JPH0788492B2 - Aqueous coating composition - Google Patents
Aqueous coating compositionInfo
- Publication number
- JPH0788492B2 JPH0788492B2 JP61258555A JP25855586A JPH0788492B2 JP H0788492 B2 JPH0788492 B2 JP H0788492B2 JP 61258555 A JP61258555 A JP 61258555A JP 25855586 A JP25855586 A JP 25855586A JP H0788492 B2 JPH0788492 B2 JP H0788492B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- parts
- weight
- paint
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用分野） 本発明は，水酸基含有アルキル（メタ）アクリレート
と，グリコールもしくはポリオキシアルキレングリコー
ルのジ（メタ）アクリレートと，α・βモノエチレン性
不飽和カルボン酸と，これらと共重合可能なビニルモノ
マーからなる共重合体を有機アミン等で水性化せしめた
水性樹脂に，水性のアミノプラスト樹脂を配合した塗料
組成物に関し，特に耐水性，グロスに優れ溶剤の含有量
を低減させることができる水性塗料組成物に関する。Detailed Description of the Invention [Object of the Invention] (Field of Industrial Application) The present invention relates to a hydroxyl group-containing alkyl (meth) acrylate, a di (meth) acrylate of glycol or polyoxyalkylene glycol, and an α / β mono Coating composition in which a water-based aminoplast resin is mixed with a water-based resin obtained by hydrolyzing a copolymer composed of an ethylenically unsaturated carboxylic acid and a vinyl monomer copolymerizable therewith with an organic amine, etc. The present invention relates to an aqueous coating composition which is excellent in gloss and can reduce the content of a solvent.
（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なわれ
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る。(Prior Art) The outer surface of a beverage can containing soft drinks or the like and a food can for packaging food prevents corrosion of the can material and enhances aesthetic product value.
Moreover, it is formed by coating with a coating film that can withstand the heat treatment step during food sterilization. Traditionally these paints are epoxy /
A method of coating an organic solvent solution of an amino resin, an acrylic / amino resin, a polyester / amino resin, or the like with a roll coater and baking and curing in a gas oven is used. However, these paints cause a large amount of solvent volatilization at the time of baking, causing air pollution, which is not preferable from the viewpoint of resource saving. Therefore, the advent of water-based paints that can solve these problems is desired.
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浮化重合法で
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，耐アルカリ性等の性能
が劣り，塗膜としての基本性能に欠けるという欠点があ
った。There are two types of known water-based paints: water dispersible and water soluble.
Water-dispersible resins are usually synthesized by a floating polymerization method using a surfactant, and the surfactant used remains in the coating film even after the coating film is formed, and there is a drawback that water resistance is reduced. there were. On the other hand, there is also a method of synthesizing a resin containing an acid component (carboxyl group) by synthesizing in an organic solvent system without using a surfactant and neutralizing with a volatile base to make the dispersion or water-soluble.
These water-based paints have a drawback in that the basic resin structure requires an acid content of 20 or more, and the performances such as water resistance and alkali resistance are inferior, and the basic performance as a coating film is lacking.
さらに上記の如き欠点を回避すべくポリエチレングリコ
ールのモノ（メタアクリレート）のようなグリコールの
モノアクリルエステルを使用することによりα・βモノ
エチレン性不飽和カルボン酸の使用量を３〜10％に低下
させた水性塗料の提案がされた（特公昭52−1735号公
報）。この水性塗料は耐水性が向上し，耐アルカリ性，
防錆力にも優れるという利点を有しているが，飲料缶，
食缶等の食品殺菌処理における沸水,117℃〜125℃のレ
トルト等の厳しい熱処理による塗膜の軟化，ブリスター
発生，グロスの低下等の塗膜物性に劣るという欠点があ
った。更に飲料缶，食缶等の外面は缶材の美的商品価値
を高めるためにグロスの優れた塗膜を被覆形成する必要
があるが，上記塗料はこのようなグロスを満足させるレ
ベルまでには至っていない。Furthermore, in order to avoid the above-mentioned drawbacks, the amount of α / β monoethylenically unsaturated carboxylic acid used is reduced to 3 to 10% by using a monoacrylic ester of glycol such as mono (methacrylate) of polyethylene glycol. The proposed water-based paint was proposed (Japanese Patent Publication No. 52-1735). This water-based paint has improved water resistance, alkali resistance,
Although it has the advantage of excellent rust prevention,
It has the drawback of poor coating film physical properties such as softening of coating film, blistering, and loss of gloss due to severe heat treatment such as boiling water and retort at 117 ° C to 125 ° C in food sterilization of food cans. In addition, the outer surface of beverage cans, food cans, etc. must be coated with a coating with excellent gloss in order to enhance the aesthetic commercial value of the can material. Not in.
また従来の水溶性塗料は，塗料の貯蔵安定性及び塗膜形
成におけるレベリング性向上のために有機溶剤を10重量
％以上含んでおり，焼付時における溶剤揮散による大気
汚染及び省資源の点でまだ不充分であった。In addition, the conventional water-soluble paint contains 10% by weight or more of organic solvent to improve the storage stability of the paint and the leveling property in coating film formation, and it is still in view of air pollution and resource saving due to solvent volatilization during baking. It was not enough.
（発明が解決しようとする問題点） 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，食缶等の食品殺菌処理時
の熱処理工程にも耐えうる耐水性を有し，缶材の美的商
品価値を高めるグロスの優れた塗膜を被覆形成し，かつ
有機溶剤含有量が低い水性塗料組成物を提供するもので
ある。(Problems to be Solved by the Invention) The present invention has been made in view of the above circumstances, and an object thereof is to be able to withstand a heat treatment step during food sterilization treatment of beverage cans, food cans, and the like. It is intended to provide a water-based coating composition which has water resistance, forms a coating film with excellent gloss that enhances the aesthetic commercial value of a can material, and has a low organic solvent content.
（問題点を解決するための手段） すなわち本発明は，水可溶成分であるポリオキシアルキ
レングリコールもしくはアルキレングリコールのジアク
リレートもしくはジメタクリレートを前架橋成分とし，
親水成分である炭素数が１〜５のヒドロキシアルキルア
クリレートまたはメタクリレートを硬化架橋成分とし，
水可溶化のためのα・βモノエチレン性不飽和カルボン
酸成分を低減したアクリル共重合体を作成し水性樹脂と
した上で，水性アミノプラスト樹脂を混合することによ
り，耐水性，グロスが優れ，有機溶剤の低減化が可能で
あることを見い出し，本発明を完成するに至った。(Means for Solving Problems) That is, in the present invention, a water-soluble component such as polyoxyalkylene glycol or diacrylate or dimethacrylate of alkylene glycol is used as a pre-crosslinking component,
Hydroxylalkyl acrylate or methacrylate having 1 to 5 carbon atoms, which is a hydrophilic component, is used as a curing crosslinking component,
Excellent water resistance and gloss by mixing an aqueous aminoplast resin after making an acrylic copolymer with reduced α / β monoethylenically unsaturated carboxylic acid component for water solubilization The inventors have found that it is possible to reduce the amount of organic solvent and have completed the present invention.
本発明に従えば， （ａ）炭素数が１〜５のヒドロキシアルキルアクリレー
トもしくはメタクリレート ５〜65重量％ （ｂ）アルキレングリコールもしくはポリオキシアルキ
レングリコールのジアクリレートもしくはジメタクリレ
ート ５〜50重量％ （ｃ）α・βモノエチレン性不飽和カルボン酸２〜20重
量％ （ｄ）上記の（ａ）ないし（ｃ）と共重合可能なビルモ
ノマーの１種または２種以上 20〜88重量％ を有機溶剤中で重合してなる共重合体を揮発性塩基で中
和せしめた水性樹脂と、水性アミンホルムアルデヒド縮
合物とを樹脂成分とすることを特徴とする水性塗料組成
物である。According to the present invention, (a) hydroxyalkyl acrylate or methacrylate having 1 to 5 carbon atoms 5 to 65% by weight (b) alkylene glycol or polyoxyalkylene glycol diacrylate or dimethacrylate 5 to 50% by weight (c) 2 to 20% by weight of α / β monoethylenically unsaturated carboxylic acid (d) 20 to 88% by weight of one or more kinds of building monomers copolymerizable with the above (a) to (c) in an organic solvent A water-based coating composition comprising a water-based resin obtained by neutralizing a copolymer obtained by polymerization in step 1) with a volatile base and a water-based amine formaldehyde condensate as resin components.
以下，本発明の組成物についてさらに詳細に説明する。Hereinafter, the composition of the present invention will be described in more detail.
本発明における炭素数が１〜５のヒドロキシアルキルア
クリレートまたはメタクリレート（ａ）は，ヒドロキシ
メチルアクリレート，ヒドロキシエチルアクリレート，
ヒドロキシプロピルアクリレート，ヒドロキシアミルア
クリレート，ヒドロキシヘキシルアクリレート及び相当
するメタクリレートがこれに該当する。好ましくは炭素
数が１〜２のヒドロキシメチルアクリレート，ヒドロキ
シエチルアクリレート及び相当するメタクリレートがよ
い。The hydroxyalkyl acrylate or methacrylate (a) having 1 to 5 carbon atoms in the present invention is hydroxymethyl acrylate, hydroxyethyl acrylate,
This includes hydroxypropyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate and the corresponding methacrylates. Preferably, hydroxymethyl acrylate, hydroxyethyl acrylate and the corresponding methacrylate having 1 to 2 carbon atoms are preferable.
アルキレングリコールもしくはポリオキシアルキレング
リコールのジアクリレートもしくはジメタクリレート
（ｂ）は次の一般式で示される。The diacrylate or dimethacrylate (b) of alkylene glycol or polyoxyalkylene glycol is represented by the following general formula.
（式中,R1,R2,R3は,HまたはCH3であり,nは１〜50の整数
を表す。） より具体的には上記式においてｎが１〜４で表されるエ
チレングリコールジアクリレート，ジエチレングリコー
ルジアクリレート，プロピレングリコールジアクリレー
ト，ジプロピレングリコールジアクリレート，トリプロ
ピレングリコールジアクリレート，テトラプロピレング
リコールジアクリレート及び相当するメタクリレートが
好ましい。 (In the formula, R 1 , R 2 , and R 3 are H or CH 3 , and n represents an integer of 1 to 50.) More specifically, in the above formula, n is 1 to 4 Glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate and the corresponding methacrylates are preferred.
α・βモノエチレン性不飽和カルボン酸（ｃ）はアクリ
ル酸，メタクリル酸，クロトン酸，マレイン酸，フマル
酸，イタコン酸などがあり，特にアクリル酸，メタクリ
ル酸が好ましい。Examples of the α / β monoethylenically unsaturated carboxylic acid (c) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, with acrylic acid and methacrylic acid being particularly preferred.
上記（ａ）ないし（ｃ）と共重合可能なビニルモノマー
（ｄ）は，例えばアクリル酸エチル，アクリル酸ブチ
ル，アクリル酸−２エチルヘキシル，アクリル酸シクロ
ヘキシル，メタクリル酸エチル，メタクリル酸ブチル，
メタクリル酸ステアリル，メタクリル酸シクロヘキシル
などのアクリル酸またはメタクリル酸のアルキルエステ
ル，またはスチレン，ビニルトルエン，α−メチルスチ
レンなどの芳香族ビニル化合物及び酢酸ビニル，ビニル
エチルエーテルなどがある。The vinyl monomer (d) copolymerizable with the above (a) to (c) is, for example, ethyl acrylate, butyl acrylate, -2 ethylhexyl acrylate, cyclohexyl acrylate, ethyl methacrylate, butyl methacrylate,
Examples thereof include alkyl esters of acrylic acid or methacrylic acid such as stearyl methacrylate and cyclohexyl methacrylate, or aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene, and vinyl acetate and vinyl ethyl ether.
本発明において（ａ）成分は共重合体樹脂中５〜65重量
％であり,5重量％以下になると架橋点が少なくなる結
果，塗膜の耐水性が劣り，また親水性基が少ないことか
ら塗料安定性に欠け，逆に65重量％以上になると架橋点
が多すぎる結果，塗膜の可とう性が劣る。In the present invention, the component (a) is 5 to 65% by weight in the copolymer resin, and when it is less than 5% by weight, the number of cross-linking points decreases, resulting in poor water resistance of the coating film and low hydrophilic groups. Insufficient coating stability, and conversely, if it exceeds 65% by weight, there are too many crosslinking points, resulting in poor flexibility of the coating film.
（ｂ）成分は共重合体成分中５〜50重量％で用いられ,5
重量％以下では前架橋効果より耐水性向上が劣り,50重
量％以上では可とう性に欠けるので,5〜50重量％が耐水
性向上と可とう性のバランスがとれる最適の範囲であ
る。The component (b) is used in an amount of 5 to 50% by weight in the copolymer component.
If the amount is less than 50% by weight, the water resistance is inferior to the pre-crosslinking effect, and if the amount is more than 50% by weight, the flexibility is insufficient. Therefore, 5 to 50% by weight is the optimum range in which the improvement in the water resistance and the flexibility are balanced.
（ｃ）成分は，水性化可能な限り少ない方が耐水性が良
好であり,2重量％以上でこの目的を達成するが,20重量
％以上をこえると，耐水性の向上があっても十分でなく
なる。また，（ｄ）成分は20〜88重量％の範囲の配合に
より組成物の塗膜硬度および可とう性を調節出来る。The component (c) has better water resistance when it is made as water-soluble as possible, and achieves this purpose at 2% by weight or more, but if it exceeds 20% by weight, even if the water resistance is improved, it is sufficient. No longer. Further, the coating hardness and flexibility of the composition can be adjusted by blending the component (d) in the range of 20 to 88% by weight.
本発明の共重合は上記（ａ）ないし（ｄ）のモノマーを
有機溶剤中で過酸化物またはアゾ化合物を触媒とし共重
合させ，前架橋したゲル可されていない共重合体として
得られる。重合条件は90〜120℃の温度で50重量％以下
の比較的低い重合固体含有量で実施することにより，ゲ
ル化せずに合成可能となる。これは得られた共重合体溶
液の紫外線吸収強度を合成前のものと比較すると，その
吸収がほとんどなくなっていることからも，仕込ビニル
モノマー全てが共重合していること示すものであり，前
架橋しゼル化しないことは驚くべきことである。The copolymer of the present invention is obtained by copolymerizing the monomers (a) to (d) described above in an organic solvent using a peroxide or an azo compound as a catalyst to obtain a pre-crosslinked non-gelling copolymer. Polymerization can be performed without gelation by carrying out the polymerization at a temperature of 90 to 120 ° C and a relatively low content of polymer solids of 50% by weight or less. This is because the UV absorption intensity of the obtained copolymer solution was compared with that before synthesis, and since the absorption was almost eliminated, all of the charged vinyl monomers were copolymerized. It is surprising that it crosslinks and does not gell.
以上の４成分よりなる共重合体を水性化するには，アン
モニアまたは有機アミン等の揮発性塩基例えばモノエタ
ノールアミン，ジメチルアミン，ジエチルアミン，トリ
エチルアミン，トリエタノールアミン，ジエチルエタノ
ールアミン等を使用する。In order to make the above-mentioned four-component copolymer aqueous, a volatile base such as ammonia or an organic amine such as monoethanolamine, dimethylamine, diethylamine, triethylamine, triethanolamine, diethylethanolamine is used.
水性化後，または水性アミンプラスト樹脂を混合した後
溶液中の有機溶剤を減圧下60〜80℃の範囲内で留去する
と，水溶性あるいは水分散性樹脂溶液が水可溶化力の差
にともない得られる。When water-soluble or water-dispersible resin solutions are water-solubilized or water-dispersible when the organic solvent in the solution is distilled off under reduced pressure within the range of 60 to 80 ° C can get.
このため合成時の有機溶剤は後工程の留去を考慮する
と，沸点が150℃以下が好ましく，合成時の温度及び合
成共重合体の有機溶剤への溶解力を考慮に入れると，沸
点が80〜150℃の範囲内のイソプロピルアルコール,n−
ブタノール，イソブチルアルコール,n−アミルアルコー
ル，イソアミルアルコール等のアルコール系溶剤及びエ
チレングリコールモノメチルエーテル，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イソ
プロピルエーテル等のエステル系溶剤が好ましい。Therefore, the boiling point of the organic solvent during synthesis is preferably 150 ° C or less in consideration of the distillation in the later step. Considering the temperature during synthesis and the dissolving power of the synthetic copolymer in the organic solvent, the boiling point is 80 ° C. Isopropyl alcohol, n-
Preference is given to alcohol solvents such as butanol, isobutyl alcohol, n-amyl alcohol, isoamyl alcohol and ester solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monoisopropyl ether.
本発明の水性アミンホルムアルデヒド縮合物は，アルキ
ルエーテル化メラミン樹脂，アルキルエーテル化尿素樹
脂，フェニレン核に２個のトリアジン環の結合したジグ
アナミンのアルキルエーテル化樹脂，アルキルエーテル
化グリコール樹脂等を単独または２種以上を混合して用
いる。好ましくは，完全にエーテル化されたヘキサメト
キシメラミンがよい。The aqueous amine-formaldehyde condensate of the present invention comprises an alkyl etherified melamine resin, an alkyl etherified urea resin, a diguanamine alkyl etherified resin having two triazine rings bonded to a phenylene nucleus, an alkyl etherified glycol resin, or the like. A mixture of two or more species is used. Preference is given to fully etherified hexamethoxymelamine.
水性化処理により水溶化あるいは水分散体化した水性樹
脂は，水性アミノプラスト樹脂と混合し，更に必要に応
じて硬化助剤としてアミンでブロックした酸触触例えば
ｐ−トルエンベンゼンスルホン酸，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
型分100部に対し0.1〜1.0部を添加して塗料化する。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，水溶性あるいは水分散性エポキシ樹
脂及びビスフェノールＡプロピレンオキサイド付加物，
エチレンオキサイド付加物等の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。また顔料を前記の
脱溶剤した共重合樹脂溶液と練肉し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。The aqueous resin which has been made water-soluble or water-dispersed by an aqueous treatment is mixed with an aqueous aminoplast resin, and if necessary, an acid contact blocked with an amine as a curing aid, such as p-toluenebenzenesulfonic acid or dodecylbenzene. Add 0.1 to 1.0 parts of sulfonic acid, dinonylnaphthalenedisulfonic acid, etc. to 100 parts of resin solids to make a paint. Also, water-soluble resins and water-dispersible resins that are commonly used as resins for water-based paints, such as water-soluble polyester resins,
Maleated fatty acid, water-soluble or water-dispersible epoxy resin and bisphenol A propylene oxide adduct,
It is also possible to mix a polyol such as an ethylene oxide adduct. Similarly, a leveling agent, a defoaming agent, and a lubricant can be added. Further, the pigment can be kneaded with the solvent-removed copolymer resin solution to prepare a pigment paste, which can be made into a paint by the same method as described above.
本発明の水性塗料組成物はロールコート，スプレー，は
け塗り等の公知の手段により塗装することができる。The aqueous coating composition of the present invention can be applied by a known means such as roll coating, spraying, brush coating and the like.
以下，本発明を実施例にて具体的に説明する。例中
「部」，「％」とあるのは「重量部」，「重量％」を示
す。Hereinafter, the present invention will be specifically described with reference to examples. In the examples, "part" and "%" mean "part by weight" and "% by weight", respectively.
（実施例） 製造例A1（アクリル樹脂溶液の製造例） 温度計，撹拌機，還流冷却器，滴下槽，窒素ガス吹込管
を備えた四ツ口フラスコにｎ−ブタノール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100℃
に保ち，滴下槽から２−ヒドロキシエチルアクリレート
15部，テトラエチレングリコールジアクリレート20部，
アクリル酸２部，エチルアクリレート63部，過酸化ベン
ゾイル２部の混合物を３時間に亘って滴下した。その後
100℃に保ち２時間反応し，過酸化ベンゾイル0.3部を添
加し,1時間反応させ終了した。40℃以下に冷却しトリエ
チルアミン３部および水200部を添加し,60％個型分，残
留ｎ−ブタノール10％の透明で粘調な樹脂溶液が得られ
た。(Example) Production Example A1 (Production Example of Acrylic Resin Solution) 100 parts of n-butanol 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 nitrogen gas was added. Temperature while stirring while introducing
Keep it in the 2-drop ethyl acrylate from the dropping tank.
15 parts, tetraethylene glycol diacrylate 20 parts,
A mixture of 2 parts of acrylic acid, 63 parts of ethyl acrylate and 2 parts of benzoyl peroxide was added dropwise over 3 hours. afterwards
The reaction was continued for 2 hours at 100 ° C, 0.3 part of benzoyl peroxide was added, and the reaction was continued for 1 hour to complete the reaction. After cooling to 40 ° C or lower, 3 parts of triethylamine and 200 parts of water were added to obtain a transparent and viscous resin solution containing 60% solids and 10% residual n-butanol.
製造例A2〜A6 製造例A1と同様の方法に従い，フラスコにあらかじめ仕
込んでおく溶剤組成，滴下するビニルモノマー組成，触
媒量，追添加する触媒量，反応温度を表−１のように変
えて合成し，更に有機アミン量を表−１のように変えて
中和した。また製造例A1と同様の方法に従い水を添加
し，減圧下80℃にて合成溶剤を水とともに留去し,60％
個型分，残留ｎ−ブタノール10％の透明で粘調の樹脂溶
液が得られた。Production Examples A2 to A6 According to the same method as in Production Example A1, the solvent composition, vinyl monomer composition to be added dropwise, catalyst amount, additional catalyst amount, and reaction temperature to be preliminarily charged in the flask were changed as shown in Table-1. Then, the amount of organic amine was changed as shown in Table 1 to neutralize. Water was added in the same manner as in Production Example A1, and the synthetic solvent was distilled off together with water at 80 ° C under reduced pressure to give 60%.
A transparent and viscous resin solution containing individual components and 10% of residual n-butanol was obtained.
製造例B1（顔料分散ペーストの製造例） アクリル樹脂溶液A1 40部，ルチル型チタン白40部およ
び水10部を混合しアトライターで分散させ，顔料分散ペ
ーストが得られた。Production Example B1 (Production Example of Pigment Dispersion Paste) 40 parts of acrylic resin solution A1, 40 parts of rutile titanium white and 10 parts of water were mixed and dispersed with an attritor to obtain a pigment dispersion paste.
製造例B2 アクリル樹脂溶液A2 40部，ルチル型チタン白40部およ
び水10部を混合しアトライターで分散させ，顔料分散ペ
ーストが得られた。Production Example B2 Acrylic resin solution A2 40 parts, rutile type titanium white 40 parts and water 10 parts were mixed and dispersed by an attritor to obtain a pigment dispersion paste.
実施例１ 製造例A1のアクリル樹脂溶液47部，ヘキサメトキシメラ
ミン（三井東圧化学株式会社製，サイメル303;以下の例
も同じ）12部，アミンブロックしたパラトルエンスルホ
ン酸（楠本化成株式会社製 NACURE2500X;以下の例も同
じ）0.4部及び水40.6部を混合し，塗料化した。Example 1 47 parts of the acrylic resin solution of Production Example A1, 12 parts of hexamethoxymelamine (manufactured by Mitsui Toatsu Chemicals, Inc., Cymel 303; the same applies to the following examples), amine-blocked paratoluenesulfonic acid (manufactured by Kusumoto Kasei Co., Ltd.) NACURE2500X; the same applies to the following examples) 0.4 parts and 40.6 parts water were mixed to form a paint.
実施例２〜８ 実施例１と同様の方法に従い，アクリル樹脂溶液，水性
アミノプラスト樹脂を表−２のように変えて塗料化し
た。Examples 2 to 8 According to the same method as in Example 1, the acrylic resin solution and the aqueous aminoplast resin were changed as shown in Table 2 to form coating materials.
実施例９ 製造例A1のアクリル樹脂溶液6.3部，製造例B1の顔料分
散ペースト62.8部，ヘキサメトキシメラミン6.3部，ア
ミンブロックしたパラトルエンスルホン酸0.2部及び水2
4.7部を混合し塗料化した。Example 9 6.3 parts of the acrylic resin solution of Preparation Example A1, 62.8 parts of the pigment dispersion paste of Preparation Example B1, 6.3 parts of hexamethoxymelamine, 0.2 parts of amine-blocked paratoluenesulfonic acid and 2 parts of water.
4.7 parts were mixed into a paint.
実施例10 製造例A2のアクリル樹脂溶液6.3部，製造例B2の顔料分
散ペースト62.5部，ヘキサメトシメラミン6.3部，アミ
ンブロックしたパラトルエンスルホン酸0.2部及び水24.
7部を混合し塗料化した。Example 10 6.3 parts of the acrylic resin solution of Preparation Example A2, 62.5 parts of the pigment dispersion paste of Preparation Example B2, 6.3 parts of hexamethocimelamine, 0.2 parts of amine-blocked paratoluenesulfonic acid and water 24.
7 parts were mixed to form a paint.
公知の水溶性アクリル樹脂と水溶性アミノプラスト樹脂
より構成される塗料及び顔料分散ペーストを分散した白
色塗料について比較例1,2として以下記す。Comparative examples 1 and 2 will be described below with respect to a white paint in which a paint composed of a known water-soluble acrylic resin and a water-soluble aminoplast resin and a pigment dispersion paste are dispersed.
比較例１ 四ツ口フラスコにブチルセロソルブ40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115℃に保
ち，滴下槽からアクリル酸20部，エチルアクリレート50
部，メチルメタクリレート25部，ヒドロキシエチルアク
リレート５部，過酸化ベンゾイル１部の混合物を３時間
に亘って滴下した。その後115℃に保ち２時間反応し，
過酸化ベンゾイル0.1部を添加し１時間反応させ終了し
た。70℃に冷却しイソプロピルアルコール60部で希釈
し，更にトリエチルアミン25部及び水30部で希釈しアク
リル樹脂溶液を得た。Comparative Example 1 A four-necked flask was charged with 40 parts of butyl cellosolve, the temperature was kept at 115 ° C. while stirring while introducing nitrogen gas, and 20 parts of acrylic acid and 50 parts of ethyl acrylate were added from a dropping tank.
Part, 25 parts of methyl methacrylate, 5 parts of hydroxyethyl acrylate, and 1 part of benzoyl peroxide were added dropwise over 3 hours. Then keep the temperature at 115 ℃ and react for 2 hours.
0.1 part of benzoyl peroxide was added and reacted for 1 hour to complete the reaction. The mixture was cooled to 70 ° C, diluted with 60 parts of isopropyl alcohol, and further diluted with 25 parts of triethylamine and 30 parts of water to obtain an acrylic resin solution.
上記アクリル樹脂溶液にヘキサメトキシメラミンを42.9
部，アミンブロックしたパラトルエンスルホン酸及び水
164部を混合し塗料化した。Hexamethoxy melamine was added to the acrylic resin solution 42.9
Parts, amine-blocked paratoluenesulfonic acid and water
164 parts were mixed to form a paint.
比較例２ 比較例１で得られたアクリル樹脂溶液55部，ルチル型チ
タン白40部及び水５部を混合しアトライターで分散させ
た後，更に同アクリル樹脂溶液12.5部とヘキサメトキシ
メラミン10部，アミンブロックしたパラトルエンスルホ
ン酸0.4部及び水37.1部を混合し塗料化した。Comparative Example 2 55 parts of the acrylic resin solution obtained in Comparative Example 1, 40 parts of rutile-type titanium white and 5 parts of water were mixed and dispersed with an attritor, and then 12.5 parts of the acrylic resin solution and 10 parts of hexamethoxymelamine were further mixed. Then, 0.4 parts of amine-blocked paratoluenesulfonic acid and 37.1 parts of water were mixed to form a paint.
比較例３ 特公昭52−1735号公報の実施例１に記載されたアクリル
樹脂溶液を用いて，アミノプラスト樹脂と触媒は実施例
１と同様にしてクリヤー系塗料を得た。Comparative Example 3 Using the acrylic resin solution described in Example 1 of Japanese Patent Publication No. 52-1735, the aminoplast resin and the catalyst were the same as in Example 1 to obtain a clear coating composition.
比較例４ 比較例３のアクリル樹脂を用いて製造例B1と同様にして
調製したチタン顔料分散ペーストを用い，ついで実施例
９と同様にして白色塗料を得た。Comparative Example 4 A white paint was obtained in the same manner as in Example 9 except that the titanium pigment-dispersed paste prepared by using the acrylic resin of Comparative Example 3 in the same manner as in Production Example B1 was used.
実施例１〜10および比較例１〜４で得られた塗料の塗料
試験，塗装焼付硬化後の塗膜物性試験及びフロー塗装性
試験を行った。結果を表−３に記す。The paint tests of the paints obtained in Examples 1 to 10 and Comparative Examples 1 to 4, the paint film physical property test after baking and curing, and the flow coatability test were performed. The results are shown in Table-3.
各試験方法は下記のとおりである。Each test method is as follows.
塗料試験 ○塗料安定性試験； 各塗料を２ケ月間常温で保存した後，樹脂のゲル化，分
離の状態を観察した。Paint test ○ Paint stability test: After each paint was stored at room temperature for two months, the state of gelation and separation of the resin was observed.
○塗料中の有機溶剤含有量試験； 塗料をメチルエチルケトンで希釈し，そのままガスクロ
マトグラフィーにて定量した。○ Organic solvent content test in paint: The paint was diluted with methyl ethyl ketone and quantified as it was by gas chromatography.
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分間焼付塗装パネルを
作成した。Coating film physical property test An electroplated tin plate having a plate thickness of 0.23 mm was coated by roll coating so that the coating film thickness would be 7 μ after drying, and a baking coated panel was prepared in a gas oven at an ambient temperature of 190 ° C. for 10 minutes.
○耐水性試験； 塗装パネルを水中に浸漬し,100℃−30分間の熱処理を行
った後，塗膜の白化状態を評価した。○ 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.
○鉛筆硬度試験； JIS規格にのっとった鉛筆硬度試験法により評価した。○ Pencil hardness test: It was evaluated by the pencil hardness test method according to JIS standard.
○密着性試験； ゴバン目剥離試験を行った。○ Adhesion test: A goose eye peel test was performed.
○耐衝撃性； デェポン式1/2インチ,500g荷重で試験した。○ Impact resistance: Tested with a 1/2 inch, 500 g load.
○グロス； 60鏡面反射率を測定した。なお，クリヤー系塗料につい
ては実施例９の白色塗料の焼付塗膜板上に塗装した後測
定した。○ Gloss: 60 The specular reflectance was measured. The clear coating material was measured after coating it on the baked coating plate of the white coating material of Example 9.
○耐錆性； 塗膜面に素地に達するクロスカットを行った試験板を用
い塩水噴霧試験72時間おこない，カット部をセロハン粘
着テープで剥離し，その剥離面積で評価した。○ Rust resistance: A salt spray test was performed for 72 hours using a test plate with a cross cut reaching the base material on the coating film surface, the cut portion was peeled off with cellophane adhesive tape, and the peeled area was evaluated.
塗装性試験 ○フロー； ロールコーターにつて塗装後直ちにガスオーブンにて焼
付け，フロー状態を評価した。Paintability test ○ Flow: A roll coater was baked immediately after coating in a gas oven to evaluate the flow state.
本発明の水性塗料組成物は，飲料缶，食缶等の食品殺菌
処理時の熱処理工程にも耐えうる耐水性を有しており，
缶材の美的商品価値を高めるグロスの優れた塗膜を被覆
形成し，かつ有機溶剤含有率が塗料中の５％以下であっ
ても優れた塗料安定性及びフロー塗装適性を有してい
る。The water-based coating composition of the present invention has water resistance capable of withstanding a heat treatment step during food sterilization treatment of beverage cans, food cans, and the like.
It forms a coating film with excellent gloss that enhances the aesthetic commercial value of can materials, and has excellent paint stability and flow coating suitability even if the organic solvent content is 5% or less of the paint.
───────────────────────────────────────────────────── フロントページの続き 審判の合議体 審判長 鳴井 義夫 審判官 柿沢 紀世雄 審判官 沼辺 征一郎 (56)参考文献 特開 昭54−85231（ＪＰ，Ａ) 特開 昭55−3488（ＪＰ，Ａ) 特開 昭61−203179（ＪＰ，Ａ) 特公 昭52−1735（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── --Continued from the front page Judgment panel for referees Chief referee Yoshio Narai Referee Referee Norio Kakizawa Referee Referee Shoichiro Numanabe (56) Reference JP 54-85231 (JP, A) JP 55-3488 (JP, JP, 3485) A) JP 61-203179 (JP, A) JP 52-1735 (JP, B2)
Claims (1)
ルアクリレートもしくはメタクリレート ５〜65重量％ （ｂ）アルキレングリコールもしくはポリオキシアルキ
レングリコールのジアクリレートもしくはジメタクリレ
ート ５〜50重量％ （ｃ）α・βモノエチレン性不飽和カルボン酸２〜20重
量％ （ｄ）上記の（ａ）ないし（ｃ）と共重合可能なビニル
モノマーの１種または２種以上 20〜88重量％ を有機溶剤中で重合してなる共重合体を揮発性塩基で中
和せしめた水性樹脂と、水性アミンホルムアルデヒド縮
合物とを樹脂成分とすることを特徴とする水性塗料組成
物。(A) Hydroxyalkyl acrylate or methacrylate having 1 to 5 carbon atoms 5 to 65% by weight (b) Diacrylate or dimethacrylate of alkylene glycol or polyoxyalkylene glycol 5 to 50% by weight (c) α 2 to 20% by weight of β-monoethylenically unsaturated carboxylic acid (d) 20 to 88% by weight of one or more vinyl monomers copolymerizable with the above (a) to (c) in an organic solvent. An aqueous coating composition comprising an aqueous resin obtained by neutralizing a copolymer obtained by polymerization with a volatile base and an aqueous amine-formaldehyde condensate as resin components.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61258555A JPH0788492B2 (en) | 1986-10-31 | 1986-10-31 | Aqueous coating composition |
| GB8809797A GB2217721B (en) | 1986-10-31 | 1988-04-26 | Aqueous coating compostion and process for the production thereof |
| DE3814665A DE3814665C2 (en) | 1986-10-31 | 1988-04-29 | Aqueous coating agent and process for its production |
| CA000565478A CA1336630C (en) | 1986-10-31 | 1988-04-29 | Aqueous coating composition, process for the production thereof and aqueous coating |
| US07/680,778 US5077348A (en) | 1986-10-31 | 1991-04-20 | Aqueous coating composition, process for the production thereof and aqueous coating |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61258555A JPH0788492B2 (en) | 1986-10-31 | 1986-10-31 | Aqueous coating composition |
| CA000565478A CA1336630C (en) | 1986-10-31 | 1988-04-29 | Aqueous coating composition, process for the production thereof and aqueous coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63113086A JPS63113086A (en) | 1988-05-18 |
| JPH0788492B2 true JPH0788492B2 (en) | 1995-09-27 |
Family
ID=25671870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61258555A Expired - Lifetime JPH0788492B2 (en) | 1986-10-31 | 1986-10-31 | Aqueous coating composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH0788492B2 (en) |
| CA (1) | CA1336630C (en) |
| DE (1) | DE3814665C2 (en) |
| GB (1) | GB2217721B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5594931B2 (en) | 2006-11-02 | 2014-09-24 | 関西ペイント株式会社 | Water-based paint composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS521735A (en) * | 1975-06-20 | 1977-01-07 | Ibu Emiiru Puribasu | Radiation heating element |
| US4062823A (en) * | 1976-09-20 | 1977-12-13 | Ford Motor Company | Hybrid water-based enamels with partially crosslinked latexes |
| JPS553488A (en) * | 1977-01-07 | 1980-01-11 | Vianova Kunstharz Ag | Waterrdilutable thermoosetting coating composition |
| JPS5485231A (en) * | 1977-12-21 | 1979-07-06 | Nippon Oil & Fats Co Ltd | Thermosetting coating composition |
| AT381499B (en) * | 1985-02-27 | 1986-10-27 | Vianova Kunstharz Ag | WATER-DISCOVERABLE COATING AGENTS, METHOD FOR THE PRODUCTION AND THEIR USE FOR BASE LAYERS WITH TWO-LAYER TOP COATING |
-
1986
- 1986-10-31 JP JP61258555A patent/JPH0788492B2/en not_active Expired - Lifetime
-
1988
- 1988-04-26 GB GB8809797A patent/GB2217721B/en not_active Expired - Lifetime
- 1988-04-29 DE DE3814665A patent/DE3814665C2/en not_active Expired - Fee Related
- 1988-04-29 CA CA000565478A patent/CA1336630C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB2217721B (en) | 1991-09-04 |
| DE3814665C2 (en) | 1995-09-07 |
| CA1336630C (en) | 1995-08-08 |
| GB8809797D0 (en) | 1988-06-02 |
| JPS63113086A (en) | 1988-05-18 |
| DE3814665A1 (en) | 1989-11-09 |
| GB2217721A (en) | 1989-11-01 |
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