JPH05320569A - Water-based paint composition - Google Patents
Water-based paint compositionInfo
- Publication number
- JPH05320569A JPH05320569A JP12506892A JP12506892A JPH05320569A JP H05320569 A JPH05320569 A JP H05320569A JP 12506892 A JP12506892 A JP 12506892A JP 12506892 A JP12506892 A JP 12506892A JP H05320569 A JPH05320569 A JP H05320569A
- Authority
- JP
- Japan
- Prior art keywords
- water
- resin
- phosphoric acid
- parts
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水性塗料組成物に関し、
耐レトルト性、加工性、塗装性に優れ、さらには顔料分
散性に優れた水性塗料組成物に関するものである。The present invention relates to an aqueous coating composition,
The present invention relates to a water-based coating composition having excellent retort resistance, processability, paintability, and pigment dispersibility.
【０００２】[0002]
【従来の技術】清涼飲料水等を収容する飲料缶及び食品
を包装する食缶の外面は、缶材の腐食を防止し、美的商
品価値を高め、かつ食品殺菌処理時の熱処理工程に耐え
うる塗膜により被覆形成されている。従来これらの塗料
は、エポキシ／アミノ系樹脂、アクリル／アミノ系樹
脂、ポリエステル／アミノ系樹脂等の有機溶剤溶液をロ
ールコーターにて塗装し、ガスオーブンにて焼付硬化す
る方法が行われている。しかしこれらの塗料は、焼付時
に多量の溶剤揮散をもたらし、大気汚染の原因となり、
省資源の点からも好ましくない。そこでこれらの問題点
を解決可能な水性塗料の出現が望まれていた。2. Description of the Related Art The outer surface of a beverage can containing soft drinks or the like and a food can for packaging food can prevent corrosion of the can material, enhance the aesthetic value of the product, and endure the heat treatment process during food sterilization. It is formed by coating. Conventionally, these paints are coated with an organic solvent solution of an epoxy / amino resin, an acrylic / amino resin, a polyester / amino resin, or the like by a roll coater and baked and cured by a gas oven. However, these paints cause a large amount of solvent volatilization during baking, causing air pollution,
It is not preferable in terms of resource saving. Therefore, the advent of water-based paints capable of solving these problems has been desired.
【０００３】公知の水性塗料は水分散性と水溶性の２タ
イプがあり、水分散性樹脂は通常、界面活性剤を用いて
乳化重合法で合成されるものが多く、使用する界面活性
剤が塗膜形成後も塗膜中に残存し、耐水性を低下させる
欠点があった。一方、界面活性剤を使用しないで有機溶
剤系で合成し、酸分（カルボキシル基）を含む樹脂を合
成し揮発性塩基で中和し分散体ないしは水溶性とする方
法もあるが、これらの水性塗料は基本となる樹脂構造中
に酸価２０以上の酸分が必要であり、耐水性、耐水密着
性、耐レトルト性等の性能が劣る欠点があった。There are two types of known water-based paints, water-dispersible and water-soluble, and many water-dispersible resins are usually synthesized by emulsion polymerization using a surfactant, and the surfactant used is Even after the coating film is formed, it remains in the coating film, and there is a drawback that water resistance is reduced. On the other hand, there is also a method of synthesizing in an organic solvent system without using a surfactant to synthesize a resin containing an acid component (carboxyl group) and neutralizing it with a volatile base to make the dispersion or water-soluble. The coating composition has an acid value of 20 or more in the basic resin structure, and has a drawback that the performance such as water resistance, water adhesion resistance, and retort resistance is poor.
【０００４】これらの欠点を改善する方法として、種々
のエポキシ樹脂が提案されている。例えば、ポリカルボ
ン酸無水物によりカルボキシル基を導入したエポキシ樹
脂や、エポキシ樹脂とリン酸類とを反応させたエポキシ
ホスフェート等がある。しかし、前者では塗膜の耐水
性、耐水密着性、レトルト性が十分ではなく、後者は塗
膜性能は良好であるが、アクリル樹脂との相溶性が悪
く、また顔料分散安定性が著しく劣る欠点があった。Various epoxy resins have been proposed as a method for improving these drawbacks. For example, there are an epoxy resin having a carboxyl group introduced by a polycarboxylic acid anhydride, an epoxy phosphate obtained by reacting an epoxy resin with phosphoric acid, and the like. However, in the former case, the water resistance, water resistance and retort resistance of the coating film are not sufficient, and in the latter case, although the coating film performance is good, the compatibility with acrylic resin is poor and the pigment dispersion stability is extremely poor. was there.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記現状に鑑
みてなされたものであり、その目的とするところは飲料
缶、食缶殺菌処理の熱処理工程、特にレトルト処理にも
耐えうる耐熱水性を有し、缶の搬送工程で傷つきにくい
高硬度で、しかも各種缶形態に加工しうる加工性の優れ
た塗膜を被覆形成し、かつ有機溶剤量が低い缶外面用水
性塗料組成物を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide hot water resistant to a heat treatment process for sterilizing treatment of beverage cans and food cans, particularly retort treatment. Provided is a water-based coating composition for an outer surface of a can, which has a high hardness and is hard to be damaged in a can conveying process, and which forms a coating film having excellent processability that can be processed into various can forms and has a low amount of an organic solvent. It is a thing.
【０００６】[0006]
【課題を解決するための手段】本発明の要旨は、（ａ）
水性アクリル樹脂３０〜６５重量部、（ｂ）水性アミノ
樹脂３０〜６０重量部、および（ｃ）エポキシ化合物に
リン酸エステルを付加して得たリン酸変性エポキシ化合
物に、カルボキシル基含有エチレン性不飽和単量体を含
むエチレン性不飽和単量体を共重合させて得られたカル
ボキシル基含有リン酸変性エポキシ樹脂を、水溶性もし
くは水分散性に調整したリン酸変性水性エポキシ樹脂５
〜２０重量部の合計１００重量部を樹脂成分として含む
水性塗料組成物に関する。すなわち、本発明は上記の
（ａ）（ｂ）（ｃ）の各成分を組み合わせることによっ
て耐熱性、耐水性に優れた塗膜を構成することができ
る。The gist of the present invention is (a)
Aqueous acrylic resin 30 to 65 parts by weight, (b) aqueous amino resin 30 to 60 parts by weight, and (c) a phosphoric acid-modified epoxy compound obtained by adding a phosphoric acid ester to an epoxy compound are added to a carboxyl group-containing ethylenic compound. A phosphoric acid-modified aqueous epoxy resin in which a carboxyl group-containing phosphoric acid-modified epoxy resin obtained by copolymerizing an ethylenically unsaturated monomer containing a saturated monomer is adjusted to be water-soluble or water-dispersible.
The present invention relates to an aqueous coating composition containing a total of 100 parts by weight of 20 parts by weight as a resin component. That is, the present invention can form a coating film having excellent heat resistance and water resistance by combining the components (a), (b) and (c) described above.
【０００７】本発明の特徴の一つである（ｃ）成分は、
エポキシ樹脂のエポキシ基とリン酸エステルの水酸基と
を反応させてリン酸変性エポキシ樹脂とし、リン酸変性
エポキシ樹脂にアクリル変性を行って、遊離カルボキシ
ル基を含有するリン酸変性エポキシ樹脂とするのであっ
て、このアクリル変性とは、リン酸変性エポキシ樹脂に
カルボキシル基含有エチレン性不飽和単量体を付加重合
させるのである。得られた遊離カルボキシル基含有リン
酸変性エポキシ樹脂を水可溶性若しくは水分散性とする
ため、アミン等の塩基性化合物を作用させて遊離カルボ
キシル基の一部もしくは全部を中和するのである。この
ようにして得られたものがリン酸変性水性エポキシ樹脂
である。The component (c), which is one of the features of the present invention, is
The epoxy group of the epoxy resin is reacted with the hydroxyl group of the phosphoric acid ester to form a phosphoric acid-modified epoxy resin, and the phosphoric acid-modified epoxy resin is subjected to acrylic modification to form a phosphoric acid-modified epoxy resin containing a free carboxyl group. The acrylic modification is to add-polymerize a carboxyl group-containing ethylenically unsaturated monomer to a phosphoric acid-modified epoxy resin. In order to make the obtained free carboxyl group-containing phosphoric acid-modified epoxy resin water-soluble or water-dispersible, a basic compound such as amine is allowed to act to neutralize some or all of the free carboxyl groups. What was obtained in this way is a phosphoric acid-modified water-based epoxy resin.
【０００８】本発明について詳細に説明する。本発明の
（ａ）成分として用いられる水性アクリル樹脂は、アク
リル酸、フマル酸等のα・βモノエチレン不飽和カルボ
ン酸モノマーとアクリル酸メチル、アクリル酸エチル等
のアクリル酸アクリルエステル、スチレン、ビニルトル
エン等のスチレン系モノマー、アクリル酸ヒドロキシエ
チル、アクリル酸ヒドロキシプロピル等のヒドロキシ基
含有モノマーを適宜選択して共重合して得られるものな
ど広範囲のものを使用できる。α・βモノエチレン性不
飽和カルボン酸の使用量はアクリル樹脂に対して３．５
重量％以上必要であり、５〜２０重量％の範囲が最適で
ある。The present invention will be described in detail. The water-based acrylic resin used as the component (a) of the present invention includes α / β monoethylenically unsaturated carboxylic acid monomers such as acrylic acid and fumaric acid, and acrylic acid acrylic esters such as methyl acrylate and ethyl acrylate, styrene and vinyl. A wide range of substances such as those obtained by appropriately selecting and copolymerizing styrene-based monomers such as toluene and hydroxy group-containing monomers such as hydroxyethyl acrylate and hydroxypropyl acrylate can be used. The amount of α / β monoethylenically unsaturated carboxylic acid used is 3.5 with respect to the acrylic resin.
It is necessary to be at least wt%, and the range of 5 to 20 wt% is optimum.
【０００９】本発明の水性アクリル樹脂は、好ましくは
親水性有機溶剤中で上記モノマーの混合物を合成して得
られる重量平均分子量が５０００〜５００００の樹脂で
ある。 水性化するために有機溶剤中のアクリル樹脂を
アンモニア、有機アミンの存在下に水性媒体中に溶解さ
せる。有機アミンとしてはトリエチルアミン、トリエタ
ノールアミン、ジエタノールアミン、モノエタノールア
ミン、モノエチルアミン、モノメチルアミン、ジメチル
アミノエタノール等が使用できる。水性アクリル樹脂
は、全塗料組成物の樹脂固形分中３０〜６５重量部使用
する。３０重量部未満では、下地素材への密着性が低下
し、水分散性、塗料の貯蔵安定性、顔料添加時の顔料分
散性が劣る。また６５重量部以上では硬度が低下し、耐
水性も劣る。The aqueous acrylic resin of the present invention is preferably a resin having a weight average molecular weight of 5,000 to 50,000 obtained by synthesizing a mixture of the above monomers in a hydrophilic organic solvent. Acrylic resin in an organic solvent is dissolved in an aqueous medium in the presence of ammonia and an organic amine in order to make it aqueous. As the organic amine, triethylamine, triethanolamine, diethanolamine, monoethanolamine, monoethylamine, monomethylamine, dimethylaminoethanol or the like can be used. The aqueous acrylic resin is used in an amount of 30 to 65 parts by weight based on the resin solid content of the entire coating composition. If it is less than 30 parts by weight, the adhesion to the base material is lowered, and the water dispersibility, the storage stability of the coating material, and the pigment dispersibility when the pigment is added are deteriorated. If it is more than 65 parts by weight, the hardness is lowered and the water resistance is poor.
【００１０】本発明の（ｂ）成分に用いられる水性アミ
ノ樹脂は、水性媒体中に溶解もしくは分散可能なアミノ
樹脂であって、メラミン樹脂、ベンゾグアナミン樹脂、
スピログアナミン樹脂等が用いられる。水性アミノ樹脂
は全塗料組成物中３０〜６０重量部を使用する。３０重
量部以下では硬度が十分でなく、６０重量部を越えると
塗膜の加工性が低下する。The aqueous amino resin used as the component (b) of the present invention is an amino resin that can be dissolved or dispersed in an aqueous medium, and includes melamine resin, benzoguanamine resin,
Spiroguanamine resin or the like is used. The aqueous amino resin is used in an amount of 30 to 60 parts by weight in the total coating composition. If it is less than 30 parts by weight, the hardness is not sufficient, and if it exceeds 60 parts by weight, the workability of the coating film is deteriorated.
【００１１】本発明の（ｃ）成分であるリン酸変性水性
エポキシ樹脂について説明する。先ず、リン酸変性エポ
キシ樹脂を得るために用いられるエポキシ樹脂はビスフ
ェノールグリシジルエーテル型、ノボラック型エポキシ
樹脂等である。本発明に用いられるリン酸エステル化合
物はモノヒドロキシリン酸ジエステルが好ましく、ジエ
チルフォスフェート、ジブチルフォスフェート、ジオク
チルフォスフェート等が使用できる。またブチルアシッ
ドフォスフェート、イソブチルアシッドフォスフェート
等のジヒドロオキシリン酸モノエステルの混合物も使用
できる。The phosphoric acid-modified aqueous epoxy resin which is the component (c) of the present invention will be described. First, the epoxy resin used to obtain the phosphoric acid-modified epoxy resin is a bisphenol glycidyl ether type or novolac type epoxy resin. The phosphoric acid ester compound used in the present invention is preferably monohydroxyphosphoric acid diester, and diethyl phosphate, dibutyl phosphate, dioctyl phosphate and the like can be used. Further, a mixture of dihydroxyoxyphosphate monoesters such as butyl acid phosphate and isobutyl acid phosphate can also be used.
【００１２】本発明のエポキシ樹脂とリン酸エステルの
反応は無溶剤、もしくは有機溶剤の存在下、７０〜１５
０℃の範囲で行われる。反応は発熱を伴う為、エポキシ
樹脂にリン酸エステルを３０分から２時間かけて徐々に
加えていく方法が適している。エポキシ樹脂とリン酸エ
ステルの反応比率はエポキシ基１当量に対しリン酸エス
テルの酸当量が０．３〜０．８の範囲が好ましい。０．
３以下では密着性、レトルト性が低下する。０．８以上
では未反応のリン酸エステルが残り塗料の安定性が低下
する。エポキシ樹脂とリン酸エステルの反応は当該リン
酸変性エポキシ樹脂の酸価が１０ｍｇＫＯＨ／ｇ以下に
なる迄行う。酸価が１０ｍｇＫＯＨ／ｇ以上になると塗
料安定性が低下する。当該リン酸変性エポキシ樹脂のリ
ン含有量は１〜１０％が好ましく１％以下では密着性、
レトルト性が劣り、また１０％以上にしても加えただけ
の効果が得られない。より好ましくは、３〜８％の範囲
である。尚、反応後にエポキシ基が多く残存するとアク
リルモノマーと共重合させる際に耐加水分解性に劣るエ
ステル化が生ずるため、反応後のオキシラン酸素含有量
を０．８％以下とすることが好ましいが、０．８％以上
の場合にはアルキルフェノール、３級脂肪酸、モノカル
ボン酸等と反応させても良い。The reaction between the epoxy resin of the present invention and the phosphoric acid ester is carried out without solvent or in the presence of an organic solvent at 70 to 15
It is carried out in the range of 0 ° C. Since the reaction is exothermic, a method of gradually adding the phosphoric acid ester to the epoxy resin over 30 minutes to 2 hours is suitable. The reaction ratio of the epoxy resin and the phosphoric acid ester is preferably such that the acid equivalent of the phosphoric acid ester is 0.3 to 0.8 with respect to 1 equivalent of the epoxy group. 0.
When it is 3 or less, the adhesiveness and retortability are deteriorated. When it is 0.8 or more, unreacted phosphoric acid ester remains and the stability of the coating composition decreases. The reaction between the epoxy resin and the phosphoric acid ester is carried out until the acid value of the phosphoric acid-modified epoxy resin becomes 10 mgKOH / g or less. When the acid value is 10 mgKOH / g or more, the stability of the coating composition is reduced. The phosphorus content of the phosphoric acid-modified epoxy resin is preferably 1 to 10%, and when the content is 1% or less, the adhesiveness is
The retort property is inferior, and even if it is 10% or more, the effect just added cannot be obtained. More preferably, it is in the range of 3 to 8%. Incidentally, if many epoxy groups remain after the reaction, esterification which is inferior in hydrolysis resistance occurs when copolymerizing with an acrylic monomer, so it is preferable to set the oxirane oxygen content after the reaction to 0.8% or less, When it is 0.8% or more, it may be reacted with an alkylphenol, a tertiary fatty acid, a monocarboxylic acid or the like.
【００１３】次に、得られたリン酸変性エポキシ樹脂に
有機溶剤溶液中でフリーラジカル発生剤の存在下にカル
ボキシル基含有エチレン性不飽和単量体を重合させてカ
ルボキシル基含有リン酸変性エポキシ樹脂とする。カル
ボキシル基含有エチレン性不飽和単量体とは、カルボキ
シル基を含有するエチレン性不飽和カルボン酸を必須成
分とし、これに必要に応じて他のエチレン性不飽和単量
体を含有させたものである。使用するカルボキシル基を
含有するエチレン性不飽和カルボン酸としては、アクリ
ル酸、メタクリル酸、フマル酸等があり、他のエチレン
性不飽和単量体としては、アクリル酸メチル、アクリル
酸エチル等のアクリル酸エステル、スチレン、ビニルト
ルエン等のスチレン系モノマー、アクリル酸ヒドロキシ
エチル、アクリル酸ヒドロキシプロピル等のヒドロキシ
ル基含有モノマーがある。カルボキシル基含有エチレン
性不飽和単量体中にエチレン性不飽和カルボン酸を３％
以上含有させることが好ましい。カルボキシル基含有エ
チレン性不飽和単量体はリン酸変性エポキシ樹脂１００
重量部に対し１０〜４０重量部が使用される。Next, the obtained phosphoric acid-modified epoxy resin is polymerized with a carboxyl group-containing ethylenically unsaturated monomer in the presence of a free radical generator in an organic solvent solution to obtain a carboxyl group-containing phosphoric acid-modified epoxy resin. And The carboxyl group-containing ethylenically unsaturated monomer is a monomer containing an ethylenically unsaturated carboxylic acid containing a carboxyl group as an essential component and other ethylenically unsaturated monomer as necessary. is there. Examples of the ethylenically unsaturated carboxylic acid containing a carboxyl group to be used include acrylic acid, methacrylic acid and fumaric acid, and other ethylenically unsaturated monomers include acrylic acid such as methyl acrylate and ethyl acrylate. Examples include acid ester, styrene-based monomers such as styrene and vinyltoluene, and hydroxyl group-containing monomers such as hydroxyethyl acrylate and hydroxypropyl acrylate. 3% ethylenically unsaturated carboxylic acid in carboxyl group-containing ethylenically unsaturated monomer
It is preferable to contain the above. Carboxyl group-containing ethylenically unsaturated monomer is phosphoric acid-modified epoxy resin 100
10 to 40 parts by weight are used relative to parts by weight.
【００１４】本発明のリン酸変性エポキシ樹脂のアクリ
ル変性は、カルボキシル基含有エチレン性単量体を３重
量％以上含むエチレン性不飽和単量体を重合して得られ
たアクリル系樹脂をリン酸変性エポキシ樹脂溶液中で反
応させることにより得ることもできる。上記で得られた
カルボキシル基含有リン酸変性エポキシ樹脂を水溶性も
しくは水分散性に調整するには、当該カルボキシル基含
有リン酸変性エポキシ樹脂をアミンまたはアンモニア等
塩基性化合物で中和する。この調整には、十分な水溶性
または水分散性が得られる様にカルボキシル基含有リン
酸変性エポキシ樹脂の酸価は３０ｍｇＫＯＨ／ｇ以上で
あることが望ましい。しかしながら、酸価が１５０ｍｇ
ＫＯＨ／ｇ以上になると耐水性が低下してくる為、酸価
は５０〜１００ｍｇＫＯＨ／ｇの範囲が好ましい。Acrylic modification of the phosphoric acid-modified epoxy resin of the present invention is carried out by polymerizing an acrylic resin obtained by polymerizing an ethylenically unsaturated monomer containing 3% by weight or more of a carboxyl group-containing ethylenic monomer with phosphoric acid. It can also be obtained by reacting in a modified epoxy resin solution. In order to adjust the carboxyl group-containing phosphoric acid modified epoxy resin obtained above to be water-soluble or water-dispersible, the carboxyl group-containing phosphoric acid modified epoxy resin is neutralized with a basic compound such as amine or ammonia. For this adjustment, the acid value of the carboxyl group-containing phosphoric acid-modified epoxy resin is preferably 30 mgKOH / g or more so that sufficient water solubility or water dispersibility can be obtained. However, the acid value is 150 mg
When the KOH / g or more, the water resistance decreases, so the acid value is preferably in the range of 50 to 100 mgKOH / g.
【００１５】この方法で得られたリン酸変性水性エポキ
シ樹脂は、塗料組成物中の５〜２０重量部使用する。５
重量部未満では塗膜の密着性が劣り、耐レトルト性、加
工性が劣る。２０重量部以上では他の樹脂との相溶性が
低下し塗料安定性、塗装性が低下する。The phosphoric acid-modified aqueous epoxy resin obtained by this method is used in an amount of 5 to 20 parts by weight in the coating composition. 5
If it is less than the weight part, the adhesion of the coating film is poor and the retort resistance and processability are poor. If it is 20 parts by weight or more, the compatibility with other resins decreases, and the paint stability and paintability decrease.
【００１６】本発明の水性塗料組成物は、樹脂成分を水
性媒体中に溶解もしくは分散させたものである。水性媒
体としては、水を主成分とし少なくとも５重量部の親水
性有機溶剤量を含むものである。親水性有機溶剤として
は、ブチルセロソルブ、ヘキシルセロソルブ、プロピレ
ングリコールメチルエーテル、プロピレングリコールブ
チルエーテル、ジエチレングリコールメチルエーテル、
ジエチレングリコールブチルエーテル等がある。親水性
有機溶剤の含有量は２０重量％以下が好ましい。 本発
明の水性塗料組成物には必要に応じて硬化助剤としてア
ミンブロックした酸触媒例えばｐ−トルエンスルホン
酸、ドデシルベンゼンスルホン酸、ジノニルナフタレン
ジスルホン酸等を樹脂固形分１００重量部に対し０．１
〜２重量部を添加して塗料化する。The aqueous coating composition of the present invention comprises a resin component dissolved or dispersed in an aqueous medium. The aqueous medium contains water as a main component and contains at least 5 parts by weight of a hydrophilic organic solvent. As the hydrophilic organic solvent, butyl cellosolve, hexyl cellosolve, propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol methyl ether,
Examples include diethylene glycol butyl ether. The content of the hydrophilic organic solvent is preferably 20% by weight or less. In the water-based coating composition of the present invention, if necessary, an amine-blocked acid catalyst such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalene disulfonic acid or the like is used as a curing aid in an amount of 0 based on 100 parts by weight of the resin solid content. .1
Add ~ 2 parts by weight to make a paint.
【００１７】また水性塗料用樹脂として一般的に用いら
れている水溶性樹脂、水分散性樹脂、例えば、水溶性ポ
リエステル樹脂、マレイン化脂肪酸、ポリオールなどを
混合することも可能である。また、同様にレベリング
剤、消泡剤、潤滑剤を添加することもできる。また、顔
料を前記アクリル樹脂の溶液と練肉して顔料ペーストを
作成し、前述と同様の方法で塗料化することができる。It is also possible to mix a water-soluble resin or water-dispersible resin, which is generally used as a resin for water-based paints, such as a water-soluble polyester resin, maleated fatty acid or polyol. Similarly, a leveling agent, a defoaming agent, and a lubricant can be added. Further, the pigment can be kneaded with the acrylic resin solution to prepare a pigment paste, which can be made into a paint by the same method as described above.
【００１８】本発明の水性塗料はロールコート、スプレ
ー、はけ塗り等の公知の手段により基材に塗装する事が
できる。基材としては、電気スズメッキ鋼板、ティンフ
リースチール、アルミニウムなどの金属基材がある。ま
た本発明の水性塗料は、１５０〜２００℃−１０分間程
度の焼き付けから２５０℃−１０秒程度の高温短時間焼
き付けまで幅広い焼き付け条件で硬化させることができ
る。The water-based paint of the present invention can be applied to a substrate by a known means such as roll coating, spraying or brush coating. As the base material, there are metal base materials such as electric tin-plated steel plate, tin-free steel and aluminum. Further, the water-based paint of the present invention can be cured under a wide range of baking conditions from baking at 150 to 200 ° C for about 10 minutes to short baking at high temperature for about 250 ° C for 10 seconds.
【００１９】[0019]
【実施例】以下実施例により本発明を説明する。例中、
部とは重量部を、％とは重量％をそれぞれ表す。 製造例１ 水性アクリル樹脂溶液Ａ１の製造 温度計、攪拌機、還流冷却器、滴下槽、窒素ガス吹込管
を備えた四口フラスコにブチルセロソルブ１００部を仕
込み、窒素ガスを導入しつつかきまぜながら温度を１０
５℃に保ち、滴下槽からスチレン３０％、エチルアクリ
レート３０％、ブチルアクリレート１０％、２−ヒドロ
キシエチルアクリレート１０％、メチルメタクリレート
１０％、アクリル酸１０％の混合物１００部に過酸化ベ
ンゾイル５部を溶解させたものを３時間にわたって滴下
した。その後１０５℃に保ち１時間反応し、過酸化ベン
ゾイル０．５部を添加し、更に１時間反応させて終了し
た。これを減圧下１００℃でブチルセロソルブを不揮発
分８３％になるまで留去し、その後、ジエタノールアミ
ン１４．６部と水を入れ固形分５０％、残留ブチルセロ
ソルブ１０％の透明で粘調な水性アクリル樹脂Ａ１を得
た。EXAMPLES The present invention will be described below with reference to examples. In the example,
Parts are parts by weight, and% is% by weight. Production Example 1 Production of Aqueous Acrylic Resin Solution A1 100 parts of butyl cellosolve was charged into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping tank, and a nitrogen gas blowing tube, and the temperature was adjusted to 10 while stirring while introducing nitrogen gas.
Keeping at 5 ° C., add 5 parts of benzoyl peroxide to 100 parts of a mixture of 30% styrene, 30% ethyl acrylate, 10% butyl acrylate, 10% 2-hydroxyethyl acrylate, 10% methyl methacrylate and 10% acrylic acid from a dropping tank. The dissolved product was added dropwise over 3 hours. Thereafter, the temperature was kept at 105 ° C., the reaction was carried out for 1 hour, 0.5 part of benzoyl peroxide was added, and the reaction was further continued for 1 hour to complete the reaction. Butyl cellosolve was distilled off under reduced pressure at 100 ° C. until the nonvolatile content became 83%, and then 14.6 parts of diethanolamine and water were added to the mixture to give a transparent and viscous aqueous acrylic resin A1 containing 50% solids and 10% residual butylcellosolve. Got
【００２０】製造例２ 水性アクリル樹脂溶液Ａ２の製
造 製造例１に従って、スチレン１５％、エチルアクリレー
ト２０％、２−ヒドロキシエチルアクリレート１５％、
メチルメタアクリレート３５％、メタアクリル酸１５％
のモノマー組成にて同様に重合させ、水性アクリル樹脂
溶液Ａ２を得た。Production Example 2 Production of Aqueous Acrylic Resin Solution A2 According to Production Example 1, styrene 15%, ethyl acrylate 20%, 2-hydroxyethyl acrylate 15%,
Methyl methacrylate 35%, methacrylic acid 15%
Polymerization was performed in the same manner with the above monomer composition to obtain an aqueous acrylic resin solution A2.
【００２１】製造例３ リン酸変性水性エポキシ樹脂溶
液Ｂ１の製造 温度計、攪拌機、還流冷却器、滴下缶を備えた反応器に
エピコート８２８（シェルエポキシ社製エポキシ樹脂エ
ポキシ当量１８６ｇ／ｅｑ）３００部を入れ１０５℃に
加熱し、次にジブチルフォスフェート２４３部を１時間
かけて滴下する。その後、更に１時間反応して酸価を４
ｍｇＫＯＨ／ｇ、オキシラン酸素含有量を０．３％、数
平均分子量１４００の生成物を得た。次にブチルセロソ
ルブ１２５部を加え１００℃で溶解する。この溶液にあ
らかじめアクリル酸５０部、スチレン３０部、ベゾイル
パーオキサイド５部混合したものを１時間かけて滴下
し、その後１００℃で更に反応を行いアクリル変性を行
った。次にジメチルアミノエタノール６２部で中和しさ
らに水４３１部を加え固形分５０％、ブチルセロソルブ
１０％の透明で粘調なリン酸変性水性エポキシ樹脂溶液
Ｂ１を得た。Production Example 3 Production of Phosphoric Acid-Modified Aqueous Epoxy Resin Solution B1 300 parts of Epicoat 828 (epoxy resin epoxy equivalent of Shell Epoxy Equivalent 186 g / eq) was placed in a reactor equipped with a thermometer, a stirrer, a reflux condenser and a dropping can. Is heated to 105 ° C., and then 243 parts of dibutyl phosphate is added dropwise over 1 hour. After that, the reaction is continued for another hour to increase the acid value to 4
A product having mgKOH / g, an oxirane oxygen content of 0.3% and a number average molecular weight of 1400 was obtained. Next, 125 parts of butyl cellosolve is added and dissolved at 100 ° C. A mixture of 50 parts of acrylic acid, 30 parts of styrene, and 5 parts of bezoyl peroxide was added dropwise to this solution over 1 hour, and then the reaction was further performed at 100 ° C. for acrylic modification. Next, it was neutralized with 62 parts of dimethylaminoethanol and further 431 parts of water was added to obtain a transparent and viscous phosphoric acid-modified aqueous epoxy resin solution B1 having a solid content of 50% and butyl cellosolve of 10%.
【００２２】製造例４ リン酸変性水性エポキシ樹脂溶
液Ｂ２の製造 製造例３と同様に、エピコート８２８を３００部、ジオ
クチルフォスフェート２４３部を反応し、酸価３ｍｇＫ
ＯＨ／ｇとした後、この樹脂をブチルセロソルブで溶解
し、この溶液にメタクリル酸５０部、スチレン２０部、
ヒドロキシエチルアクリレート１０部、ベンゾイルパー
オキサイド３部混合したものを滴下反応し次にジメチル
アミノエタノール５２部で中和し、さらに水を加え固形
分５０％、ブチルセロソルブ１０％の透明で粘調なリン
酸変性水性エポキシ樹脂溶液Ｂ２を得た。Production Example 4 Production of Phosphoric Acid-Modified Aqueous Epoxy Resin Solution B2 In the same manner as in Production Example 3, 300 parts of Epicoat 828 and 243 parts of dioctyl phosphate were reacted to give an acid value of 3 mgK.
After adjusting to OH / g, the resin was dissolved in butyl cellosolve, and 50 parts of methacrylic acid and 20 parts of styrene were added to the solution.
A mixture of 10 parts of hydroxyethyl acrylate and 3 parts of benzoyl peroxide was added dropwise to the reaction mixture, which was then neutralized with 52 parts of dimethylaminoethanol, and water was added to the mixture to give a transparent and viscous phosphoric acid having a solid content of 50% and butyl cellosolve of 10%. A modified aqueous epoxy resin solution B2 was obtained.
【００２３】製造例５ 水性エポキシ樹脂溶液Ｃ１の製
造 製造例３と同様の反応器にエピコート８２８を３００部
に安息香酸２４１部を加え１５０℃で５時間反応した
後、１００℃に冷却し、ブチルセロソルブ１２４部に溶
解し、次にこの溶液にアクリル酸５０部、スチレン３０
部、ベンゾイルパーオキサイド５部をあらかじめ混合し
たものを滴下反応し、次にジメチルアミノエタノール６
２部で中和しさらに水４３０部を加え固形分５０％、ブ
チルセロソルブ１０％の水性エポキシ樹脂溶液Ｃ１を得
た。Production Example 5 Production of Aqueous Epoxy Resin Solution C1 300 parts of Epikote 828 and 241 parts of benzoic acid were added to the same reactor as in Production Example 3 and reacted at 150 ° C. for 5 hours, followed by cooling to 100 ° C. and butyl cellosolve. Dissolve in 124 parts, then add 50 parts of acrylic acid and 30 parts of styrene to this solution.
And 5 parts of benzoyl peroxide were mixed in advance to carry out a reaction, and then dimethylaminoethanol 6
The mixture was neutralized with 2 parts and 430 parts of water was further added to obtain an aqueous epoxy resin solution C1 having a solid content of 50% and butyl cellosolve of 10%.
【００２４】製造例６ 水性エポキシ樹脂溶液Ｃ２の製
造 製造例３と同様の反応器にエピコート８２８を２００ブ
チルセロソルブ６０部をいれて１００に昇温後、ブチル
アシッドフォスフェート１００部を１時間かけて滴下し
その後２時間反応を行い酸価９０ｍｇＫＯＨ／ｇのエポ
キシフォスフェートを得た。次にジメチルアミノエタノ
ール４３部で中和し更に水１９７部加え固形分５０％、
ブチルセロソルブ１０％の水性エポキシ樹脂溶液Ｃ２を
得た。Production Example 6 Production of Aqueous Epoxy Resin Solution C2 In a reactor similar to that of Production Example 3, 200 parts of 200 butyl cellosolve was added to Epicoat 828, the temperature was raised to 100, and 100 parts of butyl acid phosphate was added dropwise over 1 hour. Then, the reaction was continued for 2 hours to obtain an epoxy phosphate having an acid value of 90 mgKOH / g. Next, it was neutralized with 43 parts of dimethylaminoethanol and further added with 197 parts of water to obtain a solid content of 50%.
A 10% aqueous epoxy resin solution C2 of butyl cellosolve was obtained.
【００２５】実施例１〜４ 表１に従って各成分を混合した後、（但し、実施例２に
おいてはアクリル樹脂と顔料を先に練肉した。）ブチル
セロソルブ及び水を添加して塗料中の有機溶剤量を１０
％、固形分を４０％に調整した。（但し、実施例２では
固形分を６０％とした。）表１は各成分の固形分の比を
百分率にて示したものである。これにｐ−トルエンスル
ホン酸アミン塩０．３％、レベリング剤を０．３％添加
して水性塗料を得た。この塗料をナチュラルコーターに
て板厚０．２３ｍｍの電気メッキブリキに塗装し、１９
０℃１０分間焼き付け硬化させた。膜厚は６〜８μであ
った。サイメル１１２３は三井サイアナミド社製ベンゾ
グアナミン樹脂である。Examples 1 to 4 After mixing the components according to Table 1, (but in Example 2, the acrylic resin and the pigment were first kneaded), butyl cellosolve and water were added and the organic solvent in the coating composition was added. Quantity 10
%, And the solid content was adjusted to 40%. (However, in Example 2, the solid content was 60%.) Table 1 shows the ratio of the solid content of each component in percentage. To this, 0.3% of p-toluenesulfonic acid amine salt and 0.3% of a leveling agent were added to obtain an aqueous paint. Apply this paint to a 0.23 mm thick electroplated tin plate with a natural coater.
It was baked and cured at 0 ° C. for 10 minutes. The film thickness was 6 to 8 µ. Cymel 1123 is a benzoguanamine resin manufactured by Mitsui Cyanamid.
【００２６】比較例１〜３ 表１にしたがって各成分を混合し、実施例１〜４と同様
の操作で水性塗料を得た。この塗料用いて、実施例１〜
４と同様の操作で塗装板を得た。実施例及び比較例で作
成した塗料の安定性及び塗膜物性について調べた結果を
表２に示した。Comparative Examples 1 to 3 The components were mixed according to Table 1, and the same procedure as in Examples 1 to 4 was carried out to obtain water-based paints. Using this paint, Examples 1 to 1
A coated plate was obtained by the same operation as in 4. Table 2 shows the results of examining the stability and coating film physical properties of the coating materials prepared in Examples and Comparative Examples.
【００２７】表２における各試験方法は下記の通りであ
る。 塗料試験 ○塗料安定性試験 塗料を２カ月間常温で保存した後、塗料中の樹脂のゲル
化分離の状態を観察した。 ○塗膜物性試験 板厚０．２３ｍｍの電気メッキブリキにロールコート塗
装により乾燥後塗膜厚７μになるように塗装し、ガスオ
ーブンにて雰囲気温度１９０℃において１０分間焼き付
けパネルを作成した。傷付き性については塗装板を塗装
面が缶外面となるようにして成形した３ピース缶を作成
して評価した。 ○耐水性試験 塗装パネルを水中に浸漬し、１００℃−３０分間熱処理
を行った後、塗膜の白化状態を評価した。The test methods in Table 2 are as follows. Paint test ○ Paint stability test After the paint was stored at room temperature for 2 months, the state of gelation separation of the resin in the paint was observed. ○ Physical property test of coating film An electroplated tin plate having a plate thickness of 0.23 mm was coated with a roll coat to a coating film thickness of 7 µ after drying, and a baking panel was prepared in a gas oven at an atmospheric temperature of 190 ° C for 10 minutes. The scratch resistance was evaluated by preparing a 3-piece can in which a coated plate was formed so that the coated surface was the outer surface of the can. ○ Water resistance test The coated panel was immersed in water and heat-treated at 100 ° C for 30 minutes, and then the whitening state of the coating film was evaluated.
【００２８】○加工性試験 エリクセン試験：ＪＩＳＺ−２２４７に準じ、下地の金
属板が割れ始めるところまで押し出し加工した後、塗膜
の状態を評価した。 ○耐衝撃性デュポン衝撃試験機を用いて、１／２インチ
径の撃針を試料上に接触させた後、５００ｇｒの錘を落
下させる。塗膜にクラックが生じない高さにより耐衝撃
性を評価した。 ○鉛筆硬度試験 ＪＩＳ規格「鉛筆引っかき試験」（ＪＩＳＮｏ．Ｋ５４
００）に登録されている方法に準じて行った。Workability test Erichsen test: According to JISZ-2247, extrusion processing was performed until the base metal plate started to crack, and then the state of the coating film was evaluated. ○ Impact resistance Using a DuPont impact tester, a firing needle having a diameter of 1/2 inch is brought into contact with the sample, and then a weight of 500 gr is dropped. Impact resistance was evaluated by the height at which the coating film did not crack. ○ Pencil hardness test JIS standard “pencil scratch test” (JIS No. K54
It was performed according to the method registered in (00).
【００２９】○密着性試験 碁盤目ハクリ試験を行った。 ○傷付き性 缶に内容物を詰め、８０℃温水中で缶外面を接触させて
塗膜の傷付き性の程度を評価した。 ○フロー ロールコーターにて塗装後直ちにガスオーブンにて焼き
付け、レベリング状態を評価した。○ Adhesion test A cross-cut peeling test was conducted. ○ Scratchability The contents were packed in a can, and the outer surface of the can was brought into contact in 80 ° C warm water to evaluate the degree of scratchability of the coating film. ○ Immediately after coating with a flow roll coater, baking was performed in a gas oven to evaluate the leveling state.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【発明の効果】本発明の水性塗料組成物は、塗膜の耐レ
トルト性、加工性に優れている。また顔料添加時の顔料
分散性に優れ、塗料の貯蔵経時安定性が良好であった。The aqueous coating composition of the present invention has excellent retort resistance and processability of the coating film. Further, the pigment dispersibility was excellent when the pigment was added, and the storage stability of the paint was good.
Claims (1)
部、 （ｂ）水性アミノ樹脂３０〜６０重量部、および、 （ｃ）エポキシ化合物にリン酸エステルを付加して得た
リン酸変性エポキシ化合物に、カルボキシル基含有エチ
レン性不飽和単量体を含むエチレン性不飽和単量体共重
合させて得られたカルボキシル基含有リン酸変性エポキ
シ樹脂を、水溶性もしくは水分散性に調整したリン酸変
性水性エポキシ樹脂５〜２０重量部の合計１００重量部
を樹脂成分として含む水性塗料組成物。1. A phosphoric acid-modified epoxy obtained by adding a phosphoric acid ester to (a) an aqueous acrylic resin 30 to 65 parts by weight, (b) an aqueous amino resin 30 to 60 parts by weight, and (c) an epoxy compound. Compound, a carboxyl group-containing phosphoric acid-modified epoxy resin obtained by copolymerizing an ethylenically unsaturated monomer containing a carboxyl group-containing ethylenically unsaturated monomer, a phosphoric acid adjusted to be water-soluble or water-dispersible An aqueous coating composition containing 5 to 20 parts by weight of a modified aqueous epoxy resin as a resin component in a total of 100 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12506892A JP2819941B2 (en) | 1992-05-18 | 1992-05-18 | Aqueous paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12506892A JP2819941B2 (en) | 1992-05-18 | 1992-05-18 | Aqueous paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05320569A true JPH05320569A (en) | 1993-12-03 |
| JP2819941B2 JP2819941B2 (en) | 1998-11-05 |
Family
ID=14901030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12506892A Expired - Fee Related JP2819941B2 (en) | 1992-05-18 | 1992-05-18 | Aqueous paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2819941B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136927A (en) * | 1997-09-24 | 2000-10-24 | Ppg Industries Ohio, Inc. | Phosphatized amine chain-extended epoxy polymeric compounds |
| JP2001139766A (en) * | 1999-11-16 | 2001-05-22 | Dainippon Ink & Chem Inc | Method for producing aqueous dispersion of thermoset resin, and water-based coating agent of thermoset resin |
| JP2003534395A (en) * | 1999-12-16 | 2003-11-18 | イー．アイ． デュ ポン ドゥ ネモアー アンド カンパニー | Anodic electrophoretic enamelling method and electrophoretic paint |
| US7060327B2 (en) * | 2003-11-13 | 2006-06-13 | Henkel Corporation | Corrosion protective methacrylate adhesives for galvanized steel and other metals |
| CN112898859A (en) * | 2019-11-19 | 2021-06-04 | 湖南崀山家俱有限公司 | Environment-friendly paint baking finish process |
-
1992
- 1992-05-18 JP JP12506892A patent/JP2819941B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136927A (en) * | 1997-09-24 | 2000-10-24 | Ppg Industries Ohio, Inc. | Phosphatized amine chain-extended epoxy polymeric compounds |
| JP2001139766A (en) * | 1999-11-16 | 2001-05-22 | Dainippon Ink & Chem Inc | Method for producing aqueous dispersion of thermoset resin, and water-based coating agent of thermoset resin |
| JP2003534395A (en) * | 1999-12-16 | 2003-11-18 | イー．アイ． デュ ポン ドゥ ネモアー アンド カンパニー | Anodic electrophoretic enamelling method and electrophoretic paint |
| US7060327B2 (en) * | 2003-11-13 | 2006-06-13 | Henkel Corporation | Corrosion protective methacrylate adhesives for galvanized steel and other metals |
| US8304024B2 (en) | 2003-11-13 | 2012-11-06 | Henkel Corporation | Corrosion protective methacrylate adhesives for galvanized steel and other metals |
| CN112898859A (en) * | 2019-11-19 | 2021-06-04 | 湖南崀山家俱有限公司 | Environment-friendly paint baking finish process |
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|---|---|
| JP2819941B2 (en) | 1998-11-05 |
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