JP2008050486A - Base coat composition for outside surface of 3p metal can and 3p metal can having cured coated film layer of the composition - Google Patents
Base coat composition for outside surface of 3p metal can and 3p metal can having cured coated film layer of the composition Download PDFInfo
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本発明は、３Ｐ金属缶の外表面に高輝度のシルバー色の意匠性有し、且つ耐レトルト性に優れた塗膜層を形成するための３Ｐ金属缶外面用ベースコート組成物、及び該塗料組成物の乾燥硬化塗膜層を有する３Ｐ金属缶に関する。 The present invention relates to a base coat composition for the outer surface of a 3P metal can and a coating composition for forming a coating layer having a high brightness silver design on the outer surface of the 3P metal can and excellent in retort resistance. The present invention relates to a 3P metal can having a dry-cured coating film layer.
近年、化粧品用、飲食物用等に使用される金属缶の意匠性を高めるために、パール系顔料を含有するワニスや、光干渉顔料を添加した塗料により、金属缶表面に塗膜を形成することが提案されている（例えば、特許文献１及び２参照）。現在、流行色として自動車車体色やパッケージの外装色として高輝度シルバー色の意匠性が求められるようになってきたが、３Ｐ金属缶用の従来の塗膜では意匠性は充分満足できるものではなかった。又３Ｐ金属缶特に飲料缶は耐レトルト性（耐蒸気性）が重要な要因となっている。しかし、アルミニウムフレーク顔料は耐水性に乏しい（著しく劣る：水分に接触すると酸化し水素ガスを発生する）。近年、アルミニウム製ＤＩ缶用にガラスフレーク顔料を用いた高輝度性を有する塗料が提案されている（例えば、特許文献３参照）しかし、ガラスフレーク顔料は高価であり、採用を妨げる要因となっている。そこで、比較的廉価なアルミニウムフレーク顔料を用いる事となるが、前述した様に、耐レトルト性に劣る為、白化・ブリスター等が発生する事となり、現在までアルミニウムフレーク顔料を用いた３Ｐ金属缶用塗料で充分な耐レトルト性を保持した塗料は存在しなかった。 In recent years, in order to improve the design of metal cans used for cosmetics, food and drinks, etc., a coating film is formed on the surface of the metal can with a varnish containing a pearl pigment or a paint added with a light interference pigment. (For example, refer to Patent Documents 1 and 2). At present, the design of high-brightness silver as an automobile body color as a trendy color and the exterior color of packages has been required, but the design properties of conventional coatings for 3P metal cans are not fully satisfactory. It was. Further, retort resistance (steam resistance) is an important factor for 3P metal cans, especially beverage cans. However, aluminum flake pigments have poor water resistance (remarkably inferior: they oxidize and generate hydrogen gas when in contact with moisture). In recent years, paints having high brightness using glass flake pigments for aluminum DI cans have been proposed (see, for example, Patent Document 3). However, glass flake pigments are expensive and hinder adoption. Yes. Therefore, relatively inexpensive aluminum flake pigments will be used, but as mentioned above, since they are inferior in retort resistance, whitening, blistering, etc. will occur, and so far for 3P metal cans using aluminum flake pigments. There was no paint that retained sufficient retort resistance.
本発明の課題は、塗装された３Ｐ金属缶に、高輝度のシルバー色の意匠性を付与するとともに、上層のＵＶインキ層及び上塗り艶ニスとの密着性、耐レトルト性に優れ、しかも環境負荷の少ないＢＰＡフリーの３Ｐ金属缶外面用ベースコート組成物、及び該塗料組成物の乾燥硬化塗膜層を有する３Ｐ金属缶を提供することにある。 The object of the present invention is to impart a high-brightness silver color design to the coated 3P metal can, as well as excellent adhesion to the upper UV ink layer and the top coat gloss varnish, retort resistance, and environmental impact. An object of the present invention is to provide a 3P metal can having a low BPA-free 3P metal can outer base coat composition and a dry-cured coating layer of the coating composition.
本発明者らは鋭意検討の結果、ＢＰＡを含まないバインダー樹脂成分と、特定の表面処理を施したアルミニウムフレーク顔料及び、特定のアクリル系ポリマー及び特定のＵＶインキアンカー剤を使用することによって、顔料の配向を制御し、意匠性を維持しつつ、上層のＵＶインキ、上塗り艶ニスの密着性、耐レトルト性も兼ね備えた３Ｐ金属缶外面用ベースコート組成物が得られることを見出し、本発明に至った。 As a result of intensive studies, the present inventors have used a binder resin component that does not contain BPA, an aluminum flake pigment that has been subjected to a specific surface treatment, a specific acrylic polymer, and a specific UV ink anchor agent. It has been found that a base coat composition for the outer surface of a 3P metal can having an upper layer UV ink, adhesion of an overcoat gloss varnish, and retort resistance can be obtained while controlling the orientation of the resin and maintaining design properties. It was.
すなわち、本発明は、第一に、（Ａ）ビスフェノール型由来原料を含まないポリエステル樹脂、（Ｂ）硬化剤を有する樹脂成分、（Ｃ）アルミニウムフレーク表面にアクリル樹脂を被覆したアルミペースト顔料、（Ｄ）数平均分子量が５，０００〜１０，０００であるイソブチルアクリレートの単独重合体、及び、（Ｅ）ＵＶインキアンカー剤を含有し、該アルミペースト顔料の含有量がバインダー樹脂成分（Ａ＋Ｂ＋Ｄ）の固形分１００質量部に対し、５〜４０質量部であることを特徴とする３Ｐ金属缶外面用ベースコート組成物を提供する。 That is, the present invention firstly includes (A) a polyester resin not containing a bisphenol type-derived raw material, (B) a resin component having a curing agent, (C) an aluminum paste pigment in which an aluminum flake surface is coated with an acrylic resin, ( D) A homopolymer of isobutyl acrylate having a number average molecular weight of 5,000 to 10,000, and (E) a UV ink anchor agent, wherein the content of the aluminum paste pigment is the binder resin component (A + B + D) Provided is a 3P metal can outer surface base coat composition, which is 5 to 40 parts by mass with respect to 100 parts by mass of a solid content.
本発明は、第二に、３Ｐ金属缶外面に、前記した３Ｐ金属缶外面用ベースコート組成物の乾燥硬化塗膜層を有することを特徴とする３Ｐ金属缶を提供する。特に高輝度シルバー色の意匠性に優れた３Ｐ金属缶を提供する。 The present invention secondly provides a 3P metal can characterized by having a dry-cured coating film layer of the above-described base coat composition for 3P metal can outer surface on the 3P metal can outer surface. In particular, a 3P metal can excellent in high brightness silver design is provided.
本発明によれば、塗装された３Ｐ金属缶に、高輝度シルバー色の意匠性を付与するとともに、上層のＵＶインキ層及び上塗り艶ニスとの密着性、耐レトルト性に優れ、しかも環境負荷の少ないＢＰＡフリーの３Ｐ金属缶外面用ベースコート組成物及び該塗料組成物の乾燥硬化塗膜層を有する３Ｐ金属缶を得ることが出来る。 According to the present invention, high-intensity silver color design is imparted to a coated 3P metal can, and it has excellent adhesion to the upper UV ink layer and top gloss varnish, retort resistance, and environmental impact. A 3P metal can having a small BPA-free 3P metal can outer base coat composition and a dry-cured coating layer of the coating composition can be obtained.
本発明の３Ｐ金属缶外面用ベースコート組成物に用いるポリエステル樹脂（Ａ）は、ビスフェノール型由来原料を含まないポリエステル樹脂であり、固形分水酸基価が５〜１０（ｍｇＫＯＨ／ｇ）、固形分酸価が１〜５（ｍｇＫＯＨ／ｇ）であり、更に、数平均分子量が１３，０００〜１８，０００であることが好ましい。 The polyester resin (A) used in the base coat composition for the outer surface of the 3P metal can of the present invention is a polyester resin that does not contain a bisphenol-type raw material, has a solid content hydroxyl value of 5 to 10 (mg KOH / g), and a solid content acid value. Is 1 to 5 (mgKOH / g), and the number average molecular weight is preferably 13,000 to 18,000.
本発明の３Ｐ金属缶外面用ベースコート組成物に、硬化剤として用いられるアミノ樹脂は、ビスフェノール型由来原料を含まないメチルブチルエーテル化ベンゾグアナミン−メラミン共縮合樹脂であることが好ましい。 The amino resin used as a curing agent in the 3P metal can outer surface base coat composition of the present invention is preferably a methylbutyl etherified benzoguanamine-melamine cocondensation resin that does not contain a bisphenol-type raw material.
本発明に用いられる、塗膜に高輝度のシルバー色の意匠性を付与する為の顔料は、（Ｃ）アルミニウムフレーク表面にアクリル樹脂を被覆し表面処理を施したアルミペースト顔料である。 The pigment for imparting high brightness silver design to the coating film used in the present invention is (C) an aluminum paste pigment obtained by coating the surface of an aluminum flake with an acrylic resin and performing a surface treatment.
前記（Ｃ）アルミペースト顔料のバインダー樹脂成分固形分１００質量部に対する配合量は、５〜４０質量部の範囲である。４０質量部を越えると塗膜の耐レトルト性が低下し、５質量部を下回ると鮮やかな意匠性を充分に発現しにくい。（Ｃ）アルミニウムフレーク顔料の平均粒径は、Ｄ５０が、１３μｍ程度であることが好ましい。本発明に用いることの出来る市販の（Ｃ）アルミニウムフレーク顔料としては、旭化成ケミカルズ社製アルミペーストＴＲ２１３０等が挙げられる。 The compounding quantity with respect to 100 mass parts of binder resin component solid content of the said (C) aluminum paste pigment is the range of 5-40 mass parts. When it exceeds 40 parts by mass, the retort resistance of the coating film is lowered, and when it is less than 5 parts by mass, it is difficult to sufficiently exhibit vivid design. (C) As for the average particle diameter of an aluminum flake pigment, it is preferable that D50 is about 13 micrometers. Examples of commercially available (C) aluminum flake pigments that can be used in the present invention include aluminum paste TR2130 manufactured by Asahi Kasei Chemicals Corporation.
アルミニウムフレーク顔料の特性を充分に発揮させるためには、偏平な顔料を塗膜内に平面状に配向させることが好ましい。しかしながら、平面状の配向は上塗り艶ニスとの密着性を阻害する傾向にある。本発明に用いられる（Ｄ）イソブチルアクリレート単独重合体は、数平均分子量が５，０００〜１０，０００の範囲にあり、上塗り艶ニスの密着性を低下させることなく、扁平な形状のアルミニウムフレーク顔料を形成塗膜内に平面状に配向させる機能を有するものである。（Ｄ）イソブチルアクリレート単量体及びその重合体が可溶な有機溶剤中で、過酸化物或いはアゾ化合物等の重合開始剤を用いて当該単量体をラジカル重合せしめることによって得ることができる。 In order to sufficiently exhibit the characteristics of the aluminum flake pigment, it is preferable that the flat pigment is oriented in a plane in the coating film. However, the planar orientation tends to inhibit the adhesion with the top coat gloss varnish. The (D) isobutyl acrylate homopolymer used in the present invention has a number average molecular weight in the range of 5,000 to 10,000, and has a flat aluminum flake pigment without reducing the adhesion of the overcoat gloss varnish. Has a function of orienting in a plane in the formed coating film. (D) It can be obtained by radical polymerization of the monomer using a polymerization initiator such as a peroxide or an azo compound in an organic solvent in which the isobutyl acrylate monomer and its polymer are soluble.
（Ｄ）イソブチルアクリレート単独重合体の分子量は、重合条件（単量体濃度、重合開始剤濃度、重合温度）の選択によって５，０００〜１０，０００の範囲でより好ましい範囲で調整することが可能である。（Ｃ）アルミニウムフレーク顔料１００質量部に対する（Ｄ）イソブチルアクリレート単独重合体の相応しい配合量は、１〜１０質量部であり、より好ましくは、２〜５質量部である。 (D) The molecular weight of the isobutyl acrylate homopolymer can be adjusted in a more preferable range within the range of 5,000 to 10,000 by selecting the polymerization conditions (monomer concentration, polymerization initiator concentration, polymerization temperature). It is. (C) The suitable compounding quantity of (D) isobutyl acrylate homopolymer with respect to 100 mass parts of aluminum flake pigments is 1-10 mass parts, More preferably, it is 2-5 mass parts.
耐レトルト性を奏するために、３Ｐ金属缶外面用ベースコート組成物では、塗膜の硬度及び、耐熱性を保持する目的で主樹脂の高いＴｇが好ましい。しかしながら、硬い高Ｔｇの塗膜ではＵＶインキの密着性を阻害させる傾向にある。事実、ＵＶインキ印刷ラインではバックトラップ等の現象が発生する。ＵＶインキアンカー剤として、単官能のＵＶモノマーを構成成分とするポリエステル樹脂を用いることによって、塗膜の硬度を低下させる事無く、上層のＵＶインキを密着させる効果を発揮する。 In order to exhibit retort resistance, the base coat composition for 3P metal can outer surface preferably has a high Tg of the main resin for the purpose of maintaining the hardness and heat resistance of the coating film. However, a hard high Tg coating tends to inhibit the adhesion of UV ink. In fact, phenomena such as back traps occur in the UV ink printing line. By using a polyester resin containing a monofunctional UV monomer as a constituent component as a UV ink anchoring agent, the effect of adhering the upper UV ink is exhibited without reducing the hardness of the coating film.
本発明の３Ｐ金属缶外面用ベースコート組成物では、キシレン、ソルベッソ１００（エクソン社製）、ソルベッソ１５０（エクソン社製）等の芳香族炭化水素、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、酢酸エトキシエチル、酢酸ブトキシエチル、メチルイソブチルケトン、イソホロン等、公知の溶剤が用いられる。 In the base coat composition for the outer surface of the 3P metal can of the present invention, aromatic hydrocarbons such as xylene, Solvesso 100 (manufactured by Exxon), Solvesso 150 (manufactured by Exxon), ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, ethoxyethyl acetate, butoxyethyl acetate, methyl isobutyl Known solvents such as ketone and isophorone are used.
本発明の３Ｐ金属缶外面用ベースコート組成物には、必要に応じて、消泡剤、レベリング剤、スポット塗装性付与剤、滑剤等、その他の任意の添加剤を用いることが出来る。 In the 3P metal can outer surface base coat composition of the present invention, other optional additives such as an antifoaming agent, a leveling agent, a spot coatability-imparting agent, and a lubricant can be used as necessary.
本発明の３Ｐ金属缶外面用ベースコート組成物は以下の方法で製造することが出来る。（Ｃ）アルミペースト顔料の沈降防止機能及び体質顔料機能を持つ沈降性硫酸バリウムを、バインダー樹脂成分である（Ａ）ポリエステル樹脂で練肉し、顔料ベースを調製する。次いで、このベースに、前記（Ａ）ポリエステル樹脂、（Ｂ）硬化剤成分、（Ｃ）アルミペースト顔料、（Ｄ）イソブチルアクリレートの単独重合体及びＵＶインキアンカー剤を加えて分散攪拌機で撹拌・混合する。（Ｃ）アルミペースト顔料は練肉せず撹拌のみで分散させるのが望ましい。 The base coat composition for 3P metal can outer surface of the present invention can be produced by the following method. (C) Precipitating barium sulfate having an anti-settling function and an extender function of an aluminum paste pigment is kneaded with (A) a polyester resin as a binder resin component to prepare a pigment base. Next, (A) polyester resin, (B) curing agent component, (C) aluminum paste pigment, (D) isobutyl acrylate homopolymer and UV ink anchor agent are added to this base, and the mixture is stirred and mixed with a dispersion stirrer. To do. (C) It is desirable to disperse the aluminum paste pigment only by stirring without kneading.
３Ｐ金属缶外面に、前記した３Ｐ金属缶外面用ベースコート組成物の乾燥硬化塗膜層を有することを特徴とする３Ｐ金属缶の塗膜層の具体的な形態としては、（１）下地処理を施した金属板に前記した３Ｐ金属缶外面用ベースコート組成物の乾燥硬化塗膜層を設ける構成、（２）下地処理を施した金属板に前記した３Ｐ金属缶外面用ベースコート組成物の乾燥硬化塗膜層を設け、更に艶ニス等の上塗り層を設ける構成、（３）下地処理を施した金属板に、前記した３Ｐ金属缶外面用ベースコート組成物の乾燥硬化塗膜層を設け、その上に印刷層を設ける構成、（４）下地処理を施した金属板に、前記した３Ｐ金属缶外面用ベースコート組成物の乾燥硬化塗膜層を設け、その上に印刷層を設け、更に艶ニス等の上塗り層を設ける構成がある。また、（１）〜（４）の各々について、金属板にサイジングニス塗装を行う構成もある。 As a specific form of the coating layer of the 3P metal can characterized by having a dry-cured coating layer of the base coat composition for the outer surface of the 3P metal can described above on the outer surface of the 3P metal can, A structure in which a dry-cured coating film layer of the above-described 3P metal can outer surface base coat composition is provided on the applied metal plate, and (2) a dry-cured coating of the above-described 3P metal can outer surface base coat composition on the metal plate subjected to the base treatment. A structure in which a film layer is provided and an overcoat layer such as a gloss varnish is further provided. (3) A dry-cured coating layer of the above-described base coat composition for 3P metal can outer surface is provided on a metal plate subjected to a base treatment, and on that, The structure which provides a printing layer, (4) The above-mentioned 3P metal can outer surface basecoat composition dry-cured coating film layer is provided on a metal plate subjected to a base treatment, and a printing layer is further provided thereon, and further a gloss varnish or the like There is a configuration in which an overcoat layer is provided. Moreover, about each of (1)-(4), there also exists a structure which performs sizing varnish coating on a metal plate.
本発明の３Ｐ金属缶に用いられる艶ニス等の上塗り層には、一般に金属缶用途に用いられるポリエステル系、アクリル系等任意のクリアー塗料が用いられる。 For the overcoat layer such as gloss varnish used for the 3P metal can of the present invention, any clear paint such as polyester or acrylic generally used for metal can applications is used.
本発明の３Ｐ金属缶外面用塗料組成物は例えば、以下の手順で金属表面に塗工される。金属板として、電気錫メッキ鋼板（ブリキ、ＥＴ板メッキ量２．８ｇ／ｍ２）上に、本発明の３Ｐ金属缶外面用塗料組成物を、好ましくは乾燥膜厚３０〜１６０ｍｇ／１００ｃｍ２、より好ましくは６０〜１３０ｍｇ／１００ｃｍ２で、乾燥条件１６０〜２００℃−１０分程度で塗工することが出来る。更に、印刷インキ及び上塗り艶ニスを施しても良い。また、金属板上に形成された公知のサイジングニス塗料の塗膜上に本発明の３Ｐ金属缶外面用塗料組成物を塗装することも可能である。 The 3P metal can outer coating composition of the present invention is applied to a metal surface by the following procedure, for example. As the metal plate, the 3P metal can outer surface coating composition of the present invention on an electrotin-plated steel plate (tinplate, ET plate plating amount 2.8 g / m 2 ), preferably a dry film thickness of 30 to 160 mg / 100 cm 2 , More preferably, it is 60-130 mg / 100 cm < 2 >, and it can apply | coat by drying conditions 160-200 degreeC-10 minutes. Furthermore, you may give printing ink and top coat gloss varnish. It is also possible to apply the coating composition for a 3P metal can outer surface of the present invention on a coating film of a known sizing varnish coating formed on a metal plate.
以下、実施例により、本発明を具体的に説明する。特に指定のない限り、実施例中の、部、％は質量部、質量％を表す。 Hereinafter, the present invention will be described specifically by way of examples. Unless otherwise specified, “part” and “%” in the examples represent “part by mass” and “% by mass”.
〔イソブチルアクリレート単独重合体（Ｄ）の合成〕
攪拌機、還流冷却器、滴下ロート、温度計、窒素ガス導入管を具備した容量１リットルの４ツ口フラスコにエチレングリコールモノブチルエーテル１５０部、ソルベッソ１００（エクソン社製）１５０部を仕込み、１００℃まで昇温した。同温度を保持しつつ、滴下ロートからアクリル酸イソブチル３００部とｔ−ブチルパーオキシベンゾエイト６．０部との混合溶液を３時間に亘って連続滴下した。滴下終了１時間後にジ−ｔ−ブチルパーオキサイド０．９部を添加し、更に２時間同温度で反応を行った。生成したポリマー溶液の不揮発分は５０．１％、粘度は（ガードナー）Ｔ−Ｕであり、ポリマーの分子量は６６００（ＧＰＣ数平均）であった。これを、エチレングリコールモノブチルエーテルで希釈し、不揮発分１０％のイソブチルアクリレート単独重合体（Ｄ）を得た。
[Synthesis of Isobutyl Acrylate Homopolymer (D)]
150 parts of ethylene glycol monobutyl ether and 150 parts of Solvesso 100 (manufactured by Exxon) are charged in a 1-liter four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet tube, up to 100 ° C. The temperature rose. While maintaining the same temperature, a mixed solution of 300 parts of isobutyl acrylate and 6.0 parts of t-butyl peroxybenzoate was continuously dropped from a dropping funnel over 3 hours. One hour after the completion of dropping, 0.9 part of di-t-butyl peroxide was added, and the reaction was further performed at the same temperature for 2 hours. The produced polymer solution had a non-volatile content of 50.1%, a viscosity of (Gardner) TU, and a molecular weight of the polymer of 6600 (GPC number average). This was diluted with ethylene glycol monobutyl ether to obtain an isobutyl acrylate homopolymer (D) having a nonvolatile content of 10%.
〔ノルマルブチルアクリレート単独重合体の合成〕
攪拌機、還流冷却器、滴下ロート、温度計、窒素ガス導入管を具備した容量１リットルの４ツ口フラスコにエチレングリコールモノブチルエーテル１５０部、ソルベッソ１００（エクソン社製）１５０部を仕込み、１００℃まで昇温した。同温度を保持しつつ、滴下ロートからアクリル酸ノルマルブチル３００部とｔ−ブチルパーオキシベンゾエイト６．０部との混合溶液を３時間に亘って連続滴下した。滴下終了１時間後にジ−ｔ−ブチルパーオキサイド０．９部を添加し、更に２時間同温度で反応を行った。生成したポリマー溶液の不揮発分は５０．２％、粘度は（ガードナー）Ｔ−Ｕであり、ポリマーの分子量は６６００（ＧＰＣ数平均）であった。これを、エチレングリコールモノブチルエーテルで希釈し、不揮発分１０％の、比較例用ノルマルブチルアクリレート重合体を得た。
[Synthesis of normal butyl acrylate homopolymer]
150 parts of ethylene glycol monobutyl ether and 150 parts of Solvesso 100 (manufactured by Exxon) are charged in a 1-liter four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet tube, up to 100 ° C. The temperature rose. While maintaining the same temperature, a mixed solution of 300 parts of normal butyl acrylate and 6.0 parts of t-butyl peroxybenzoate was continuously dropped from a dropping funnel over 3 hours. One hour after the completion of dropping, 0.9 part of di-t-butyl peroxide was added, and the reaction was further performed at the same temperature for 2 hours. The produced polymer solution had a nonvolatile content of 50.2%, a viscosity of (Gardner) TU, and a molecular weight of the polymer of 6600 (GPC number average). This was diluted with ethylene glycol monobutyl ether to obtain a normal butyl acrylate polymer for comparative example having a nonvolatile content of 10%.
（上塗り艶ニスの調製）
ＢＰＡフリーの高分子ポリエステル樹脂ベッコライトＭ−６１８６−６０（大日本インキ化学工業株式会社製）を５０部、ベンゾグアナミン樹脂スーパーベッカミンＬ−７５０−６０（大日本インキ化学工業株式会社製）２０部、スーパーベッカミン１７−５０８（大日本インキ化学工業株式会社製）を２０部、ノルマルブタノール４部、ソルベッソ１００（エクソン社製）３部、消泡剤、ウエットインキ適性付与シリコーン助剤、ワックス等をバットタンクに配合し６０℃まで攪拌・昇温反応後、４０℃以下に冷却しソルベッソ１００（エクソン社製）で粘度を調節した。不揮発分４８．０％、粘度７０秒（２５℃、フォードカップＮｏ．４）のポリエステル系上塗り艶ニスを得た。
(Preparation of top coat gloss varnish)
50 parts of BPA-free high molecular polyester resin Beckolite M-6186-60 (Dainippon Ink Chemical Co., Ltd.), 20 parts of benzoguanamine resin Super Becamine L-750-60 (Dainippon Ink Chemical Co., Ltd.) Superbecamine 17-508 (Dainippon Ink Chemical Co., Ltd.) 20 parts, normal butanol 4 parts, Solvesso 100 (Exxon Corporation) 3 parts, antifoaming agent, wet ink suitability imparting silicone auxiliaries, wax, etc. Was mixed in a vat tank, stirred and heated to 60 ° C., cooled to 40 ° C. or lower, and the viscosity was adjusted with Solvesso 100 (manufactured by Exxon). A polyester-based topcoat gloss varnish having a nonvolatile content of 48.0% and a viscosity of 70 seconds (25 ° C., Ford Cup No. 4) was obtained.
（実施例１）
ビスフェノール型由来原料を含まない、固形分水酸基価が８（ｍｇＫＯＨ／ｇ）、固形分酸価が５（ｍｇＫＯＨ／ｇ）で、数平均分子量が１５，０００であるポリエステル樹脂（Ａ）６０部に、沈降性硫酸バリウム３０部、及びブチルセロソルブアセテート３０部を配合し、ロールミルで練肉し、沈降性硫酸バリウム濃度２５％のベースを得た。沈降性硫酸バリウムベース２０．０部に対し、前記ポリエステル樹脂（Ａ）を４１．０部、ビスフェノール型由来原料を含まないメチルブチルエーテル化ベンゾグアナミン−メラミン共縮合樹脂であるアミノ樹脂（Ｂ）を１２．５部添加、アクリル樹脂で表面処理を施したアルミペースト顔料（Ｃ）（旭化成メタルズ社製アルミペーストＴＲ−２１３０、平均粒径１３μｍ）を１０．０部、数平均分子量６６００のイソブチルアクリレート単独重合体（Ｄ）を０．０８部、ヒドロキシエチルアクリレートを構成成分とするＵＶインキアンカー剤（Ｅ）を３．０部配合し混合撹拌、ソルベッソ１００で粘度調整を実施し、２００メッシュで濾過した後、不揮発分４０％、粘度１２０秒（２５℃、フォードカップＮｏ．４）の３Ｐ金属缶外面用塗料組成物を得た。得られた３Ｐ金属缶外面用塗料組成物をブリキ板（スズメッキ量２．８ｇ／ｍ２）上に焼き付け乾燥後の膜厚が約６０ｍｇ／１００ｃｍ２になるように塗装し、１６０℃１０分間焼き付けを行った。その上に更に、ポリエステル系の上塗り艶ニスを乾燥膜厚約７０ｍｇ／１００ｃｍ２となるよう塗装して、塗装金属板を得た。
(Example 1)
In 60 parts of a polyester resin (A) having a solid content hydroxyl value of 8 (mg KOH / g), a solid content acid value of 5 (mg KOH / g) and a number average molecular weight of 15,000, which does not include a bisphenol-type raw material Then, 30 parts of precipitated barium sulfate and 30 parts of butyl cellosolve acetate were blended and kneaded with a roll mill to obtain a base having a precipitated barium sulfate concentration of 25%. 12. 21.0 parts of the precipitating barium sulfate base, 41.0 parts of the polyester resin (A), and 12.1 of the amino resin (B), which is a methylbutyl etherified benzoguanamine-melamine cocondensation resin not containing a bisphenol-derived material. 5 parts added, 10.0 parts of aluminum paste pigment (C) (aluminum paste TR-2130 manufactured by Asahi Kasei Metals Co., Ltd., average particle size 13 μm) surface-treated with acrylic resin, isobutyl acrylate homopolymer having a number average molecular weight of 6600 0.08 parts of (D), 3.0 parts of UV ink anchoring agent (E) containing hydroxyethyl acrylate as a constituent component, mixing and stirring, adjusting the viscosity with Solvesso 100, and filtering through 200 mesh, 3P metal can outer coating with non-volatile content of 40% and viscosity of 120 seconds (25 ° C, Ford Cup No. 4) To obtain a composition. The obtained 3P metal can outer coating composition was baked on a tin plate (tin plating amount 2.8 g / m 2 ) so that the film thickness after drying was about 60 mg / 100 cm 2 and baked at 160 ° C. for 10 minutes. Went. Further thereon, a polyester-based topcoat gloss varnish was applied so as to have a dry film thickness of about 70 mg / 100 cm 2 to obtain a coated metal plate.
（実施例２）
ビスフェノール型由来原料を含まない、固形分水酸基価が８（ｍｇＫＯＨ／ｇ）、固形分酸価が５（ｍｇＫＯＨ／ｇ）で、数平均分子量が１５，０００であるポリエステル樹脂（Ａ）６０部に沈降性硫酸バリウム３０部、及びブチルセロソルブアセテート３０部を配合し、ロールミルで練肉し、沈降性硫酸バリウム濃度２５％のベースを得た。沈降性硫酸バリウムベース２０．０部に対し、前記ポリエステル樹脂（Ａ）を４１．０部、ビスフェノール型由来原料を含まないメチルブチルエーテル化ベンゾグアナミン−メラミン共縮合樹脂であるアミノ樹脂（Ｂ）を１２．５部添加、アクリル樹脂で表面処理を施したアルミペースト顔料（Ｃ）（旭化成メタルズ社製アルミペーストＴＲ−２１００、平均粒径１０μｍ）を１０．０部、数平均分子量６６００のイソブチルアクリレート単独重合体（Ｄ）を０．０８部、ヒドロキシエチルアクリレートを構成成分とするＵＶインキアンカー剤（Ｅ）を３．０部配合し混合撹拌、ソルベッソ１００で粘度調整を実施し、２００メッシュで濾過した後、不揮発分４０％、粘度１２０秒（２５℃、フォードカップＮｏ．４）の３Ｐ金属缶外面用塗料組成物を得た。得られた塗料組成物を用いて実施例１と同様の条件で塗装金属板を得た。
(Example 2)
In 60 parts of a polyester resin (A) having a solid content hydroxyl value of 8 (mg KOH / g), a solid content acid value of 5 (mg KOH / g) and a number average molecular weight of 15,000, which does not include a bisphenol-type raw material 30 parts of precipitated barium sulfate and 30 parts of butyl cellosolve acetate were blended and kneaded with a roll mill to obtain a base having a precipitated barium sulfate concentration of 25%. 12. 21.0 parts of the precipitating barium sulfate base, 41.0 parts of the polyester resin (A), and 12.1 of the amino resin (B), which is a methylbutyl etherified benzoguanamine-melamine cocondensation resin not containing a bisphenol-derived material. 5 parts added, 10.0 parts of aluminum paste pigment (C) (Alumina paste TR-2100 manufactured by Asahi Kasei Metals Co., Ltd., average particle size 10 μm) surface-treated with acrylic resin, isobutyl acrylate homopolymer having a number average molecular weight of 6600 0.08 parts of (D), 3.0 parts of UV ink anchoring agent (E) containing hydroxyethyl acrylate as a constituent component, mixing and stirring, adjusting the viscosity with Solvesso 100, and filtering through 200 mesh, 3P metal can outer coating with non-volatile content of 40% and viscosity of 120 seconds (25 ° C, Ford Cup No. 4) To obtain a composition. Using the obtained coating composition, a coated metal plate was obtained under the same conditions as in Example 1.
（比較例１）
実施例１，２と同様に、前記ポリエステル樹脂（Ａ）を６０部に沈降性硫酸バリウム３０部、及びブチルセロソルブアセテート３０部を配合し、ロールミルで練肉し、沈降性硫酸バリウム濃度２５％のベースを得た。沈降性硫酸バリウムベース２０．０部に対し、前記ポリエステル樹脂（Ａ）を４１．０部、ビスフェノール型由来原料を含まないメチルブチルエーテル化ベンゾグアナミン−メラミン共縮合樹脂であるアミノ樹脂（Ｂ）を１２．５部添加、表面未処理のアルミペースト顔料（旭化成メタルズ社製アルミペーストＯ−２１３０、平均粒径１３μｍ）を１０．０部、数平均分子量６６００のイソブチルアクリレート単独重合体（Ｄ）を０．０８部、ヒドロキシエチルアクリレートを構成成分とするＵＶインキアンカー剤（Ｅ）を３．０部配合し混合撹拌、ソルベッソ１００で粘度調整を実施し、２００メッシュで濾過した後、不揮発分４０％、粘度１２０秒（２５℃、フォードカップＮｏ．４）の３Ｐ金属缶外面用塗料組成物を得た。得られた塗料組成物を用いて実施例１と同様の条件で塗装金属板を得た。
(Comparative Example 1)
In the same manner as in Examples 1 and 2, 60 parts of the polyester resin (A) was mixed with 30 parts of precipitated barium sulfate and 30 parts of butyl cellosolve acetate, kneaded with a roll mill, and a base having a precipitated barium sulfate concentration of 25%. Got. 12. 21.0 parts of the precipitating barium sulfate base, 41.0 parts of the polyester resin (A), and 12.1 of the amino resin (B), which is a methylbutyl etherified benzoguanamine-melamine cocondensation resin not containing a bisphenol-derived material. 5 parts added, untreated surface aluminum paste pigment (Asahi Kasei Metals Co., Ltd. aluminum paste O-2130, average particle size 13 μm) 10.0 parts, number average molecular weight 6600 isobutyl acrylate homopolymer (D) 0.08 3.0 parts of UV ink anchoring agent (E) containing hydroxyethyl acrylate as a constituent component, mixing and stirring, adjusting the viscosity with Solvesso 100, filtering through 200 mesh, 40% non-volatile content, viscosity 120 A coating composition for the outer surface of a 3P metal can with a second (25 ° C., Ford Cup No. 4) was obtained. Using the obtained coating composition, a coated metal plate was obtained under the same conditions as in Example 1.
（比較例２）
実施例１，２と同様に、前記ポリエステル樹脂（Ａ）を６０部に沈降性硫酸バリウム３０部、及びブチルセロソルブアセテート３０部を配合し、ロールミルで練肉し、沈降性硫酸バリウム濃度２５％のベースを得た。沈降性硫酸バリウムベース２０．０部に対し、前記ポリエステル樹脂（Ａ）を４１．０部、ビスフェノール型由来原料を含まないメチルブチルエーテル化ベンゾグアナミン−メラミン共縮合樹脂であるアミノ樹脂（Ｂ）を１２．５部添加、アクリル樹脂で表面処理を施したアルミペースト顔料（Ｃ）（旭化成メタルズ社製アルミペーストＴ−２１３０、平均粒径１３μｍ）を１０．０部、数平均分子量６６００のノルマルブチルアクリレート単独重合体を０．０８部、ヒドロキシエチルアクリレートを構成成分とするＵＶインキアンカー剤（Ｅ）を３．０部配合し混合撹拌、ソルベッソ１００で粘度調整を実施し、２００メッシュで濾過した後、不揮発分４０％、粘度１２０秒（２５℃、フォードカップＮｏ．４）の３Ｐ金属缶外面用塗料組成物を得た。得られた塗料組成物を用いて実施例１と同様の条件で塗装金属板を得た。
(Comparative Example 2)
In the same manner as in Examples 1 and 2, 60 parts of the polyester resin (A) was mixed with 30 parts of precipitated barium sulfate and 30 parts of butyl cellosolve acetate, kneaded with a roll mill, and a base having a precipitated barium sulfate concentration of 25%. Got. 12. 21.0 parts of the precipitating barium sulfate base, 41.0 parts of the polyester resin (A), and 12.1 of the amino resin (B), which is a methylbutyl etherified benzoguanamine-melamine cocondensation resin not containing a bisphenol-derived material. 5 parts added, 10.0 parts of aluminum paste pigment (C) (Alumina paste T-2130 manufactured by Asahi Kasei Metals Co., Ltd., average particle size 13 μm) surface-treated with an acrylic resin, and a normal butyl acrylate single weight having a number average molecular weight of 6600 After blending 0.08 parts of union and 3.0 parts of UV ink anchoring agent (E) containing hydroxyethyl acrylate as constituents, mixing and stirring, adjusting viscosity with Solvesso 100, filtering through 200 mesh, non-volatile content 40%, viscosity 120 seconds (25 ° C, Ford Cup No. 4) 3P metal can outer coating set To obtain things. Using the obtained coating composition, a coated metal plate was obtained under the same conditions as in Example 1.
（比較例３）
実施例１，２と同様に、前記ポリエステル樹脂（Ａ）を６０部に沈降性硫酸バリウム３０部、及びブチルセロソルブアセテート３０部を配合し、ロールミルで練肉し、沈降性硫酸バリウム濃度２５％のベースを得た。沈降性硫酸バリウムベース２０．０部に対し、前記ポリエステル樹脂（Ａ）を４１．０部、ビスフェノール型由来原料を含まないメチルブチルエーテル化ベンゾグアナミン−メラミン共縮合樹脂であるアミノ樹脂（Ｂ）を１２．５部添加、アクリル樹脂で表面処理を施したアルミペースト顔料（Ｃ）（旭化成メタルズ社製アルミペーストＴ−２１３０、平均粒径１３μｍ）を１０．０部、数平均分子量６６００のイソブチルアクリレート単独重合体（ｄ−１）を０．０８部配合し混合撹拌、ソルベッソ１００で粘度調整を実施し、２００メッシュで濾過した後、不揮発分４０％、粘度１２０秒（２５℃、フォードカップＮｏ．４）の３Ｐ金属缶外面用塗料組成物を得た。得られた塗料組成物を用いて実施例１と同様の条件で塗装金属板を得た。
(Comparative Example 3)
In the same manner as in Examples 1 and 2, 60 parts of the polyester resin (A) was mixed with 30 parts of precipitated barium sulfate and 30 parts of butyl cellosolve acetate, kneaded with a roll mill, and a base having a precipitated barium sulfate concentration of 25%. Got. 12. 21.0 parts of the precipitating barium sulfate base, 41.0 parts of the polyester resin (A), and 12.1 of the amino resin (B), which is a methylbutyl etherified benzoguanamine-melamine cocondensation resin not containing a bisphenol-derived material. 5 parts added, 10.0 parts of aluminum paste pigment (C) (Alumina paste T-2130 manufactured by Asahi Kasei Metals Co., Ltd., average particle size 13 μm) surface-treated with acrylic resin, isobutyl acrylate homopolymer having a number average molecular weight of 6600 0.08 parts of (d-1) was mixed, mixed and stirred, adjusted for viscosity with Solvesso 100, filtered through 200 mesh, and after 40% non-volatile content, viscosity of 120 seconds (25 ° C., Ford Cup No. 4). A coating composition for the outer surface of the 3P metal can was obtained. Using the obtained coating composition, a coated metal plate was obtained under the same conditions as in Example 1.
（評価方法）
（ＵＶインキの密着性）：ダイキュアーＮＷＢ墨インキ（大日本インキ化学工業株式会社製）をＲＩテスターで展色した後、ＵＶ照射条件：高圧水銀灯１２０Ｗ、４０ｍ/ｍｉｎの条件で硬化させ、×印セロハン粘着テープ剥離試験を行い、剥離の有無を目視評価で行った。
(Evaluation methods)
(Adhesion of UV ink): Dicure NWB black ink (manufactured by Dainippon Ink & Chemicals, Inc.) was developed with an RI tester, then cured under UV irradiation conditions: high-pressure mercury lamp 120W, 40 m / min, x mark A cellophane adhesive tape peeling test was performed, and the presence or absence of peeling was visually evaluated.
（耐レトルト性）：塗装金属板を、水を半分入れた金属容器に半浸漬し１３０℃で３０分スチーム処理を施した後の、外観の変化（塗膜の白濁・ブリスター等）を目視で評価した。 (Retort resistance): Visual observation of changes in appearance (white turbidity, blistering, etc. of coating film) after half-immersion of coated metal plate in metal container with half water and steam treatment at 130 ° C for 30 minutes evaluated.
（上塗り艶ニスの密着性）：１３０℃で３０分間スチーム処理後の塗装板の気相部・液相部を×印セロハン粘着テープ剥離試験を行い、剥離の有無を目視で判定した。 (Adhesion of top coat gloss varnish): A gas phase portion and a liquid phase portion of the coated plate after the steam treatment at 130 ° C. for 30 minutes were subjected to a x mark cellophane adhesive tape peeling test, and the presence or absence of peeling was visually determined.
（レトルト後意匠性）：１３０℃で３０分間スチーム処理後の塗装板の意匠性を目視で判定した。結果を表１に示す。 (Design property after retort): The design property of the coated plate after the steam treatment at 130 ° C. for 30 minutes was visually determined. The results are shown in Table 1.
判定基準 優れる：○−△−×：劣る ３段階評価 Judgment criteria Excellent: ○-△ -x: Inferior Three-step evaluation
結果が示すように、本発明の３Ｐ金属缶外面用塗料組成物は、耐レトルト性、・上層のＵＶインキ層、上塗り艶ニスの密着性を兼ね備えるとともに、塗膜として、高輝度シルバー色の意匠性を発揮することが出来る。 As the results show, the coating composition for the outer surface of the 3P metal can of the present invention combines retort resistance, the adhesion of the upper UV ink layer and the top coat gloss varnish, and has a high brightness silver design as a coating film. The ability to demonstrate.
本発明の３Ｐ金属缶外面用塗料組成物及び該塗料組成物の乾燥硬化塗膜を有する３Ｐ金属缶は、高輝度のシルバー色の意匠性を有し、且つ耐レトルト性に優れた塗膜層を有するため、飲食物用のＢＰＡフリー金属缶、特にレトルト条件の厳しいコーヒー飲料用３Ｐ金属缶として有用に用いられる。
The 3P metal can outer surface coating composition of the present invention and the 3P metal can having a dry-cured coating film of the coating composition have a high-intensity silver design and are excellent in retort resistance. Therefore, it is useful as a BPA-free metal can for foods and drinks, particularly as a 3P metal can for coffee beverages with severe retort conditions.
Claims (6)
The 3P metal can according to claim 4, further comprising a desired printing layer using UV ink as an upper layer of the coating composition layer for the outer surface of the 3P metal can.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006229064A JP2008050486A (en) | 2006-08-25 | 2006-08-25 | Base coat composition for outside surface of 3p metal can and 3p metal can having cured coated film layer of the composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006229064A JP2008050486A (en) | 2006-08-25 | 2006-08-25 | Base coat composition for outside surface of 3p metal can and 3p metal can having cured coated film layer of the composition |
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| Publication Number | Publication Date |
|---|---|
| JP2008050486A true JP2008050486A (en) | 2008-03-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006229064A Pending JP2008050486A (en) | 2006-08-25 | 2006-08-25 | Base coat composition for outside surface of 3p metal can and 3p metal can having cured coated film layer of the composition |
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| JP (1) | JP2008050486A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2443738C1 (en) * | 2010-06-09 | 2012-02-27 | Открытое акционерное общество "Ракетно-космическая корпорация "Энергия" имени С.П. Королева" | Thermostatic coating composition |
| CN109486309A (en) * | 2018-11-16 | 2019-03-19 | 安庆瑞泰化工有限公司 | Super siccative varnish of a kind of car repair and preparation method thereof |
| JP2023150168A (en) * | 2022-03-31 | 2023-10-16 | 大日本塗料株式会社 | Coating composition, method for producing coated metal article, and coated metal article |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2443738C1 (en) * | 2010-06-09 | 2012-02-27 | Открытое акционерное общество "Ракетно-космическая корпорация "Энергия" имени С.П. Королева" | Thermostatic coating composition |
| CN109486309A (en) * | 2018-11-16 | 2019-03-19 | 安庆瑞泰化工有限公司 | Super siccative varnish of a kind of car repair and preparation method thereof |
| JP2023150168A (en) * | 2022-03-31 | 2023-10-16 | 大日本塗料株式会社 | Coating composition, method for producing coated metal article, and coated metal article |
| JP7432645B2 (en) | 2022-03-31 | 2024-02-16 | 大日本塗料株式会社 | Coating composition, method for producing metal coatings, and metal coatings |
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