JPS624755A - Paint for metallic can - Google Patents

Paint for metallic can

Info

Publication number
JPS624755A
JPS624755A JP14262585A JP14262585A JPS624755A JP S624755 A JPS624755 A JP S624755A JP 14262585 A JP14262585 A JP 14262585A JP 14262585 A JP14262585 A JP 14262585A JP S624755 A JPS624755 A JP S624755A
Authority
JP
Japan
Prior art keywords
paint
resin
epoxy
parts
polybutadiene
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
Application number
JP14262585A
Other languages
Japanese (ja)
Inventor
Tetsuhisa Nakamura
哲久 中村
Shinichi Azuma
慎一 東
Kaoru Yamaguchi
薫 山口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Ink SC Holdings Co Ltd
Original Assignee
Toyo Ink Mfg Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyo Ink Mfg Co Ltd filed Critical Toyo Ink Mfg Co Ltd
Priority to JP14262585A priority Critical patent/JPS624755A/en
Publication of JPS624755A publication Critical patent/JPS624755A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To provide the titled paint which has excellent quick-curability, gives a coating film having excellent heat resistance, processability, etc. and is suitable for use as paint for the inner surface of a metallic can, containing a compsn. obtd by blending a thermosetting resin with a liquid epoxy-modified poly butadiene as a film-forming component. CONSTITUTION:Polybutadiene contg. at least 50wt% 1,4-butadiene unit is treated with peracetic acid to eposicize it, thus preparing an epoxy-modified polybutadiene which is liquid at room temp. 5-100pts.wt. thermosetting resin (e.g. bisphenol type epoxy resin, resol resin or amino resin) is blended with 100pts.wt. said epoxy-modified polybutadiene to obtain a compsn. which is then used as a main component for a film-forming component. The compsn. is dissolved in an org. solvent (e.g. cyclohexane or methyl cellosolve) to obtain the desired paint for a metallic can.

Description

【発明の詳細な説明】 〔発明の目的〕 (産業上の利用分野) 本発明は金属缶用塗料、特に、溶接缶のサイドシーム部
を塗装する補正塗料として、また金属缶の内面塗料とし
て有用な金属缶用塗料に関する。
[Detailed Description of the Invention] [Objective of the Invention] (Industrial Field of Application) The present invention is useful as a paint for metal cans, particularly as a correction paint for painting the side seam of welded cans, and as a paint for the inner surface of metal cans. Regarding paints for metal cans.

(従来の技術) 金属缶は、他の容器に比べて強度があり、内容物である
食品を長期保存可能な特徴をもっており、広範囲の用途
で使用されている。近年、金属缶は紙。
(Prior Art) Metal cans are stronger than other containers and have the characteristics of being able to preserve the food they contain for a long period of time, and are used in a wide range of applications. In recent years, metal cans have been replaced by paper.

プラスチック等の他の容器と同様に、美的観点から消費
者に強くアピールするため2多種の形態の缶型が作られ
始めている。特に、ビード加工、マルチネックイン等の
加工が加えられるようになっている。
As with other containers, such as plastics, cans are beginning to come in a variety of formats to appeal strongly to consumers from an aesthetic point of view. In particular, processes such as bead processing and multi-neck-in processing are being added.

製缶方法もこのような動きに対応可能なように、従来の
接着缶、半田缶から缶強度が極めて高く、設備スペース
が小さくてすむというコスト面の有利さもある。溶接缶
が広く使われ始めている。一方1缶素材の防食、加工性
向上のため、電気メツキ鋼板、ティンフリースチール等
の各種金属素材には塗膜が付着形成されているが、前記
加工に耐え、さらに9食品等め内容物を長期保存可能な
防食性を兼ね備えた塗膜を形成させるのは、一般に困難
であり、実用的に不十分な点も多い。
The can manufacturing method is also able to cope with such movements, and has the advantage of being extremely strong compared to conventional adhesive cans and solder cans, and requiring less equipment space, which is advantageous in terms of cost. Welded cans are beginning to be widely used. On the other hand, in order to prevent corrosion and improve processability of single can materials, various metal materials such as electroplated steel sheets and tin-free steel are coated with coatings, which can withstand the above processing and also protect the contents such as 9 foods. It is generally difficult to form a coating film that has corrosion resistance and can be stored for a long period of time, and there are many practical problems.

特に、溶接缶の場合には2缶胴素材の両切断面の端面を
重ね合せ(ラップシーム)して、溶接するために、切断
面が未塗装のまま缶内面に露出し、素材が電気メツキブ
リキであれば溶接時の熱によって錫カリフローし、また
、ティンフリースチールであれば溶接し易いように削っ
である金属表面から腐食が起り易い。これを防ぐため溶
接部の缶内面部、場合によっては外面部にも補正塗料を
塗布し、保護皮膜を形成する必要があるが、かかる溶接
部の溶接段差は比較的大きく、この部分は特に厚い塗膜
を形成する必要があり、加工が加わると耐蝕性が良好な
塗膜であれば、クランクが発生しやすく、耐蝕性と加工
性が共に良好な塗膜を形成するのは一般に困難であるた
め、補正塗料の性能が溶接缶の性能を左右する重要な要
素となっている。
In particular, in the case of welded cans, the end surfaces of both cut surfaces of the two can body materials are overlapped (lap seam) and welded, so the cut surfaces are exposed to the inside of the can without being painted, and the materials are exposed to electroplated tin. If so, tin cauliflow occurs due to the heat during welding, and if it is tin-free steel, corrosion is likely to occur from the metal surface, which is shaved to make it easier to weld. To prevent this, it is necessary to apply correction paint to the inner surface of the can, and in some cases to the outer surface of the weld, to form a protective film, but the welding step in such welds is relatively large, and this part is especially thick. It is necessary to form a coating film, and if a coating film with good corrosion resistance is processed, cranking is likely to occur, and it is generally difficult to form a coating film with good corrosion resistance and processability. Therefore, the performance of the correction paint is an important factor that affects the performance of welded cans.

このように金属缶用塗料は、近年、ビード、マルチネッ
クイン等の厳しい加工にも耐え、かつ2食品等の内容物
を長期保存可能な塗膜を形成すること。
In this way, paints for metal cans have recently been developed to withstand severe processing such as beading and multi-neck-in, and to form coatings that can preserve the contents of foodstuffs and the like for long periods of time.

特に、溶接缶補正塗料は、短時間の焼き付は条件で厚い
塗膜を形成するすることが必要とされている。
In particular, weld can correction paints are required to form a thick coating under the condition of short-term baking.

このような種々の要求を満足させるための塗料について
はいくつかの提案がなされている。一つは、塩化ビニル
樹脂系のオルガノゾル組成物を主成分とするものであり
(特開昭55−49174号公報)。
Several proposals have been made regarding paints to satisfy these various demands. One is one whose main component is a vinyl chloride resin-based organosol composition (Japanese Unexamined Patent Publication No. 55-49174).

あるいは、エポキシ−アクリル系、エポキシ−アミノ系
もしくはエポキシ−フェノール系の各種の熱硬化性塗料
にポリエステル樹脂を添加した金属缶用塗料が知られて
いる(特開昭50−32230号公報。
Alternatively, metal can paints are known in which a polyester resin is added to various types of epoxy-acrylic, epoxy-amino, or epoxy-phenol thermosetting paints (Japanese Patent Laid-Open Publication No. 32230/1983).

特開昭55−5936号公報)。JP-A No. 55-5936).

しかしながら、熱可塑性樹脂を含む塗料は短時間で塗膜
を形成することが可能であるが、飲料や食品を内容物と
する場合には、耐酸性および殺菌のため高温レトルト処
理に対するだけの十分の耐蝕性、耐内容物性の点で欠点
がある。また、エポキシ樹脂系の上記熱硬化性塗料およ
びポリエステル樹脂含有熱硬化性塗料は、一般に、溶接
缶補正塗料の焼付条件である2分以下、特に、30秒以
下の短時間焼付では、220〜260℃程度の高温であ
っても十分硬化せず、耐蝕性に優れた塗膜が形成されが
たい。しかも、厚膜での加工性が劣り、比較的加工性が
優れることを特徴とするポリエステル樹脂含有熱硬化性
塗料でも十分な性能を出すに至っていない。
However, although paints containing thermoplastic resins can form a film in a short time, when the content is beverages or food, they require sufficient acid resistance and sterilization to withstand high-temperature retort processing. It has drawbacks in terms of corrosion resistance and content resistance. In addition, the above-mentioned epoxy resin-based thermosetting paints and polyester resin-containing thermosetting paints generally have a 220 to 260 It does not cure sufficiently even at temperatures as high as ℃, making it difficult to form a coating film with excellent corrosion resistance. Moreover, the processability of thick films is poor, and even thermosetting paints containing polyester resin, which are characterized by relatively excellent processability, have not yet achieved sufficient performance.

(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。(Problem to be solved by the invention) The present invention has been made in view of the above-mentioned current situation.

その目的とするところは、ビード、マルチネックイン等
の厳しい加工にも耐え、かつ1食品等の内容物を長期保
存可能な塗膜を形成すること、特に、溶接缶補正塗料と
しては、短時間の焼付条件で厚い塗膜を形成し、加工性
、耐内容物性に優れた塗膜を形成することが可能な金属
缶用塗料を提供するものである。
The purpose is to form a coating film that can withstand severe processing such as beading and multi-neck-in, and can preserve the contents of food products for a long period of time. The purpose of the present invention is to provide a paint for metal cans that can form a thick coating film under the following baking conditions and is capable of forming a coating film with excellent workability and resistance to contents.

〔発明の構成〕[Structure of the invention]

(問題点を解決するための手段) すなわち2本発明は、塗膜形成成分が主として。 (Means for solving problems) That is, in the present invention, the main component is a coating film forming component.

常温で液状であって、1.4ブタジエン単位を50重量
%以上含むポリブタジェンをエポキシ化したエポキシ変
性ポリブタジェン100.!置部に対して熱硬化性樹脂
5重量部ないし100重量部未満を配合した組成物から
なる速硬化性に優れた有機溶剤ベースの金属缶用塗料で
ある。
Epoxy-modified polybutadiene 100, which is liquid at room temperature and is obtained by epoxidizing polybutadiene containing 50% by weight or more of 1.4 butadiene units. ! This is an organic solvent-based paint for metal cans with excellent rapid curing properties, which is made of a composition containing 5 parts by weight to less than 100 parts by weight of a thermosetting resin based on the holding part.

本発明におけるエポキシ変性ポリブタジェンは。The epoxy-modified polybutadiene in the present invention is.

液状ポリブタジェン系樹脂を過酢酸、過ギ酸等の過酸で
変性することにより得ることができる。液状ポリブタジ
ェン系樹脂中に導入されるエポキシ基は。
It can be obtained by modifying a liquid polybutadiene resin with a peracid such as peracetic acid or performic acid. The epoxy group introduced into the liquid polybutadiene resin.

一分子当り2〜20個である。The number is 2 to 20 per molecule.

上記液状ポリブタジェン系樹脂は、1,4−ブタジェン
単位を50重量%、好ましくは70重量%以上含むもの
である。繰り返し単位の残部は、1.2−ブタジェン単
位からなるものが好ましいが、この他にα−メチルスチ
レン、スチレン等のブタジェン以外のモノマーを含んで
いてもよい。数平均分子量としては、500〜1000
0好ましくは、1000〜5000のものが使用される
。また1分子の両末端に水酸基、カルボキシル基、エポ
キシ基等の官能基を有していても良い。
The liquid polybutadiene resin contains 50% by weight, preferably 70% by weight or more of 1,4-butadiene units. The remainder of the repeating units preferably consist of 1,2-butadiene units, but may also contain monomers other than butadiene, such as α-methylstyrene and styrene. The number average molecular weight is 500 to 1000
0 Preferably, those of 1000 to 5000 are used. Further, one molecule may have a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group at both ends.

本発明における熱硬化性樹脂としては、エポキシ樹脂、
フェノール樹脂、アミノ樹脂、アルキド樹脂。
As the thermosetting resin in the present invention, epoxy resin,
Phenolic resin, amino resin, alkyd resin.

熱硬化性アクリル樹脂等がある。好ましくは、ビスフェ
ノール型エポキシ樹脂とレゾール樹脂あるいはアミン樹
脂の組み合わせである。 ゛ ビスフェノール型エポキシ樹脂は、ビスフェノールA型
エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、
ビスフェノールF型エポキシ樹脂等に代表されるエポキ
シ樹脂である。特に、ビスフェノールAとエピクロルヒ
ドリンとの反応で得られるもので平均のエポキシ当量と
して1500〜4000のエポキシ樹脂が好ましく使用
できる。また、ビスフェノール型エポキシ樹脂を、リノ
ール酸、リルン酸、脱水ひまし油脂肪酸、大豆油脂肪酸
、やし油脂肪酸等の高級不飽和脂肪酸でエステル化した
ものも同様に使用できる。
There are thermosetting acrylic resins, etc. Preferably, it is a combination of a bisphenol type epoxy resin and a resol resin or an amine resin.゛Bisphenol type epoxy resin includes bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin,
This is an epoxy resin typified by bisphenol F type epoxy resin. In particular, epoxy resins obtained by the reaction of bisphenol A and epichlorohydrin and having an average epoxy equivalent of 1,500 to 4,000 can be preferably used. Furthermore, bisphenol type epoxy resins esterified with higher unsaturated fatty acids such as linoleic acid, lilunic acid, dehydrated castor oil fatty acids, soybean oil fatty acids, and coconut oil fatty acids can also be used.

レゾール樹脂は2石炭酸、クレゾール類、エチルフェノ
ール類、その他のアルキルフェノール類あるいはビスフ
ェノール類等のフェノール類とホルムアルデヒド、アセ
トアルデヒド等のアルデヒド類とを塩基性触媒の存在下
で反応させて得られたもの、又は、それらをアルコール
類と反応させたアルキルエーテル化フェノール樹脂を使
用することが出来る。
Resole resins are those obtained by reacting phenols such as dicarbolic acid, cresols, ethylphenols, other alkylphenols or bisphenols with aldehydes such as formaldehyde and acetaldehyde in the presence of a basic catalyst, or , alkyl etherified phenolic resins obtained by reacting them with alcohols can be used.

アミノ樹脂は、尿素、メラミン、トリアジン化合物とホ
ルムアルデヒドとを反応させたもの、又は。
Amino resin is a product obtained by reacting urea, melamine, a triazine compound with formaldehyde, or.

これに炭素数1〜4のm個アルコールを用いてエーテル
化したものであってもよい。
This may be etherified using m alcohols having 1 to 4 carbon atoms.

本発明においてエポキシ変性ポリブタジェンと熱硬化性
樹脂との配合比率は、エポキシ変性ポリブタジェン10
0重量部に対して熱硬化性樹脂が5重量部から100重
量未満である。好ましくは熱硬化性樹脂は、20重量部
以上%である。熱硬化性樹脂の量が少なくなるに従って
塗膜硬度および耐内容物性に劣る傾向があり、逆に10
0重量部より多いと加工性および速硬化性が劣る傾向が
ある。
In the present invention, the blending ratio of epoxy-modified polybutadiene and thermosetting resin is 10% of epoxy-modified polybutadiene.
The thermosetting resin is 5 parts by weight to less than 100 parts by weight relative to 0 parts by weight. Preferably, the amount of thermosetting resin is 20 parts by weight or more. As the amount of thermosetting resin decreases, the coating film hardness and content resistance tend to deteriorate;
When the amount is more than 0 parts by weight, processability and fast curing properties tend to be poor.

本発明の金属缶用塗料はエポキシ変性ポリブタジェンと
熱硬化性樹脂を有機溶剤に溶解して使用される。上記有
機溶剤としては、アセトン、メチルエチルケトン、メチ
ルイソブチルケトン、シクロヘキサノン、キシレンその
他のアルキルベンゼン等の芳香族類、メチルセロソルブ
、エチルセロソルブ、ブチルセロソルブ等のセロソルブ
類、メチルセロソルブアセテート ブチルセロソルブア
セテート酢酸エチル、酢酸ブチル等のエステル類、イソ
プロピルアルコール、ブチルアルコール、ジアセトンア
ルコール等のアルコール類等、またはこれらの混合溶剤
を用いることができる。
The paint for metal cans of the present invention is used by dissolving epoxy-modified polybutadiene and thermosetting resin in an organic solvent. Examples of the organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, xylene, and other alkylbenzenes, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl acetate, butyl acetate, etc. Esters, alcohols such as isopropyl alcohol, butyl alcohol, diacetone alcohol, etc., or mixed solvents thereof can be used.

本発明の金属缶用塗料は、エポキシ変性ポリブタジェン
と熱硬化性樹脂を主成分とするものであるが。
The paint for metal cans of the present invention mainly contains epoxy-modified polybutadiene and a thermosetting resin.

これ以外に熱可塑性樹脂を全樹脂成分の30重量%以内
で配合することができる。特に補正塗料として用いる場
合、溶接部段差と切断部のパリに対する被覆性を向上さ
せるため、ポリアミド樹脂、カルボキシル基変性ポリオ
レフィン樹脂、ポリエステル樹脂。
In addition to this, a thermoplastic resin may be blended within 30% by weight of the total resin components. In particular, when used as a correction paint, polyamide resin, carboxyl group-modified polyolefin resin, and polyester resin are used to improve coverage of welded part steps and cut parts.

ポリ塩化ビニル樹脂、ポリアセタール樹脂等の熱可塑性
樹脂の微粒子を塗料中に分散させて用いることができる
Fine particles of thermoplastic resin such as polyvinyl chloride resin and polyacetal resin can be dispersed in the paint.

本発明の金属缶用塗料には、硬化促進のためリン酸、リ
ン酸エステルW4.p−1ルエンスルホン酸。
The paint for metal cans of the present invention contains phosphoric acid, phosphate ester W4. p-1 luenesulfonic acid.

トリメリット酸等の酸性物質、オクチル酸亜鉛、ナフテ
ン酸亜鉛等の塩類あるいはアルミニウムアルコラード、
アルキルチタネート等の有機金属化合物系硬化助剤また
液状ポリブタジェンに側鎖として含まれる炭素−炭素二
重結合の反応剤としてトリメチルアミン、トリエチルア
ミン、ジメチルアミノエタノール等のアミン触媒あるい
はベンゾイルパーオキサイド等の有機過酸化物等のラジ
カル発生剤を添加することができる。
Acidic substances such as trimellitic acid, salts such as zinc octylate and zinc naphthenate, or aluminum alcoholade,
Organometallic compound-based curing aids such as alkyl titanates, amine catalysts such as trimethylamine, triethylamine, dimethylaminoethanol, etc., or organic peroxides such as benzoyl peroxide as reagents for carbon-carbon double bonds contained as side chains in liquid polybutadiene. A radical generating agent such as a compound or the like can be added.

本発明に係る金属缶用塗料には、他の慣用的添加剤9例
えば着色用染顔料、防錆顔料、充填剤、界面活性剤、潤
滑剤等を添加することができる。
Other conventional additives 9 such as coloring dyes and pigments, antirust pigments, fillers, surfactants, lubricants, etc. can be added to the paint for metal cans according to the present invention.

本発明の金属缶用塗料を塗装する方法としては。A method for applying the paint for metal cans of the present invention is as follows.

スプレー、ロールコート、ハケ塗り、流し塗り等の公知
の手段を用いることができる。
Known means such as spraying, roll coating, brush coating, flow coating, etc. can be used.

以下2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。
The present invention will be specifically explained below using two examples. In the examples, "parts" and "%" indicate "parts by weight" and "% by weight."

(実施例) (エポキシ樹脂溶液(a)の調整) エピコート1009 (油化シェルエポキシ■製ビスフ
ェノールA型エポキシ樹脂、エポキシ当量2650)1
00部をジエチレングリコール七ノエチルエーテルアセ
テート100部に90℃にて溶解し。
(Example) (Preparation of epoxy resin solution (a)) Epicoat 1009 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy ■, epoxy equivalent: 2650) 1
00 parts was dissolved in 100 parts of diethylene glycol heptanoethyl ether acetate at 90°C.

エポキシ樹脂溶液(a)とした。This was referred to as epoxy resin solution (a).

(エポキシ樹脂溶液(b)の調整) エピコート1007 (油化シェルエポキシ■製ビスフ
ェノールA型エポキシ樹脂、エポキシ当量1950)を
エピコート1009の代わりに使用した以外は、エポキ
シ樹脂溶液(a)と同様に調整した。
(Preparation of epoxy resin solution (b)) Prepared in the same manner as epoxy resin solution (a), except that Epicote 1007 (bisphenol A epoxy resin manufactured by Yuka Shell Epoxy ■, epoxy equivalent: 1950) was used instead of Epicote 1009. did.

(エポキシエステル樹脂溶液(C)の調整)AER66
7(旭化成工業■製ビスフェノールA型エポキシ樹脂)
100部、大豆油脂肪酸40部。
(Preparation of epoxy ester resin solution (C)) AER66
7 (Bisphenol A epoxy resin manufactured by Asahi Kasei Corporation)
100 parts, soybean oil fatty acid 40 parts.

キシレン10部を220℃に3時間反応させ、酸価が1
0以下になったところで反応を終了し、ツルペッツ10
0. ツルペッツ150.ジエチレングリコ−ルモノエ
チルエーテルアセテートを各々65部を加えて冷却し、
エポキシエステル樹脂溶液(c)とした。
10 parts of xylene was reacted at 220°C for 3 hours, and the acid value was 1.
The reaction is terminated when it becomes 0 or less, and Tsurpets 10
0. Tsurpets 150. Add 65 parts each of diethylene glycol monoethyl ether acetate and cool.
This was used as an epoxy ester resin solution (c).

(レゾール樹脂(d)の調整) p−クレゾール108部、ホルムアルデヒドの40%n
−7’タノ一ル溶液56部、25%アンモニア14部を
100℃にて3時間反応させた後、キシレン、シクロヘ
キサノンおよびn−ブタノール各110部を加えて樹脂
成分を抽出し、更に説水して固型分35%のレゾール樹
脂溶液(d)とした。
(Adjustment of resol resin (d)) 108 parts of p-cresol, 40% n of formaldehyde
- After reacting 56 parts of 7' tanol solution and 14 parts of 25% ammonia at 100°C for 3 hours, 110 parts each of xylene, cyclohexanone and n-butanol were added to extract the resin component, and further water was added. A resol resin solution (d) having a solid content of 35% was obtained.

実施例1〜5 末端水酸基および分子内エポキシ基含有液状ポリブタジ
ェン(f)(出光石油化学社製、1,4−ブタジェン8
0%、1,2−ブタシェフ20%2分子量2800 i
商品名Po1yPd R−45EPI)と上記エポキシ
樹脂溶液(a)、エポキシ樹脂溶液(b)、エポキシエ
ステル樹脂溶液(c)レゾール樹脂溶液(d)、アミノ
樹脂溶液(e)(日本ライヒホールド社製;商品名ベッ
カミンL−105−60)を固型分比で表1となるよう
に混合し、硬化触媒としてリン酸およびアルミニウムジ
イソプロピレートを添加もしくは添加することなく、ジ
エチレングリコールモ、ノブチルエーテル/エチレング
リコールモノエチルエーテルアセテート/イソプロピル
アルコール=40/40/20の混合溶剤で粘度25℃
で50秒(#4フォードカップ)となるように調整し実
施例1〜5の金属缶ベース塗料とした。
Examples 1 to 5 Liquid polybutadiene (f) containing a terminal hydroxyl group and an intramolecular epoxy group (manufactured by Idemitsu Petrochemical Co., Ltd., 1,4-butadiene 8
0%, 1,2-butashev 20%2 molecular weight 2800 i
Product name PolyPd R-45EPI) and the above epoxy resin solution (a), epoxy resin solution (b), epoxy ester resin solution (c), resol resin solution (d), amino resin solution (e) (manufactured by Nippon Reichhold Co., Ltd.; (trade name Beckamine L-105-60) was mixed so that the solid content ratio was as shown in Table 1, and diethylene glycol, butyl ether/ethylene glycol was prepared with or without addition of phosphoric acid and aluminum diisopropylate as a curing catalyst. Viscosity at 25°C with a mixed solvent of monoethyl ether acetate/isopropyl alcohol = 40/40/20.
The coating time was adjusted to 50 seconds (#4 Ford Cup) and used as metal can base paints of Examples 1 to 5.

また、同様にして比較例1〜3の金属缶ベース塗料を調
整した。
In addition, metal can base paints of Comparative Examples 1 to 3 were prepared in the same manner.

実施例1〜5および比較例1〜3で得られた塗料につい
て塗料試験および塗装試験を行い、結果を表2に示した
A paint test and a coating test were conducted on the paints obtained in Examples 1 to 5 and Comparative Examples 1 to 3, and the results are shown in Table 2.

各試験方法は下記のとおりである。Each test method is as follows.

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2分
離の状態を観察した。
Paint stability test: After each paint was stored at room temperature for 2 months, the state of gelation and separation of the resin was observed.

折曲げ加工性試験: 板厚0.23鶴の電気メツキブリキにロールコート塗装
により前記金属缶ベース塗料を乾燥後塗膜厚5μになる
ように塗装し、ガスオープンにて雰囲気温度190℃に
おいて10分間焼付け、塗装パネルを作成した。塗装パ
ネルを3 cm X 5 cmに切断し、マン)=Lz
/Izl/8インチ径で折曲げた後、塗装パネルと同一
厚さの鋼板一枚をはさみ、塗膜表面を傷つけないように
ポリエチレンフィルムでカバーした上で。
Bending workability test: The metal can base paint was applied by roll coating to a 0.23-thick electroplated tin plate so that the film thickness after drying was 5 μm, and the temperature was 190°C with the gas open for 10 minutes. Baked and painted panels were created. Cut the painted panel into 3 cm x 5 cm,
/Izl/ After bending it to a diameter of 8 inches, sandwich a steel plate with the same thickness as the painted panel and cover it with polyethylene film to avoid damaging the paint surface.

折曲げ試験機(1にg、30cm高さ)で折曲げ、加工
部を硫酸銅溶液に浸漬して、銅の析出状態(付着)より
、折曲げ加工性を評価した。
It was bent using a bending tester (1 g, 30 cm height), and the processed part was immersed in a copper sulfate solution to evaluate the bending workability based on the state of copper precipitation (adhesion).

打ちぬき加工性試験: 塗装パネルを塗膜が外側になるように高さ9鶴、直径3
6mのキャップを打ちぬき、塗膜の加工状態を評価する
Punching workability test: Painted panels were cut to a height of 9 mm and a diameter of 3 mm with the paint film facing outward.
Punch out a 6m cap and evaluate the processing condition of the coating film.

鉛筆硬度試験: 塗装パネルの塗膜硬度を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: The coating hardness of the painted panel was evaluated using a pencil hardness test method in accordance with JIS standards.

耐内容物性試験: 塗装パネルを3cffI×7CI11に切断し、コーヒ
ーに浸ff1L、125℃にて40分間レトルト処理し
、更に37℃3ケ月間保存し、腐蝕状態および塗膜の白
化状態を評価した(コーヒー)。 同様にトマトジュー
スに浸漬し、97℃にて30分間加温し、更に37℃3
ケ月間保存し腐蝕状態および塗膜の白化状態を評価した
(トマトジュース)。
Content resistance test: Painted panels were cut into 3cffI x 7CI11 pieces, immersed in ff1L of coffee, retorted at 125°C for 40 minutes, and further stored at 37°C for 3 months to evaluate the state of corrosion and whitening of the paint film. (coffee). Similarly, it was soaked in tomato juice, heated at 97℃ for 30 minutes, and further heated at 37℃3.
The product was stored for several months and the state of corrosion and whitening of the paint film were evaluated (tomato juice).

表2から明らかなように実施例1〜5で得られた塗料は
、加工性に優れ、塗膜硬度、耐内容物性にも優れた性能
を有しているのに対して、比較例1〜3で得られた塗料
は、塗膜硬度、耐内容物性は優れているものの、加工性
が劣り、金属缶ベース塗料として本発明で得られた塗料
の方が、比較例の塗料より。
As is clear from Table 2, the paints obtained in Examples 1 to 5 have excellent processability, film hardness, and resistance to contents, whereas Comparative Examples 1 to 5 Although the paint obtained in step 3 has excellent coating hardness and content resistance, it has poor processability, and the paint obtained according to the present invention as a metal can base paint is better than the paint of the comparative example.

加工性と耐内容物性のバランスにおいて優れた性能を有
している。
It has excellent performance in terms of balance between processability and content resistance.

実施例1〜5で得られた塗料を溶接缶の溶接部の補正塗
料として以下の方法に従い塗装焼付し、物性試験を行っ
た。
The paints obtained in Examples 1 to 5 were used as correction paints for the welded parts of welded cans and baked according to the following method, and physical property tests were conducted.

板圧0.23+nの錫メッキ鋼板にアプリケーターによ
り乾燥後塗膜30μになるように塗装し、ガスバーナー
にて30秒間焼付た。焼付は30秒後に板温が230℃
に達するようにセントした。
It was applied to a tin-plated steel plate with a plate thickness of 0.23+n using an applicator so that the film thickness after drying was 30 μm, and baked for 30 seconds with a gas burner. The board temperature reaches 230℃ after 30 seconds of baking.
Cents to reach.

次に、このようにして作成した塗装パネルを用いて、前
記金属缶ベース塗料と同様の折り曲げ加工性試験、鉛筆
硬度試験、耐内容物性試験、打ちぬき加工性試験を行っ
た。耐内容物試験としてはコーヒーとトマトジュースの
他に以下の方法に示すツナによる試験を行った。
Next, using the thus-prepared painted panel, the same bending workability test, pencil hardness test, contents resistance test, and punching workability test as for the metal can base paint were conducted. In addition to coffee and tomato juice, the contents resistance test was conducted using tuna according to the following method.

耐内容物性試験(ツナ): 塗装パネルを3鶴×7鶴に切断し、ツナに浸漬し117
℃にて90分間レトルト処理し50℃にて1゜5ケ月保
存し、硫化黒変の発生状態および塗膜の白化状態を評価
した。
Content resistance test (Tuna): Cut the painted panel into 3 cranes x 7 cranes, immerse it in tuna, and test 117
It was retorted at 50°C for 90 minutes and stored for 1.5 months at 50°C, and the state of occurrence of black sulfide discoloration and the state of whitening of the coating film were evaluated.

実施例および比較例で得られた塗料の溶接缶補正塗料と
しての塗膜試験の結果を表3に示す。
Table 3 shows the results of a coating film test of the coatings obtained in Examples and Comparative Examples as welded can correction coatings.

実施例1〜5で得られた塗料は、加工性に優れた特徴を
有し、塗膜硬度、耐内容物性にも優れた特徴を有してい
るのに対し、比較例1〜3で得られた塗料は、加工性が
劣り、耐内容物性とのバランスが悪く、溶接缶補正塗料
として実用的ではない。
The paints obtained in Examples 1 to 5 had excellent processability, and also had excellent coating hardness and resistance to contents, whereas the paints obtained in Comparative Examples 1 to 3 The resulting paint has poor processability and poor balance with content resistance, making it impractical as a welding can correction paint.

実施例6〜8 実施例3で得られた塗料に対し、平均粒子径工4μのナ
イロン12微粉末、平均粒子径2μのナイロン微粉末を
、および平均粒子径5μの塩ビペーストレジン(住友化
学工業■製、商品名スミリッ)XI3)の微粉末を固形
分比で表4となるように高速攪拌しながら混合し、溶接
缶補正塗料を得た。
Examples 6 to 8 For the paint obtained in Example 3, nylon 12 fine powder with an average particle size of 4μ, nylon fine powder with an average particle size of 2μ, and PVC paste resin (Sumitomo Chemical Co., Ltd.) with an average particle size of 5μ A fine powder of Sumiri (trade name) XI3), manufactured by 1 Co., Ltd., was mixed with high speed stirring so that the solid content ratio was as shown in Table 4 to obtain a welding can correction paint.

実施例6〜8で得られた溶接缶補正塗料を実施例5と同
様の方法で試験し塗膜性能を調べた。
The weld can correction paints obtained in Examples 6 to 8 were tested in the same manner as in Example 5 to examine coating film performance.

結果を表5に示す。The results are shown in Table 5.

〔発明の効果〕〔Effect of the invention〕

本発明の金属缶用塗料は、金属缶用の内面塗料もしくは
、外面塗料用のベース塗料として従来用いられてきたビ
スフェノール型エポキシ樹脂を主成分とする塗料に匹敵
する耐内容物性、耐熱性を有している上に、ポリブタジ
ェンの柔軟性に起因する塗膜加工性を兼備えている。ま
た、金属缶の内面用塗料として必要な塗膜硬度にも優れ
る。
The paint for metal cans of the present invention has content resistance and heat resistance comparable to paints containing bisphenol-type epoxy resin as a main component, which have been conventionally used as base paints for interior paints or exterior paints for metal cans. In addition, it has excellent coating processability due to the flexibility of polybutadiene. It also has excellent coating hardness, which is required as a paint for the inner surface of metal cans.

また、溶接缶用の補正塗料として使用した場合。Also, when used as a correction paint for welding cans.

220℃以上で60秒間、場合によっては15秒という
高温、短時間で乾燥焼付することが可能である。
It is possible to dry and bake at a high temperature of 220° C. or higher for 60 seconds, or in some cases for 15 seconds in a short time.

手続補正書(自発) 昭和60年11月22−日Procedural amendment (voluntary) November 22, 1985 - Sunday

Claims (1)

【特許請求の範囲】 1、塗膜形成成分が主として、常温で液状であって、1
、4ブタジエン単位を50重量%以上含むポリブタジエ
ンをエポキシ化したエポキシ変性ポリブタジエン100
重量部に対して熱硬化性樹脂5重量部ないし100重量
部未満を配合した組成物からなる速硬化性に優れた有機
溶剤ベースの金属缶用塗料。 2、熱硬化性樹脂がビスフェノール型エポキシ樹脂、レ
ゾール樹脂およびアミノ樹脂から選ばれる1種もしくは
2種以上の樹脂である特許請求の範囲第1項記載の金属
缶用塗料。 3、金属缶の内面用塗料である特許請求の範囲第1項記
載の金属缶用塗料。
[Scope of Claims] 1. The coating film-forming component is mainly liquid at room temperature, 1.
, epoxy-modified polybutadiene 100 obtained by epoxidizing polybutadiene containing 50% by weight or more of 4-butadiene units.
An organic solvent-based paint for metal cans with excellent rapid curing properties, comprising a composition containing 5 parts by weight to less than 100 parts by weight of a thermosetting resin. 2. The paint for metal cans according to claim 1, wherein the thermosetting resin is one or more resins selected from bisphenol-type epoxy resins, resol resins, and amino resins. 3. The paint for metal cans according to claim 1, which is a paint for the inner surface of metal cans.
JP14262585A 1985-07-01 1985-07-01 Paint for metallic can Pending JPS624755A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14262585A JPS624755A (en) 1985-07-01 1985-07-01 Paint for metallic can

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14262585A JPS624755A (en) 1985-07-01 1985-07-01 Paint for metallic can

Publications (1)

Publication Number Publication Date
JPS624755A true JPS624755A (en) 1987-01-10

Family

ID=15319690

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14262585A Pending JPS624755A (en) 1985-07-01 1985-07-01 Paint for metallic can

Country Status (1)

Country Link
JP (1) JPS624755A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015209463A (en) * 2014-04-25 2015-11-24 関西ペイント株式会社 Coating composition and coated metal can
US9617446B2 (en) 2010-12-29 2017-04-11 Akzo Nobel Coatings International B.V. Adhesion promoter resin compositions and coating compositions having the adhesion promoter resin compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5364238A (en) * 1976-11-22 1978-06-08 Toyo Ink Mfg Co Ltd Coating compositions
JPS5388038A (en) * 1977-01-13 1978-08-03 Sumitomo Chem Co Ltd Coating composition
JPS5490139A (en) * 1977-12-23 1979-07-17 Ciba Geigy Ag Anhydrous trimellitic acid ester mixture and lacquer containing said mixture
JPS54139942A (en) * 1978-04-24 1979-10-30 Yoshizaki Kozo Can coating material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5364238A (en) * 1976-11-22 1978-06-08 Toyo Ink Mfg Co Ltd Coating compositions
JPS5388038A (en) * 1977-01-13 1978-08-03 Sumitomo Chem Co Ltd Coating composition
JPS5490139A (en) * 1977-12-23 1979-07-17 Ciba Geigy Ag Anhydrous trimellitic acid ester mixture and lacquer containing said mixture
JPS54139942A (en) * 1978-04-24 1979-10-30 Yoshizaki Kozo Can coating material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9617446B2 (en) 2010-12-29 2017-04-11 Akzo Nobel Coatings International B.V. Adhesion promoter resin compositions and coating compositions having the adhesion promoter resin compositions
JP2015209463A (en) * 2014-04-25 2015-11-24 関西ペイント株式会社 Coating composition and coated metal can

Similar Documents

Publication Publication Date Title
JP6571720B2 (en) Polyertel-based coating composition for metal substrate
JP6511097B2 (en) Methods and Materials for Functionalization of Polymers and Coatings Comprising Functionalized Polymers
US4076676A (en) Aqueous coating composition from aminoplast and reaction product of tertiary amine and polymer containing terminal epoxy groups
EP0204511B1 (en) Aqueous epoxy resin dispersions for can coating use
US3123582A (en) Liquid coating composition and metal
KR860000867B1 (en) Side seam-coated tinplate welded can
JPS624756A (en) Paint for metallic can
EP3268439B1 (en) Container coating compositions
JPS624755A (en) Paint for metallic can
JPH068399B2 (en) Paint for can manufacturing
JPH032257A (en) Composition capable of forming lubricant coating film
JPS61268768A (en) Coating for application to metallic can
JPH0292916A (en) Resin composition and coating compound composition for can
JPH05269917A (en) Laminated metal panel for can making and primer used therein
JPH0613667B2 (en) Metal coating composition
JP2865401B2 (en) Resin composition for baking type can inner coating
JP2780616B2 (en) Epoxy paint
JP4910371B2 (en) Polyolefin adhesive coating composition
EP0070008A2 (en) Aluminum thrihydrate modified zinc-rich coatings
JP2005054074A (en) Anticorrosive zinc-containing coating composition for stainless steel
US2923431A (en) Protective coating
JPS6143664A (en) Correcting coating compound
JP3209609B2 (en) Aqueous coating composition
JP3528240B2 (en) Laminated body and method for producing the same
EP1218114A2 (en) Paint composition