樹脂として昭和高分子製ショウノールＣＫＳ−３８９４（固形分５０％溶液）１．２ｇ、ブチルジグリコール２ｇ、ブタノール１ｇと水８．８ｇの混合物を加えて水性塗料組成物を得た。
[Example 3] Synthesis of polymer emulsion (PE-3) A reaction vessel was charged with 250 g of an aqueous 25% solid copolymer (B-1) solution and 250 g of water, and heated and stirred at 80 ° C under a nitrogen atmosphere. Below, 76.3 g of styrene, 30 g of ethyl acrylate, 18.8 g of Nn-butoxymethylacrylamide and 0.5 g of potassium persulfate were separately added dropwise over 2 hours. In addition, the glass transition temperature of the copolymer calculated | required from the said monomer is 55 degreeC.
0.05 g of potassium persulfate was further added twice every hour after the completion of the dropwise addition to obtain a polymer emulsion (PE-3) having a solid content of 30%.
To 20 g of this polymer emulsion (PE-3), 1.2 g Showa High Polymer Shounol CKS-3894 (50% solids solution), 2 g butyl diglycol, 1 g butanol and 8.8 g water were added as phenolic resins. Thus, an aqueous coating composition was obtained.
［比較例１］
実施例１で得たポリマーエマルジョン（ＰＥ−１）に、フェノール樹脂を加えなかった以外は実施例１と同様にして水性塗料組成物を得た。
[Comparative Example 1]
An aqueous coating composition was obtained in the same manner as in Example 1 except that no phenol resin was added to the polymer emulsion (PE-1) obtained in Example 1.
［塗膜の評価］
実施例１、比較例１、２で得た各塗料を用い、アルミ板にバーコーター＃１８で塗工し、ガスオーブンを用い雰囲気温度２００℃で２分間焼き付け、評価用テストパネルを得て、以下のようにして塗膜の性能を評価した。結果を表１に示す。各評価の方法を以下に説明する。
＜外観＞テストパネルを目視で評価する。
○：問題なし
△：ややブツあるいは発泡あり
×：著しくブツあるいは発泡あり
[Evaluation of coating film]
Using each paint obtained in Example 1 and Comparative Examples 1 and 2, it was coated on an aluminum plate with a bar coater # 18, and baked at 200 ° C. for 2 minutes using a gas oven to obtain a test panel for evaluation. The performance of the coating film was evaluated as follows. The results are shown in Table 1. Each evaluation method will be described below.
<Appearance> Visually evaluate the test panel.
○: No problem △: Slightly fuzzed or foamed ×: Remarkably fuzzy or foamed
＜硬化性＞ ２ポンドハンマーにガーゼを巻きＭＥＫを含浸させ、テストパネルの塗膜上を往復させ、塗膜が溶解するまでの回数を求める。
◎：２００回以上
○：１００回以上２００回未満
△：５０回以上１００回未満
×：５０回未満
<Curing property> A gauze is wound around a 2 pound hammer, impregnated with MEK, reciprocated on the coating film of the test panel, and the number of times until the coating film is dissolved is obtained.
◎: 200 times or more ○: 100 times or more and less than 200 times Δ: 50 times or more and less than 100 times x: Less than 50 times
＜耐食性＞ テストパネルを４０×８０mmに切断し、塗膜を素地に達するようにクロスカットした後、テストパネルを市販のスポーツ飲料に浸漬したまま、レトルト釜で１０５℃−３０分レトルト処理を行い、その後、その状態で７０℃のオーブンに３日間入れた。その後、カット部からの片側の錆発生巾を測定した。
○：０〜２mm未満
△：２mm以上〜６mm未満
×：６mm以上
<Corrosion resistance> After cutting the test panel to 40x80mm and cross-cutting the coating film to reach the substrate, perform retort treatment at 105 ° C for 30 minutes in a retort kettle while immersing the test panel in a commercial sports drink. Then, it was placed in an oven at 70 ° C. for 3 days in that state. Thereafter, the rust generation width on one side from the cut portion was measured.
○: 0 to less than 2 mm △: 2 mm or more to less than 6 mm ×: 6 mm or more
＜耐レトルト密着性＞ テストパネルを水に浸漬したまま、レトルト釜で１２５℃−３０分レトルト処理を行い、塗膜の状態を目視で評価した。その塗面にセロハン粘着テープを貼着し、強く剥離したのちの塗面の評価を行った。
○：全く剥離なし
△：少し剥離
×：著しく剥離
<Retort resistant adhesion> While the test panel was immersed in water, retort treatment was performed at 125 ° C. for 30 minutes in a retort kettle, and the state of the coating film was visually evaluated. A cellophane adhesive tape was attached to the coated surface, and the coated surface was evaluated after peeling strongly.
○: No peeling at all Δ: Little peeling ×: Remarkably peeling
＜耐レトルト白化＞ テストパネルを水に浸漬したまま、レトルト釜で１２５℃−３０分レトルト処理を行い、塗膜の白化性について目視で評価した。
○：問題なし
△：やや白化
×：著しく白化
<Retort resistance whitening> While the test panel was immersed in water, a retort treatment was performed in a retort kettle at 125 ° C for 30 minutes, and the whitening property of the coating film was visually evaluated.
○: No problem △: Slightly white ×: Remarkably white
＜密着性＞ ＪＩＳ Ｋ−５４００碁盤目テープ法に準拠し、テストパネルに１ｍｍ×１ｍｍのマス目を１００個作成した後、粘着セロハンテープを貼着し、急激に剥した後の剥がれた碁盤目塗膜の数を数え、下記基準で評価した。
○：０個
○：１〜５個
△：６〜３９個
×：４０個以上
<Adhesiveness> In accordance with JIS K-5400 cross cut tape method, 100 squares of 1 mm x 1 mm were prepared on a test panel, and then adhesive cellophane tape was attached and peeled off after abrupt peeling. The number of coating films was counted and evaluated according to the following criteria.
○: 0 ○ ○: 1 to 5 Δ: 6 to 39 ×: 40 or more
＜加工性＞ テストパネルを大きさ40mm×50mmに切断し、塗膜を外側にして、試験部位が40mmになるように２つ折りにし、この２つ折りにした試験片の間に厚さ０．２６mmのアルミ板を２枚はさみ、１ｋｇの荷重を高さ４０ｃｍから折り曲げ部に落下させた後に、折り曲げ先端部に６．０Ｖ×６秒通電し、加工性５ｃｍ巾の電流値（mA）を測定した。
◎＋：０．５ｍＡ未満
◎ ：０．５ｍＡ以上〜１．５ｍＡ未満
○＋：１．５ｍＡ以上〜３．０ｍＡ未満
○ ：３．０ｍＡ以上〜５．０ｍＡ未満
△ ：５．０ｍＡ以上〜１５．０ｍＡ未満
× ：１５．０ｍＡ以上
<Machinability> The test panel is cut to a size of 40 mm x 50 mm, the coating is on the outside, and it is folded in half so that the test site is 40 mm, and the thickness is 0.26 mm between the folded test pieces. The aluminum plate was sandwiched between two pieces, a 1 kg load was dropped from the height of 40 cm onto the bent part, and then the end of the bent part was energized for 6.0 V × 6 seconds, and a current value (mA) of a workability of 5 cm width was measured. .
◎ +: Less than 0.5 mA ◎: 0.5 mA to less than 1.5 mA ○ +: 1.5 mA to less than 3.0 mA ○: 3.0 mA to less than 5.0 mA Δ: 5.0 mA to more than 15. Less than 0 mA x: 15.0 mA or more
＜水フレーバー性＞ 各水性塗料組成物を０．１ｍｍアルミ箔に両面塗工し２００℃１分間加熱して硬化させた後（膜厚１５〜２０ミクロン）、塗板を１０ｃｍ×２５ｃｍ（両面５００ｃｍ2）の大きさに切断する。この塗板を活性炭処理した水道水５００ｇとともに耐熱瓶に入れ、１２５℃−３０分のレトルト処理を行い、その後、風味試験を実施する。風味試験の比較対照として、塗板を入れないブランクも同様に処理する。
◎：無味
○：僅かに味がする
△：味がする
×：かなり味がする
<Water flavor property> Each water-based coating composition was coated on both sides of 0.1 mm aluminum foil and cured by heating at 200 ° C. for 1 minute (film thickness 15 to 20 microns), and then the coated plate was 10 cm × 25 cm (both sides 500 cm 2). ). This coated plate is put into a heat-resistant bottle together with 500 g of tap water treated with activated carbon, subjected to a retort treatment at 125 ° C. for 30 minutes, and then a flavor test is performed. As a comparison for the flavor test, a blank without a coated plate is treated in the same manner.
◎: Tasteless ○: Slightly tasted △: Tasteful x: Tasteful
Claims (10)
水（Ｇ）の存在下に、
ラジカル重合してなるポリマーエマルジョン（３）、及びフェノール樹脂（６）
を含有することを特徴とする水性塗料組成物。 An emulsified component (A) containing an ethylenically unsaturated monomer (A1) and not containing a polyester, an ethylene containing an ethylenically unsaturated monomer (b1) having a COOH group, and having a crosslinkable functional group other than a COOH group Acrylic copolymer (B), basic compound (C) and water (D) obtained by copolymerizing ethylenically unsaturated monomer (b) not containing organic unsaturated monomer (b2) in the absence of an organic solvent. A monomer emulsion (1) containing
In the presence of water (G)
Polymer emulsion (3) obtained by radical polymerization, and phenol resin (6)
A water-based paint composition comprising:
ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を有機溶剤の不存在下に共重合してなるアクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）を含有してなるポリマー水溶液ないしエマルジョン（２）の存在下に、
ラジカル重合してなるポリマーエマルジョン（４）、及びフェノール樹脂（６）
を含有することを特徴とする水性塗料組成物。 An emulsified component (A) containing an ethylenically unsaturated monomer (A1) and not containing a polyester, an ethylene containing an ethylenically unsaturated monomer (b1) having a COOH group, and having a crosslinkable functional group other than a COOH group Acrylic copolymer (B), basic compound (C) and water (D) obtained by copolymerizing ethylenically unsaturated monomer (b) not containing organic unsaturated monomer (b2) in the absence of an organic solvent. A monomer emulsion (1) containing
An ethylenically unsaturated monomer (e) containing an ethylenically unsaturated monomer (e1) having a COOH group and not containing an ethylenically unsaturated monomer (e2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. In the presence of an aqueous polymer solution or emulsion (2) containing an acrylic copolymer (E), a basic compound (F) and water (G) copolymerized in the presence,
Polymer emulsion (4) obtained by radical polymerization and phenol resin (6)
A water-based paint composition comprising:
ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を有機溶剤の不存在下に共重合してなるアクリル系共重合体（Ｅ）、塩基性化合物（Ｆ）及び水（Ｇ）を含有してなるポリマー水溶液ないしエマルジョン（２）の存在下に、
ラジカル重合してなるポリマーエマルジョン（５）、及びフェノール樹脂（６）
を含有することを特徴とする水性塗料組成物。 Ethylenically unsaturated monomer (A1),
An ethylenically unsaturated monomer (e) containing an ethylenically unsaturated monomer (e1) having a COOH group and not containing an ethylenically unsaturated monomer (e2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. In the presence of an aqueous polymer solution or emulsion (2) containing an acrylic copolymer (E), a basic compound (F) and water (G) copolymerized in the presence,
Polymer emulsion (5) obtained by radical polymerization and phenol resin (6)
A water-based paint composition comprising:
かつ、
エチレン性不飽和モノマー（ｂ）及び（ｅ）が、Ｎ−アルコキシアルキル（メタ）アクリルアミド、Ｎ−ヒドロキシアルキル（メタ）アクリルアミド及び（メタ）アクリルアミドからなる群より選ばれるアミド系モノマーを含有しないことを特徴とする請求項項１ないし３いずれか記載の水性塗料組成物。 The ethylenically unsaturated monomer (A1) does not contain an amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide,
And,
The ethylenically unsaturated monomers (b) and (e) do not contain an amide monomer selected from the group consisting of N-alkoxyalkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide and (meth) acrylamide. The water-based coating composition according to any one of claims 1 to 3.
該アクリル系共重合体（Ｂ）の水溶液ないし水性分散体の存在下に、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルは含有しない被乳化成分（Ａ）を、水に分散し、モノマーエマルジョン（１）を得、
該モノマーエマルジョン（１）を水に滴下し、上記モノマー（Ａ１）を重合してなるポリマーエマルジョン（３）とフェノール樹脂（６）とを混合することを特徴とする水性塗料組成物の製造方法。 An ethylenically unsaturated monomer (b) containing an ethylenically unsaturated monomer (b1) having a COOH group and not containing an ethylenically unsaturated monomer (b2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. Acrylic copolymer (B) is obtained by copolymerization in the presence, and the acrylic copolymer (B) is dissolved or dispersed in water in the presence of the basic compound (C). Obtaining an aqueous solution or dispersion of (B),
In the presence of an aqueous solution or dispersion of the acrylic copolymer (B), the emulsified component (A) containing the ethylenically unsaturated monomer (A1) and not the polyester is dispersed in water, and the monomer is dispersed. Emulsion (1) was obtained
A method for producing an aqueous coating composition, which comprises dropping the monomer emulsion (1) into water and mixing a polymer emulsion (3) obtained by polymerizing the monomer (A1) and a phenol resin (6).
該アクリル系共重合体（Ｂ）の水溶液ないし水性分散体の存在下に、エチレン性不飽和モノマー（Ａ１）を含有し、ポリエステルは含有しない被乳化成分（Ａ）を、水に分散し、モノマーエマルジョン（１）を得、
ＣＯＯＨ基を有するエチレン性不飽和モノマー（ｅ１）を含有し、ＣＯＯＨ基以外の架橋性官能基を有するエチレン性不飽和モノマー（ｅ２）を含有しないエチレン性不飽和モノマー（ｅ）を有機溶剤の不存在下に共重合し、アクリル系共重合体（Ｅ）を得、該アクリル系共重合体（Ｅ）を塩基性化合物（Ｆ）の存在下に水に溶解ないし分散せしめ、アクリル系共重合体（Ｅ）の水溶液ないし水性分散体を得、
前記モノマーエマルジョン（１）を、前記アクリル系共重合体（Ｅ）の水溶液ないし水性分散体に滴下し、モノマー（Ａ１）を重合してなるポリマーエマルジョン（４）とフェノール樹脂（６）とを混合することを特徴とする水性塗料組成物の製造方法。 An ethylenically unsaturated monomer (b) containing an ethylenically unsaturated monomer (b1) having a COOH group and not containing an ethylenically unsaturated monomer (b2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. Acrylic copolymer (B) is obtained by copolymerization in the presence, and the acrylic copolymer (B) is dissolved or dispersed in water in the presence of the basic compound (C). Obtaining an aqueous solution or dispersion of (B),
In the presence of an aqueous solution or dispersion of the acrylic copolymer (B), the emulsified component (A) containing the ethylenically unsaturated monomer (A1) and not the polyester is dispersed in water, and the monomer is dispersed. Emulsion (1) was obtained
An ethylenically unsaturated monomer (e) containing an ethylenically unsaturated monomer (e1) having a COOH group and not containing an ethylenically unsaturated monomer (e2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. Acrylic copolymer (E) is obtained by copolymerization in the presence, and the acrylic copolymer (E) is dissolved or dispersed in water in the presence of the basic compound (F). Obtaining an aqueous solution or dispersion of (E),
The monomer emulsion (1) is dropped into an aqueous solution or dispersion of the acrylic copolymer (E), and the polymer emulsion (4) obtained by polymerizing the monomer (A1) and the phenol resin (6) are mixed. A method for producing a water-based coating composition characterized by comprising:
エチレン性不飽和モノマー（Ａ１）を、前記アクリル系共重合体（Ｅ）の水溶液ないし水性分散体に滴下し、モノマー（Ａ１）を重合してなるポリマーエマルジョン（５）とフェノール樹脂（６）とを混合することを特徴とする水性塗料組成物の製造方法。
An ethylenically unsaturated monomer (e) containing an ethylenically unsaturated monomer (e1) having a COOH group and not containing an ethylenically unsaturated monomer (e2) having a crosslinkable functional group other than a COOH group is used as an organic solvent. Acrylic copolymer (E) is obtained by copolymerization in the presence, and the acrylic copolymer (E) is dissolved or dispersed in water in the presence of the basic compound (F). Obtaining an aqueous solution or dispersion of (E),
An ethylenically unsaturated monomer (A1) is dropped into an aqueous solution or dispersion of the acrylic copolymer (E), and the polymer emulsion (5) obtained by polymerizing the monomer (A1), the phenol resin (6), A method for producing a water-based coating composition, comprising mixing
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8092876B2 (en) | 2004-10-20 | 2012-01-10 | Valspar Sourcing, Inc. | Coating compositions for cans and methods of coating |
| US8465846B2 (en) | 2003-04-02 | 2013-06-18 | Valspar Sourcing, Inc. | Aqueous dispersions and coatings |
| US8747979B2 (en) | 2009-07-17 | 2014-06-10 | Valspar Sourcing, Inc. | Coating compositions and articles coated therewith |
| US8840966B2 (en) | 2009-09-18 | 2014-09-23 | Valspar Sourcing, Inc. | Polyurethane coating composition |
| WO2015147180A1 (en) * | 2014-03-28 | 2015-10-01 | 東洋インキＳｃホールディングス株式会社 | Water-based paint, production method for water-based paint, and coated can |
| US10563010B2 (en) | 2009-04-09 | 2020-02-18 | The Sherwin-Williams Company | Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8465846B2 (en) | 2003-04-02 | 2013-06-18 | Valspar Sourcing, Inc. | Aqueous dispersions and coatings |
| US8911874B2 (en) | 2003-04-02 | 2014-12-16 | Valspar Sourcing, Inc. | Aqueous dispersions and coatings |
| US10336909B2 (en) | 2004-10-20 | 2019-07-02 | The Sherwin-Williams Company | Coating compositions for aluminum beverage cans and methods of coating same |
| US8142868B2 (en) | 2004-10-20 | 2012-03-27 | Valspar Sourcing, Inc. | Coating compositions for cans and methods of coating |
| US8173265B2 (en) | 2004-10-20 | 2012-05-08 | Valspar Sourcing, Inc. | Coating compositions for cans and methods of coating |
| US8617663B2 (en) | 2004-10-20 | 2013-12-31 | Valspar Sourcing, Inc. | Coating compositions for cans and methods of coating |
| US9862854B2 (en) | 2004-10-20 | 2018-01-09 | Valspar Sourcing, Inc. | Coating compositions for aluminum beverage cans and methods of coating same |
| US9415900B2 (en) | 2004-10-20 | 2016-08-16 | Valspar Sourcing, Inc. | Coating compositions for aluminum beverage cans and methods of coating same |
| US8092876B2 (en) | 2004-10-20 | 2012-01-10 | Valspar Sourcing, Inc. | Coating compositions for cans and methods of coating |
| US10961344B2 (en) | 2009-04-09 | 2021-03-30 | The Sherwin-Williams Company | Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom |
| US10563010B2 (en) | 2009-04-09 | 2020-02-18 | The Sherwin-Williams Company | Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom |
| US9061798B2 (en) | 2009-07-17 | 2015-06-23 | Valspar Sourcing, Inc. | Coating composition and articles coated therewith |
| US8747979B2 (en) | 2009-07-17 | 2014-06-10 | Valspar Sourcing, Inc. | Coating compositions and articles coated therewith |
| US9011999B2 (en) | 2009-09-18 | 2015-04-21 | Valspar Sourcing, Inc. | Coating composition including an unsaturated polymer |
| US9487672B2 (en) | 2009-09-18 | 2016-11-08 | Valspar Sourcing, Inc. | Polyurethane coating composition |
| US9206332B2 (en) | 2009-09-18 | 2015-12-08 | Valspar Sourcing, Inc. | Coating composition including an unsaturated polymer |
| US8840966B2 (en) | 2009-09-18 | 2014-09-23 | Valspar Sourcing, Inc. | Polyurethane coating composition |
| JP2015193834A (en) * | 2014-03-28 | 2015-11-05 | 東洋インキＳｃホールディングス株式会社 | Water based paint, manufacturing method of water based paint, and coated can |
| WO2015147180A1 (en) * | 2014-03-28 | 2015-10-01 | 東洋インキＳｃホールディングス株式会社 | Water-based paint, production method for water-based paint, and coated can |
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