JPH0812929A - Water-based coating resin composition - Google Patents
Water-based coating resin compositionInfo
- Publication number
- JPH0812929A JPH0812929A JP14757194A JP14757194A JPH0812929A JP H0812929 A JPH0812929 A JP H0812929A JP 14757194 A JP14757194 A JP 14757194A JP 14757194 A JP14757194 A JP 14757194A JP H0812929 A JPH0812929 A JP H0812929A
- Authority
- JP
- Japan
- Prior art keywords
- water
- vinylic monomer
- resin
- formula
- coating
- 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.)
- Pending
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水性缶コーティング、
特に缶外面コーティングにおいて、缶塗膜の初期あるい
は熱殺菌処理（以下「レトルト」或いは「レトルト処
理」と記す）工程後においても、塗膜の必要性能である
加工性、密着性、硬度および良好な外観が得られる水性
塗料用樹脂組成物に関する。The present invention relates to an aqueous can coating,
Especially in the coating of the outer surface of the can, even after the initial stage of the can coating film or after the heat sterilization treatment (hereinafter referred to as "retort" or "retort treatment") step, the required performance of the coating is processability, adhesion, hardness and good performance. The present invention relates to a resin composition for water-based paints that gives an appearance.
【０００２】[0002]
【従来の技術】清涼飲料水等を収容する飲料缶および食
品等を収容する食缶の外面は、缶素材の腐食を防止し、
美的商品価値を高め、かつ缶の加工性およびレトルト処
理工程に耐え得る塗膜により被覆形成されている。2. Description of the Related Art The outer surface of a beverage can containing soft drinks or the like and a food can containing food prevents corrosion of the can material.
The coating is formed by a coating film that enhances aesthetic commercial value and can withstand the processability of cans and the retort treatment process.
【０００３】従来、これ等の缶外面用塗料は、アクリル
樹脂、ポリエステル樹脂、エポキシ樹脂等と、硬化剤を
有機溶媒に溶解して調製されているが、近年、消防法等
の多くの有機溶剤使用に関する法規制が強化され、塗料
の水性化が広く要望されている。Conventionally, these external paints for cans have been prepared by dissolving an acrylic resin, a polyester resin, an epoxy resin and the like and a curing agent in an organic solvent. In recent years, however, many organic solvents such as the Fire Service Act have been prepared. There are widespread demands for water-based paints because of stricter regulations on use.
【０００４】現在、水性缶外面用塗料としては、一般的
にアクリル樹脂、アクリル／エポキシ樹脂に酸性基をも
たせ、それを揮発性塩基成分により中和し、硬化剤とし
てのアミノ樹脂と配合し、僅かな有機溶剤を含んだ水溶
液としてロールコーター等により塗装し、焼付炉で焼付
硬化する方法が行われている。At present, as a paint for the outer surface of an aqueous can, an acrylic resin or an acrylic / epoxy resin is generally provided with an acidic group, which is neutralized with a volatile base component and then blended with an amino resin as a curing agent. A method in which an aqueous solution containing a small amount of an organic solvent is applied by a roll coater or the like and then baked and cured in a baking oven is used.
【０００５】また、缶外面用塗料としては、クリヤーコ
ート用およびホワイトコート用があり、缶のデザイン等
により、クリヤーコートのみ、あるいはホワイトコート
／クリヤーコートといった塗装がなされている。Further, there are clear coat and white coat as the paint for the outer surface of the can. Depending on the design of the can, clear coat only or white coat / clear coat is applied.
【０００６】[0006]
【発明が解決しようとする課題】公知の水性塗料用樹脂
は、水分散性と水溶性の２つのタイプがあり、水分散性
樹脂は界面活性剤等を用いて乳化重合法で合成されるも
のが多く、界面活性剤が塗膜中に残存するため、耐水性
が低下したり、構造粘性によりロールコーター適性に劣
る欠点を有している。There are two types of known resins for water-based coatings, water-dispersible and water-soluble. The water-dispersible resin is synthesized by emulsion polymerization using a surfactant or the like. In many cases, since the surfactant remains in the coating film, the water resistance is lowered and the structural viscosity makes the roll coater less suitable.
【０００７】水溶性樹脂は、一般的にアクリル樹脂が多
く使用されているが、水溶化するためには分子内にカル
ボキシル基等が必要であり、耐水性に劣る一つの原因と
なっている。As the water-soluble resin, an acrylic resin is generally used in many cases, but a carboxyl group or the like is required in the molecule to make it water-soluble, which is one of the causes of poor water resistance.
【０００８】また、缶外面硬化塗膜は、搬送時の傷つき
に対しての塗膜硬度、さらにはレトルト処理後の加工密
着性および外観等の性能が必要であり、かかる性能をバ
ランス良く向上させる為に、アクリル樹脂としては加水
分解性の少ないモノマー等の選択、官能基モノマーの
種、量の選択、さらに分子量、Ｔｇの検討がなされ、エ
ポキシ樹脂グラフトおよび併用等も行われている。[0008] Further, the cured coating film on the outer surface of the can is required to have coating hardness against scratches during transportation, and further, processing adhesion and appearance after retort treatment. Therefore, as the acrylic resin, selection of a monomer having a low hydrolyzability, selection of the species and amount of the functional group monomer, examination of the molecular weight and Tg have been made, and epoxy resin grafting and combination use have also been carried out.
【０００９】しかしながら、かかる樹脂系は、缶搬送時
の傷つきに対しての充分な塗膜硬度、レトルト処理後の
加工部密着性および外観といった塗膜性能をバランス良
く満足させる事が出来ていない。However, such a resin system is not able to satisfy a well-balanced coating performance such as sufficient coating hardness against scratches during can transportation, adhesion of processed portion after retort treatment and appearance.
【００１０】本発明は、上記の問題点について鋭意検討
した結果、硬化塗膜がレトルト処理後に於いても良好な
加工部密着性と硬度および外観を有する水性塗料用樹脂
組成物を提供したものである。As a result of earnest studies on the above problems, the present invention provides a resin composition for water-based coatings, in which a cured coating film has good adhesion to processed parts, hardness and appearance even after retort treatment. is there.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、前記の問
題点についてアクリル樹脂を鋭意検討した結果、アミノ
樹脂との主な架橋成分である共重合物（Ａ）中のＯＨ基
含有ビニル性単量体として、ＯＨ基がアクリル主鎖から
離れ、加水分解性にも優れかつ１級のＯＨ基で架橋反応
性に優れたビニル性単量体（ａ）を成分とし、かつ少な
くとも１種以上の他のビニル性単量体と共重合された、
酸価２０〜１００の共重合物（Ａ）とアミノ樹脂（Ｂ）
からなる水性塗料用樹脂組成物により、初期およびレト
ルト処理工程において、加工部密着性、硬度および外観
の良好な塗膜が得られる事を見いだし、本発明に到達し
た。Means for Solving the Problems As a result of intensive studies on acrylic resins for the above problems, the present inventors have found that OH group-containing vinyl in the copolymer (A), which is a main cross-linking component with amino resins, is used. The vinyl monomer (a) having an OH group separated from the acrylic main chain and excellent in hydrolyzability and excellent in cross-linking reactivity with a primary OH group as a polymerizable monomer, and at least one kind Copolymerized with other vinylic monomers above,
Copolymer (A) having an acid value of 20 to 100 and amino resin (B)
It was found that a resin composition for water-based coating composition consisting of (1) can provide a coating film having good adhesion, hardness and appearance in the processed part in the initial and retort treatment steps, and reached the present invention.
【００１２】すなわち本発明は、１分子中に１級のＯＨ
基を持つビニル性単量体（ａ）を成分とし、かつ少なく
とも１種以上の他のビニル性単量体とを共重合された酸
価２０〜１００の共重合物（Ａ）４０〜９０重量％とア
ミノ樹脂（Ｂ）６０〜１０重量％からなる水性塗料用樹
脂組成物である。That is, according to the present invention, a primary OH is present in one molecule.
40-90% by weight of a copolymer (A) having an acid value of 20 to 100, which is a copolymer of a vinylic monomer (a) having a group and is copolymerized with at least one or more other vinylic monomers. % And 60 to 10% by weight of the amino resin (B) is a resin composition for water-based paint.
【００１３】以下本発明を詳細に説明する。The present invention will be described in detail below.
【００１４】本発明で用いられる１分子中に１級のＯＨ
基を持つビニル性単量体（ａ）は、下記の構造式で表さ
れ、Primary OH in one molecule used in the present invention
The vinylic monomer (a) having a group is represented by the following structural formula,
【００１５】[0015]
【化３】 式中のＲ，Ｒ1 ，Ｒ2 ，Ｒ3 は下記で構成されるEmbedded image In the formula, R, R 1 , R 2 and R 3 are composed of
【００１６】[0016]
【化４】 であり、式中のｎ，ｍおよびｍ’は平均付加モル数であ
り、それぞれ、ｎ＝１〜１５、好ましくは４〜１２、さ
らに好ましくは５〜１０であり、ｍ＝１〜１０、好まし
くは１〜４、さらに好ましくは１〜３であり、またｍ’
＝１〜５、好ましくは１〜２、さらに好ましくは１であ
る。[Chemical 4] And n, m and m ′ in the formula are average addition mole numbers, respectively, n = 1 to 15, preferably 4 to 12, more preferably 5 to 10, and m = 1 to 10, preferably Is 1-4, more preferably 1-3, and m ′.
= 1-5, preferably 1-2, and more preferably 1.
【００１７】ここで式中のｎとｍ、またはｎとｍ’の合
計が２未満であると、充分な加工性が得られず、２０を
越えると充分な硬度が得られなかったり、単量体（ａ）
としての分子量が増大し、ＯＨ基量として不足する傾向
になる。If the sum of n and m or n and m'in the formula is less than 2, sufficient workability cannot be obtained, and if it exceeds 20, sufficient hardness cannot be obtained, or a simple amount is not obtained. Body (a)
As a result, the molecular weight of OH group increases, and the OH group content tends to be insufficient.
【００１８】さらに詳細には、ｎ＝１以下ではレトルト
処理後の加工密着性、外観が劣り、１５を越えると塗料
化時の水溶化等が劣る。更にｍまたはｍ’が１未満で
は、架橋反応性が悪く、その結果レトルト処理後の外観
等が劣り、ｍ＝１０（ｍ’＝５）を越えると、レトルト
処理後の加工密着性、外観が劣る。More specifically, when n = 1 or less, the process adhesion and appearance after retort treatment are poor, and when it is more than 15, the water-solubility at the time of coating is poor. Further, when m or m ′ is less than 1, the crosslinking reactivity is poor, and as a result, the appearance after retort treatment is poor, and when m = 10 (m ′ = 5) is exceeded, the processing adhesion and appearance after retort treatment are poor. Inferior.
【００１９】さらにビニル性単量体（ａ）が共重合物
（Ａ）中の固形分として１重量％未満では、レトルト処
理後の加工部密着性、硬度、外観等（以下「レトルト性
能」と記す）を充分に満足させる事が出来ない。Further, when the vinylic monomer (a) is less than 1% by weight as a solid content in the copolymer (A), the adhesion, hardness, appearance and the like of the processed portion after retort treatment (hereinafter referred to as "retort performance"). Note) cannot be fully satisfied.
【００２０】本発明に用いられる共重合物（Ａ）中に含
まれるビニル性単量体（ａ）以外のビニル性単量体とし
ては、例えばカルボキシル基含有ビニル性単量体では
（メタ）アクリル酸、マレイン酸、フマル酸、イタコン
酸等が挙げられ、これらは１種または２種以上を組み合
わせて用いてもよい。また、ビニル性単量体（ａ）以外
のヒドロキシル基含有ビニル性単量体では、例えば、ヒ
ドロキシメチル（メタ）アクリレート、２ヒドロキシエ
チル（メタ）アクリレート、２ヒドロキシプロピル（メ
タ）アクリレート、ヒドロキシブチル（メタ）アクリレ
ート等が挙げられる。これらは単量体（ａ）との併用で
もよい。更に非官能ビニル性単量体としては、例えば、
メチル（メタ）アクリレート、エチル（メタ）アクリレ
ート、プロピル（メタ）アクリレート、ｎブチル（メ
タ）アクリレート、ｉブチル（メタ）アクリレート、ｔ
ブチル（メタ）アクリレート、２エチルヘキシル（メ
タ）アクリレート、シクロヘキシル（メタ）アクリレー
ト、ラウリル（メタ）アクリレート、ベンジル（メタ）
アクリレート、ステアリル（メタ）アクリレート、イソ
ボルニル（メタ）アクリレート、フェノキシエチル（メ
タ）アクリレート、ジメチルアミノエチル（メタ）アク
リレート、Ｎ−ｎブトキシメチル（メタ）アクリルアミ
ド、スチレン、αメチルスチレン、ビニルトルエン等が
挙げられ、１種または２種以上を併用してもよい。As the vinylic monomer other than the vinylic monomer (a) contained in the copolymer (A) used in the present invention, for example, a carboxyl group-containing vinylic monomer is (meth) acrylic. Acid, maleic acid, fumaric acid, itaconic acid and the like can be mentioned, and these may be used alone or in combination of two or more kinds. Examples of hydroxyl group-containing vinyl monomers other than the vinyl monomer (a) include hydroxymethyl (meth) acrylate, 2hydroxyethyl (meth) acrylate, 2hydroxypropyl (meth) acrylate, and hydroxybutyl ( Examples thereof include (meth) acrylate. These may be used in combination with the monomer (a). Further, as the non-functional vinyl monomer, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth)
Acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Nn-butoxymethyl (meth) acrylamide, styrene, α-methylstyrene, vinyltoluene and the like. However, one kind or two or more kinds may be used in combination.
【００２１】前記ビニル性単量体とビニル性単量体
（ａ）は、ラジカル重合されて共重合物（Ａ）となる
が、重合開始剤としては、有機過酸化物系、アゾ系等が
用いられ、有機過酸化物系では例えば、ベンゾイルパー
オキサイド、ｔブチルパーオキシ２エチルヘキサノエー
ト、ジ−ｔブチルパーオキサイド、ｔブチルパーオキシ
ベンゾエート等が挙げられ、アゾ系では例えばアゾビス
イソブチロニトリル、アゾビスジメチルバレロニトリル
等が挙げられる。The vinylic monomer and the vinylic monomer (a) are radically polymerized to form a copolymer (A). As the polymerization initiator, an organic peroxide type or an azo type is used. Examples of the organic peroxide type include benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, di-t-butyl peroxide, t-butyl peroxybenzoate, and the like, and azo type, for example, azobisisobutyrate. Examples thereof include ronitrile and azobisdimethylvaleronitrile.
【００２２】さらに共重合物（Ａ）は、主に溶液重合に
より得られ、その溶媒としては親水性の溶剤が用いられ
るが、例えば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ブチルエーテル、エチレングリ
コールモノイソブチルエーテル、エチレングリコールモ
ノイソプロピルエーテル、プロピレングリコールモノメ
チルエーテルアセテート、プロピレングリコールモノエ
チルエーテルアセテート等が挙げられる。Further, the copolymer (A) is mainly obtained by solution polymerization, and a hydrophilic solvent is used as the solvent, for example, ethylene glycol monomethyl ether,
Examples thereof include ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.
【００２３】以上の様に合成された共重合物（Ａ）は水
溶化させるための酸価として、固形分酸価で２０〜１０
０であり、この値が２０未満であると水溶化が困難にな
り、１００を越えるとレトルト性能等が劣る。The copolymer (A) synthesized as described above has an acid value of 20 to 10 in terms of solid content as an acid value for solubilizing water.
It is 0, and if this value is less than 20, water solubility becomes difficult, and if it exceeds 100, retort performance and the like are poor.
【００２４】水性塗料用樹脂組成物中の量として、共重
合物（Ａ）は４０〜９０重量％の範囲で使用するが、４
０重量％未満では塗膜のレトルト性能が劣り、９０重量
％を越えると塗膜の硬度が劣る。The amount of the copolymer (A) used in the resin composition for water-based paints is 40 to 90% by weight.
If it is less than 0% by weight, the retort performance of the coating film is poor, and if it exceeds 90% by weight, the hardness of the coating film is poor.
【００２５】塗料化の際、共重合物（Ａ）中の酸価は、
揮発性塩基成分により中和され、その後アミノ樹脂
（Ｂ）等と混合され、水希釈後水性塗料となるが、この
時、中和に用いる揮発性塩基成分としては、主に３級ア
ミンであり、例えばトリエタノールアミン、ジメチルエ
タノールアミン、ジエチルエタノールアミン、モルホリ
ン等が挙げられ、さらに中和率として５０〜１５０％中
和される。The acid value in the copolymer (A) during coating is
It is neutralized with a volatile base component, then mixed with an amino resin (B) and the like, and diluted with water to form an aqueous coating. At this time, the volatile base component used for neutralization is mainly a tertiary amine. Examples thereof include triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, and the like, and the neutralization rate is 50 to 150%.
【００２６】本発明に用いられるアミノ樹脂（Ｂ）は、
例えばアルキルエーテル化メラミン樹脂、アルキルエー
テル化ベンゾグアナミン樹脂、アルキルエーテル化グリ
コウリル樹脂、フェニレン核またはジシクロペンタン核
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
ルエーテル化樹脂等が挙げられる。またアルキル基とし
ては水性化の観点よりメチル基が望ましい。The amino resin (B) used in the present invention is
Examples thereof include alkyl etherified melamine resins, alkyl etherified benzoguanamine resins, alkyl etherified glycouril resins, and diguanamine alkyl etherified resins in which two triazine rings are bonded to a phenylene nucleus or a dicyclopentane nucleus. Further, as the alkyl group, a methyl group is preferable from the viewpoint of making it aqueous.
【００２７】アミノ樹脂（Ｂ）は、架橋剤として固形分
で６０〜１０重量％使用され、６０重量％を越えると塗
膜の加工性が劣り、１０重量％未満では塗膜の硬度、レ
トルト性が劣る。The amino resin (B) is used as a cross-linking agent in a solid content of 60 to 10% by weight. If it exceeds 60% by weight, the processability of the coating film is poor, and if it is less than 10% by weight, the hardness and retortability of the coating film. Is inferior.
【００２８】本発明の水性塗料用樹脂組成物には、必要
に応じて硬化助剤として、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
タレンスルホン酸等あるいは酸触媒のアミンブロック体
等を添加する事が出来る。In the resin composition for water-based coating composition of the present invention, if necessary, an acid catalyst such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, or an acid-catalyzed amine block is used as a curing aid. The body etc. can be added.
【００２９】更に本発明の水性塗料用樹脂組成物には、
従来より公知のレベリング剤、消泡剤、潤滑剤、顔料等
を分散、混合等により添加することが出来る。Further, the resin composition for water-based paint of the present invention comprises
Conventionally known leveling agents, defoaming agents, lubricants, pigments and the like can be added by dispersing, mixing or the like.
【００３０】本発明の水性塗料用樹脂組成物の塗装方法
は、例えばロールコート、スプレー、刷毛塗り等公知の
手段を用いる事が出来る。As a method for coating the resin composition for water-based coating composition of the present invention, known means such as roll coating, spraying, brush coating can be used.
【００３１】本発明の水性塗料用樹脂組成物によれば、
従来塗料の塗膜の欠点であるレトルト処理後の加工部密
着性、硬度、外観等が良好で、かつ初期塗膜の硬度、外
観にも優れたバランスの良い塗膜を得る事が出来る。According to the resin composition for an aqueous paint of the present invention,
It is possible to obtain a well-balanced coating film which has good adhesion, hardness, and appearance of processed parts after retort treatment, which are defects of coating films of conventional paints, and which is excellent in hardness and appearance of the initial coating film.
【００３２】[0032]
【実施例】以下、本発明を更に具体的に説明するため、
実施例および比較例を挙げて説明するが、本発明はこれ
らの実施例に限定されるものではない。EXAMPLES In order to more specifically describe the present invention,
Examples and comparative examples will be described below, but the present invention is not limited to these examples.
【００３３】尚、例中の％とは重量％を、部とは重量部
を表す。In the examples,% means% by weight, and parts means parts by weight.
【００３４】製造例１〜４ （共重合物（Ａ）１〜４の合成）：温度計、攪伴機、還
流冷却器、滴下槽、窒素ガス導入管を取り付けた４つ口
フラスコにブチルセロソルブ４０．０部を仕込んだ後、
１４０℃まで昇温し下記表１に記載のビニル性単量体
（ａ）および他のビニル性単量体と触媒等との混合物を
５時間かけて滴下重合した。Production Examples 1 to 4 (Synthesis of Copolymers (A) 1 to 4): Butylcellosolve 40 in a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping tank, and a nitrogen gas introducing pipe. After preparing 0.0 copies,
The temperature was raised to 140 ° C., and the vinylic monomer (a) shown in Table 1 below and a mixture of another vinylic monomer and a catalyst were subjected to dropwise polymerization over 5 hours.
【００３５】この様にして合成された共重合物（Ａ）１
〜４の樹脂組成を表１に記載した。Copolymer (A) 1 thus synthesized
The resin compositions of 4 are shown in Table 1.
【００３６】[0036]
【表１】 ここで共重合物（Ａ）１〜４で用いた、ビニル性単量体
（ａ）−１〜３中のｎ、ｍまたはｍ’の平均付加モル数
は、下記による。[Table 1] The average number of moles of n, m or m ′ added in the vinyl monomers (a) -1 to 3 used in the copolymers (A) 1 to 4 is as follows.
【００３７】 比較製造例５〜１０ （共重合物５〜１０の合成）：製造例１〜４と同様な装
置および合成条件で共重合成分の組成を変え、比較共重
合物を合成した。ここで比較製造例５〜１０の組成を表
２に示す。[0037] Comparative Production Examples 5-10 (Synthesis of Copolymers 5-10): Comparative copolymers were synthesized by changing the composition of the copolymerization components under the same apparatus and synthesis conditions as in Production Examples 1-4. Table 2 shows the compositions of Comparative Production Examples 5 to 10.
【００３８】[0038]
【表２】 ここで表２中の比較製造例７，８に用いた、ＯＨ基含有
ビニル性単量体であるポリプロピレングリコールモノメ
タクリレートおよびポリエチレングリコールモノメタク
リレートのｎ，ｍまたはｍ’の平均付加モル数は、下記
による。[Table 2] Here, the average addition mole number of n, m or m ′ of polypropylene glycol monomethacrylate and polyethylene glycol monomethacrylate which are the OH group-containing vinylic monomers used in Comparative Production Examples 7 and 8 in Table 2 is as follows. by.
【００３９】 平均付加モル数 ポリプロピレングリコールモノメタクリレート ｎ：５ ｍ：０ ポリエチレングリコールモノメタクリレート ｎ：０ ｍ：８ 以上の様に合成された、表１（製造例１〜４）および、
表２（比較製造例５〜１０）に記載の樹脂（共重合物）
と、アミノ樹脂、中和用塩基成分等を用い、ホワイトコ
ート用およびクリヤーコート用として、下記、表３に示
した成分を有する水性塗料用樹脂組成物Ａ〜Ｌを調製し
た。Average number of added moles Polypropylene glycol monomethacrylate n: 5 m: 0 Polyethylene glycol monomethacrylate n: 0 m: 8 Table 1 (Production Examples 1 to 4) synthesized as described above, and
Resins (copolymers) described in Table 2 (Comparative Production Examples 5 to 10)
And amino resin, a neutralizing base component and the like were used to prepare aqueous resin compositions A to L having the components shown in Table 3 below for white coat and clear coat.
【００４０】[0040]
【表３】 ここで上記表３中の各成分は以下の通りである。[Table 3] Here, each component in the above Table 3 is as follows.
【００４１】中和剤（ＤＭＥＡ）：ジメチルエタノール
アミン アミノ樹脂（マイコート１０６）：メチル化ベンゾグア
ナミン 三井サイテック（株）社製 触媒（キャタリスト６０００）：架橋補助用酸触媒 三
井東圧化学（株）社製 白顔料：ＴｉＯ2 （二酸化チタン） （試験例１：ホワイトコート塗膜）上記表３記載の水性
塗料用樹脂組成物Ａ〜Ｊを、厚さ０．３ｍｍのブリキ板
にバーコーターで乾燥時膜厚が約１０μｍになるよう塗
装し、塗装板の温度が２００℃で３０秒間焼き付けて試
験片を作成した。得られた試験片の塗膜性能として、初
期硬度、レトルト性能試験を行い、さらに、水性塗料用
樹脂組成物としての塗料安定性も合わせて、下記表４に
示す。試験方法および判定方法は以下に示す。Neutralizer (DMEA): Dimethylethanolamine Amino resin (Mycoat 106): Methylated benzoguanamine Mitsui Cytec Co., Ltd. Catalyst (Catalyst 6000): Crosslinking acid catalyst Mitsui Toatsu Chemical Co., Ltd. White pigment manufactured by the company: TiO 2 (titanium dioxide) (Test Example 1: White coat coating film) Resin compositions A to J for water-based paint described in Table 3 above were dried on a tin plate having a thickness of 0.3 mm with a bar coater. Coating was performed so that the film thickness was about 10 μm, and the coated plate was baked at a temperature of 200 ° C. for 30 seconds to prepare a test piece. As the coating film performance of the obtained test piece, an initial hardness and retort performance test were conducted, and the coating stability as a resin composition for water-based coating is also shown in Table 4 below. The test method and determination method are shown below.
【００４２】（塗料安定性）水性塗料用樹脂組成物をそ
れぞれ試験管にとり、恒温（２０℃）にて経時（７日，
３０日）での分離の有無を観察した。(Paint Stability) Each of the resin compositions for water-based paints was placed in a test tube and kept at a constant temperature (20 ° C.) for 7 days,
The presence or absence of separation in 30 days) was observed.
【００４３】○：変化無し △：若干分離（全体の５％以下） ×：分離（全体の５％以上） （塗膜硬度試験）塗膜の初期硬度を鉛筆硬度（ＪＩＳ
Ｋ５４０１）により測定した。◯: No change Δ: Slightly separated (5% or less of the whole) X: Separated (5% or more of the whole) (Film hardness test) The initial hardness of the paint film was determined by pencil hardness (JIS).
K5401).
【００４４】（レトルト性能試験：外観）定量のイオン
交換水を入れた高温高圧滅菌器中に試験片を入れ、１３
０℃×３０分後取りだし試験片の外観を観察した。(Retort Performance Test: Appearance) The test piece was placed in a high temperature high pressure sterilizer containing a fixed amount of ion-exchanged water, and 13
After 30 minutes at 0 ° C., the appearance of the taken-out test piece was observed.
【００４５】○：良好 △：やや不良（若干の艶退けまたは痕跡あり） ×：不良（艶退けまたはブリスターおよび痕跡あり） （レトルト性能試験：加工部密着性）あらかじめデュポ
ン衝撃機、エリクセン試験機により加工された、試験片
を高温高圧滅菌器中に入れ、１３０℃×３０分後取りだ
し、試験片の加工部をテープ剥離した後、塗膜の剥離お
よび割れを観察した。◯: Good Δ: Slightly poor (slightly delustered or with traces) ×: Defect (rejected with gloss or blister and traces) (Retort performance test: adhesion of processed part) Using DuPont impactor or Erichsen tester in advance The processed test piece was placed in a high-temperature and high-pressure sterilizer and taken out after 130 ° C. for 30 minutes. The processed part of the test piece was peeled off with a tape, and peeling and cracking of the coating film were observed.
【００４６】○：良好 ：準良好（わずかな割れ） △：やや不良（若干剥離） ×：不良（剥離）◯: Good: Semi-good (slight cracking) Δ: Slightly poor (slightly peeled) ×: Bad (peeled)
【００４７】[0047]
【表４】 表４に示した結果から明らかな様に、実施例Ａ〜Ｄで調
整した水性塗料用樹脂組成物は、塗膜のレトルト性（外
観、加工部密着性）に優れ、かつ、硬度も良好でありバ
ランスのとれた塗膜となる事が分かった。これに対し、
比較例Ｅ〜Ｊで調整した水性塗料用樹脂組成物は、特に
レトルト性（外観、加工部密着性）において劣っている
事が分かった。[Table 4] As is clear from the results shown in Table 4, the resin compositions for water-based coatings prepared in Examples A to D were excellent in the retortability of the coating film (appearance, adhesion to the processed portion), and also had good hardness. It was found that the coating film had a good balance. In contrast,
It was found that the resin compositions for water-based paints prepared in Comparative Examples E to J were inferior especially in the retort property (appearance, adhesion of processed part).
【００４８】（試験例２：ホワイト／クリヤー塗膜）試
験例１と同様に作成したホワイトコートの試験片Ａ〜Ｊ
上に、表３において調整されたクリヤーコート用として
の実施例Ｋおよび比較例Ｌの水性塗料用樹脂組成物をそ
れぞれバーコーターで乾燥膜厚が１５μｍになる様に塗
装し、塗装板の温度が２００℃×３０秒間焼き付け、試
験片を作成した。得られた試験片の塗膜性能を、試験例
１と同様に塗膜硬度、レトルト性能試験を行い、温度が
かかった時の硬度を観るため湯中硬度試験を加え表５に
示す。また、試験方法および判定方法は試験例１と同様
であるが、湯中硬度試験方法を下記に示す。(Test Example 2: White / clear coating film) White coat test pieces A to J prepared in the same manner as in Test Example 1
The resin compositions for water-based coating compositions of Example K and Comparative Example L for clear coat prepared in Table 3 were each coated with a bar coater so that the dry film thickness was 15 μm, and the temperature of the coated plate was A test piece was prepared by baking at 200 ° C for 30 seconds. The coating film performance of the obtained test piece is shown in Table 5 by conducting a coating film hardness and retort performance test in the same manner as in Test Example 1 and adding a hot water hardness test to observe the hardness when a temperature is applied. The test method and determination method are the same as in Test Example 1, but the in-water hardness test method is shown below.
【００４９】（湯中硬度試験）試験片を８０℃の温水中
に浸漬し、５分後温水中で鉛筆硬度（ＪＩＳ Ｋ５４０
１）を測定した。(Hardness test in hot water) The test piece was immersed in warm water of 80 ° C., and after 5 minutes, the pencil hardness (JIS K540 was measured in the warm water.
1) was measured.
【００５０】[0050]
【表５】 ここで、表５中の水性塗料用樹脂組成物での、実施例お
よび比較例は下記の通りである。[Table 5] Here, Examples and Comparative Examples of the resin composition for water-based paint in Table 5 are as follows.
【００５１】 ホワイトコート：Ａ〜Ｄ（実施例） クリヤーコート：Ｋ（実施例） 〃 ：Ｅ〜Ｊ（比較例） 〃 ：Ｌ（比較例） 表５に示した結果から、クリヤーコート用としての水性
塗料用樹脂組成物の実施例Ｋは、いずれのホワイトコー
ト上においても硬度、レトルト性が比較例Ｌより良好で
優れている事が分かった。尚、比較例Ｌは、特に湯中硬
度、レトルト性に劣る事が分かった。White coat: A to D (Example) Clear coat: K (Example) 〃: E to J (Comparative example) 〃: L (Comparative example) From the results shown in Table 5, the results are shown as clear coat. It was found that Example K of the resin composition for water-based paints had better and better hardness and retortability than Comparative Example L on any of the white coats. It was found that Comparative Example L was particularly poor in hot water hardness and retortability.
【００５２】[0052]
【発明の効果】以上説明したように、本発明の水性塗料
用樹脂組成物はホワイトコート用途およびクリヤーコー
トにおいて、水溶化が良好で、かつ塗膜硬度（含む湯中
硬度）、レトルト性（外観、加工部密着性）等の各塗膜
性能も良好であり、バランスのとれた良好な塗膜を提供
する事ができる。As described above, the resin composition for water-based paints of the present invention has good water solubilization in white coat applications and clear coats, and has coating film hardness (including in-water hardness) and retortability (appearance). , The adhesion of the processed part) and the like, and thus a well-balanced and good coating film can be provided.
Claims (3)
単量体（ａ）を成分とし、かつ少なくとも１種以上の他
のビニル性単量体と共重合された酸価２０〜１００の共
重合物（Ａ）４０〜９０重量％とアミノ樹脂（Ｂ）６０
〜１０重量％からなる水性塗料用樹脂組成物。1. An acid value of 20 to 20 which is obtained by copolymerizing a vinylic monomer (a) having a primary OH group in one molecule with at least one or more other vinylic monomers. 100-copolymer (A) 40 to 90% by weight and amino resin (B) 60
A resin composition for an aqueous paint, which comprises from 10 to 10% by weight.
ことを特徴とする請求項１に記載の水性塗料用樹脂組成
物。 【化１】 ［但し、式中のＲ，Ｒ1 ，Ｒ2 ，Ｒ3 は 【化２】 であり、 式中のｎはいわゆるプロピレンオキサイドで付加された
モル数であり、ｍ，ｍ’はエチレンオキサイドまたはテ
トラメチレンオキサイドが付加されたモル数であり、そ
れぞれの付加モル数はｎ＝１〜１５、ｍ＝１〜１０、
ｍ’＝１〜５である。2. The resin composition for water-based paint according to claim 1, wherein the vinylic monomer (a) is represented by the following formula. Embedded image [However, R, R 1 , R 2 and R 3 in the formula are as follows: And n in the formula is the number of moles added with so-called propylene oxide, m and m ′ are the number of moles added with ethylene oxide or tetramethylene oxide, and each number of added moles is n = 1 to 15, m = 1 to 10,
m '= 1-5.
得られ、ビニル性単量体（ａ）が１〜８０重量％含有さ
れることを特徴とする請求項１に記載の水性塗料用樹脂
組成物。3. The aqueous coating composition according to claim 1, wherein the copolymer (A) is obtained by radical polymerization and contains the vinylic monomer (a) in an amount of 1 to 80% by weight. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14757194A JPH0812929A (en) | 1994-06-29 | 1994-06-29 | Water-based coating resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14757194A JPH0812929A (en) | 1994-06-29 | 1994-06-29 | Water-based coating resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0812929A true JPH0812929A (en) | 1996-01-16 |
Family
ID=15433373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14757194A Pending JPH0812929A (en) | 1994-06-29 | 1994-06-29 | Water-based coating resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812929A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002064691A2 (en) * | 2001-02-13 | 2002-08-22 | Johnson Polymer, Inc. | Aqueous coating compositions comprising styrene-surfactant-copolymer and aminoplast crosslinker |
-
1994
- 1994-06-29 JP JP14757194A patent/JPH0812929A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002064691A2 (en) * | 2001-02-13 | 2002-08-22 | Johnson Polymer, Inc. | Aqueous coating compositions comprising styrene-surfactant-copolymer and aminoplast crosslinker |
| WO2002064691A3 (en) * | 2001-02-13 | 2002-12-19 | Johnson Polymer Inc | Aqueous coating compositions comprising styrene-surfactant-copolymer and aminoplast crosslinker |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3106745B2 (en) | Coating film forming method and coated product obtained by the method | |
| JPH04255766A (en) | Copolymer capable of being diluted by water, its manufacture and use, and water-base coating composition | |
| US6048924A (en) | Aqueous resin composition and aqueous paint | |
| US6627316B1 (en) | Resin composition for water borne coatings and water borne coating composition | |
| JPH0978026A (en) | Water-based coating composition | |
| JPH0812929A (en) | Water-based coating resin composition | |
| JPH05320568A (en) | Water-based paint composition | |
| JPH0853598A (en) | Water-dispersible acrylic graft copolymer,its production andwater-based coating material | |
| JP3229688B2 (en) | Water-based paint | |
| JPH07316489A (en) | Water-based coating composition and metallic sheet or plate coated therewith | |
| JP3982021B2 (en) | Aqueous resin composition | |
| JPH0873804A (en) | Aqueous resin composition for metal coating | |
| JPH1077440A (en) | Water-base coating material for exterior of can | |
| JPH11199824A (en) | Aqueous coating material composition | |
| WO1998011165A1 (en) | Aqueous resin composition and aqueous paint | |
| JP3826513B2 (en) | Water-based paint composition and coated metal | |
| JP2001342422A (en) | Resin composition for water-based coating material and water-based coating composition | |
| JPH10259229A (en) | Water-based coating composition and coating film produced from the composition | |
| JP2006299140A (en) | Method for producing acrylic copolymer for water-borne coating composition | |
| JPH10231442A (en) | Resin for water-based coating material and water-based coating material containing the same | |
| JPH09104838A (en) | Resin composition for aqueous coating | |
| JPH06172698A (en) | Aqueous resin composition | |
| JPH06256708A (en) | Aqueous resin composition for metal coating | |
| JPH0538482A (en) | Forming method for three-layer topcoat film | |
| JPH0665535A (en) | Water-based metal-coating resin composition |