JPH07233348A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH07233348A JPH07233348A JP6051212A JP5121294A JPH07233348A JP H07233348 A JPH07233348 A JP H07233348A JP 6051212 A JP6051212 A JP 6051212A JP 5121294 A JP5121294 A JP 5121294A JP H07233348 A JPH07233348 A JP H07233348A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- wax
- resin composition
- weight
- aluminum foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】食品、飲料品用などに用いられる
アルミニウム箔製深絞り容器用塗料、特に絞り比が高い
深絞り成形の２段成形加工においてもショックライン
（１段目コーナー部）の塗膜剥れの防止のための塗料に
関する。[Industrial application] Paint for aluminum foil deep-drawing containers used for foods, beverages, etc., especially in the two-stage forming process of deep-drawing with a high drawing ratio. The present invention relates to a paint for preventing peeling of a coating film.
【０００２】[0002]
【従来の技術】エポキシ樹脂は熱硬化性樹脂であり、用
途に応じた硬化剤と組み合わせ、硬化（橋かけ）するこ
とでさまざまな特性を持った硬化樹脂を得ることができ
る。特に耐熱性、機械的性質のバランス、接着特性、耐
食性などに優れていること、成形が容易なことから溶剤
型塗料、粉体塗料、水性塗料などの形態で種々な分野の
塗料、もちろんアルミニウム箔容器にも用いられてい
る。2. Description of the Related Art Epoxy resin is a thermosetting resin, and a curable resin having various characteristics can be obtained by combining (curing) with a curing agent suitable for the intended use. In particular, it is excellent in heat resistance, balance of mechanical properties, adhesive properties, corrosion resistance, etc., and it is easy to mold, so it is a solvent type paint, powder paint, water-based paint, etc. It is also used in containers.
【０００３】一方、アルミニウム箔は外観が美麗である
こと、軽量であること、特に最も優れた特徴として加工
が容易であること及び安価であることから、食品、飲料
品、医薬品などの容器、包装用材料として広く用いられ
ている。アルミニウム箔成形容器の外面は、装飾、防食
性などを付与する目的で塗装やフィルムラミネートが施
されているのが普通であり、これら塗装またはフィルム
ラミネートは、アルミニウム箔の成形加工前に塗装等が
なされている材料を用いてアルミニウム箔容器等に加工
されるのが一般的である。On the other hand, the aluminum foil has a beautiful appearance, is light in weight, and is most easily processed and inexpensive as its most excellent characteristics. Therefore, it is a container or a package for foods, beverages, pharmaceuticals and the like. Widely used as a material. The outer surface of the aluminum foil molding container is usually coated or film-laminated for the purpose of imparting decoration, anticorrosiveness, etc. It is generally processed into an aluminum foil container or the like by using the made material.
【０００４】塗装タイプのアルミニウム箔から製造され
る容器の中で、深絞り成形の２段成形が必要とされる容
器において、特に絞り比が高いときは、ショックライン
での塗膜の剥れが発生しやすく、この結果脱落した塗膜
片が金型に蓄積されることにより潤滑不良や、クリヤラ
ンス変化を引き起こし、製品不良や材料破断などによっ
てラインの連続成形ができなくなる。Among containers manufactured from paint-type aluminum foil, which requires two-stage deep drawing, particularly when the drawing ratio is high, the coating film peels off at the shock line. It is liable to occur, and as a result, pieces of the coating film that have fallen off accumulate in the mold, causing lubrication failure and clearance change, and it becomes impossible to continuously form the line due to product failure or material breakage.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、塗装された
アルミニウム箔を絞り比２．７以上の深絞り２段成形に
おいても、ショックラインでの塗膜剥れが発生しない、
密着性及び延性に優れた塗膜を形成する樹脂組成物及び
そのような深絞り成形ができる塗装アルミニウム箔の開
発を目的とする。DISCLOSURE OF THE INVENTION According to the present invention, even when a coated aluminum foil is subjected to deep drawing two-stage forming with a drawing ratio of 2.7 or more, peeling of the coating film at the shock line does not occur.
It is an object of the present invention to develop a resin composition that forms a coating film having excellent adhesion and ductility and a coated aluminum foil that enables such deep drawing.
【０００６】[0006]
【課題を解決するための手段】本発明は、 （ａ）ブロックイソシアネートを付加重合させたフェノ
ール系グリシジルエーテル型エポキシ樹脂６０〜９５重
量部 （ｂ）ビスフェノール系ジグリシジルエーテルを予備縮
合させたアミノ樹脂４０〜５重量部 からなるアルミニウム塗装用エポキシ系樹脂組成物、及
び該エポキシ樹脂組成物を０．５〜１０ｇ／ｍ2 焼き付
け塗装された深絞り成形用アルミニウム箔を開発するこ
とにより、上記の目的を達成した。The present invention comprises: (a) 60-95 parts by weight of a phenolic glycidyl ether type epoxy resin obtained by addition polymerization of a blocked isocyanate; (b) an amino resin precondensed with a bisphenol diglycidyl ether. By developing an epoxy resin composition for aluminum coating consisting of 40 to 5 parts by weight and an aluminum foil for deep drawing forming by baking coating the epoxy resin composition at 0.5 to 10 g / m 2 , Was achieved.
【０００７】本発明に用いることができる（ａ）成分と
して、フェノール系グリシジルエーテル型エポキシ樹脂
としては、代表的なものとしてビスフェノールＡ型エポ
キシ樹脂をあげることができる。これ以外にビスフェノ
ールＦ型、フェノールノボラック型なども使用できる
が、ビスフェノールＡ型が入手が容易であり、コストも
安価で性能も優れているところからこの使用が好まし
い。As the component (a) which can be used in the present invention, a typical glycidyl ether type epoxy resin of phenol type is a bisphenol A type epoxy resin. Other than this, bisphenol F type, phenol novolac type, etc. can be used, but bisphenol A type is preferable because it is easily available, inexpensive and excellent in performance.
【０００８】このエポキシ樹脂に付加重合させるブロッ
クイソシアネートのイソシアネートとしては、２，４−
または２，６−トリレンジイソシアネート（ＴＤＩ）、
４，４’−ジフェニルメタンジイソシアネート（ＭＤ
Ｉ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、パ
ラフェニレンジイソシアネート等のジイソシアネート化
合物であり、ブロック剤としてフェノール、アセト酢酸
エチル、アセチルアセトン、メチルエチルケトンオキシ
ム、ε−カプロラクタム等でブロックしたブロックイソ
シアネートを用いる。これを前記エポキシ樹脂に、ブロ
ックイソシアネート：エポキシ樹脂の配合比は０．５：
９．５〜５．５の比率で付加重合させ、分子量が少なく
とも４０００以上、好ましくは４，０００〜５０，００
０のエポキシ樹脂としたものを用いる。The isocyanate of the blocked isocyanate to be addition-polymerized with this epoxy resin is 2,4-
Or 2,6-tolylene diisocyanate (TDI),
4,4'-diphenylmethane diisocyanate (MD
I), hexamethylene diisocyanate (HDI), paraphenylene diisocyanate, and other diisocyanate compounds, and block isocyanates blocked with phenol, ethyl acetoacetate, acetylacetone, methyl ethyl ketone oxime, ε-caprolactam, etc. are used as blocking agents. This was added to the epoxy resin, and the compounding ratio of blocked isocyanate: epoxy resin was 0.5:
Addition polymerization is carried out at a ratio of 9.5 to 5.5, and the molecular weight is at least 4000 or more, preferably 4,000 to 50,000.
The epoxy resin of 0 is used.
【０００９】一方、硬化剤として用いられる（ｂ）成分
は、アミノ樹脂として尿素−ホルムアルデヒド、メラミ
ン−ホルムアルデヒド、ベンゾグアナミン−ホルムアル
デヒド等のプレポリマーであり、これにビスフェノール
系ジグリシジルエーテル、例えばビスフェノールＡジグ
リシジルエーテルを、アミノ樹脂：エポキシ樹脂の配合
比は１０：９０〜５０：５０で予備縮合させて用いる。On the other hand, the component (b) used as a curing agent is a prepolymer such as urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde as an amino resin, to which a bisphenol diglycidyl ether such as bisphenol A diglycidyl ether is added. The ether is used by precondensing with a blending ratio of amino resin: epoxy resin of 10:90 to 50:50.
【００１０】（ａ）成分のブロックイソシアネートとエ
ポキシ樹脂の付加物６０〜９５重量部に対し、（ｂ）成
分のビスフェノール系ジグリシジルエーテルを予備縮合
したアミノ樹脂は４０〜５重量部（合計１００重量部と
して）配合される。40 to 5 parts by weight of the amino resin obtained by precondensing the bisphenol diglycidyl ether of the component (b) (total 100 parts by weight) with respect to 60 to 95 parts by weight of the addition product of the blocked isocyanate and the epoxy resin as the component (a). Blended).
【００１１】（ｂ）成分が４０重量部を越えて配合され
ると、塗膜の伸びが低下し、ショックラインの塗膜剥れ
が起きやすくなる。一方、（ｂ）成分の配合が５重量部
に満たないときは、塗膜が軟らかくなって傷つきやすく
なる問題が生ずる。このエポキシ樹脂系組成物はそのま
までも使用できるが、潤滑剤としてワックスをエポキシ
樹脂組成物全重量の０．０１〜５重量％配合することに
よりアルミニウム箔の成形性を向上させることができ
る。When the component (b) is blended in an amount of more than 40 parts by weight, the elongation of the coating film is lowered and the coating film tends to peel off at the shock line. On the other hand, when the content of the component (b) is less than 5 parts by weight, the coating film becomes soft and easily scratched. The epoxy resin composition can be used as it is, but the formability of the aluminum foil can be improved by adding a wax as a lubricant in an amount of 0.01 to 5% by weight based on the total weight of the epoxy resin composition.
【００１２】このワックスとしてはシリコーン樹脂、ポ
リエチレンワックス、ポリプロピレンワックス、フッ素
系ワックス、高級脂肪酸またはその誘導体をあげること
ができる。Examples of the wax include silicone resin, polyethylene wax, polypropylene wax, fluorine-based wax, higher fatty acid or its derivative.
【００１３】添加量が０．０１重量％を下回るときは成
形性改良の効果が明らかでない。一方、５重量％を越え
る配合は成形性の改良の向上はなく、ムダになるだけで
ある。When the addition amount is less than 0.01% by weight, the effect of improving the moldability is not clear. On the other hand, if the amount exceeds 5% by weight, the improvement in moldability is not improved, and only waste is produced.
【００１４】以上、（ａ）成分、（ｂ）成分及びワック
ス等の添加剤を、塗料として使用する場合溶剤に固形分
濃度２０〜５０重量％に希釈して用いる。この場合の溶
剤としては、メチルエチルケトン、トルエン、イソプロ
ピルアルコールブチルセロソルブ、酢酸ブチル、キシレ
ン等の単独または混合溶剤として用いる。As described above, the components (a) and (b) and additives such as wax are diluted with a solvent to a solid concentration of 20 to 50% by weight when used as a paint. As the solvent in this case, methyl ethyl ketone, toluene, isopropyl alcohol butyl cellosolve, butyl acetate, xylene or the like is used alone or as a mixed solvent.
【００１５】深絞り成形用アルミニウム箔としては、通
常使用されている純アルミニウム系の厚さ約３０μｍ〜
２００μｍ程度のアルミニウム箔であり、これに焼き付
け後の塗膜が０．５〜１０ｇ／ｍ2 程度塗装されたもの
である。０．５ｇ／ｍ2 を下回る塗装量ではピンホール
が発生する恐れがある。１０ｇ／ｍ2 を上回る塗装はム
ダであるだけでなく、塗膜剥離の傾向を増大させる。As the deep-drawing aluminum foil, a generally used pure aluminum-based foil having a thickness of about 30 μm to
It is an aluminum foil having a thickness of about 200 μm, to which a coating film after baking is applied at about 0.5 to 10 g / m 2 . If the coating amount is less than 0.5 g / m 2 , pinholes may occur. Coatings above 10 g / m 2 are not only wasteful, but also increase the tendency for film peeling.
【００１６】塗膜の乾燥（焼き付け）は、樹脂組成物の
構成、ラインスピード等と関連して一概に決めることは
できないが、一般的に１８０〜３５０℃、５〜１２０ｓ
ｅｃくらいを基準にして行われる。焼き付け温度が１８
０℃に達しないときは塗膜の硬化が不十分となりやす
く、一方３５０℃を上回るときは塗膜の劣化を起こしや
すい。適切な条件は簡単なテストで容易に求められる。The drying (baking) of the coating film cannot be unconditionally determined in relation to the constitution of the resin composition, the line speed, etc., but it is generally 180 to 350 ° C., 5 to 120 s.
It is performed based on ec. Baking temperature is 18
If the temperature does not reach 0 ° C, curing of the coating tends to be insufficient, while if it exceeds 350 ° C, the coating tends to deteriorate. Appropriate conditions are easily determined by simple tests.
【００１７】[0017]
【作用】エポキシ樹脂は組み合わせる硬化剤により、異
なる特性のエポキシ樹脂が得られる。一般に広く用いら
れている硬化剤として酸無水物、ポリアマイド、イソシ
アネート系化合物があるが、これらはいずれも貯蔵安定
性が悪いという問題がある。また硬化剤としてエポキシ
樹脂と付加重合していない、ブロックイソシアネートを
用いた場合には貯蔵安定性は問題なくなるが、焼き付け
時にエポキシ樹脂との反応が速すぎて塗膜の硬化が進み
すぎ、塗膜の延性が低下する。[Function] Epoxy resins having different characteristics can be obtained depending on the curing agent used in combination. Generally used curing agents are acid anhydrides, polyamides, and isocyanate compounds, but these all have the problem of poor storage stability. When block isocyanate is used, which is not addition-polymerized with an epoxy resin as a curing agent, the storage stability is not a problem, but the reaction with the epoxy resin is too fast during baking, and the coating film cures too fast. Ductility is reduced.
【００１８】またフェノール系グリシジールエーテル型
エポキシ樹脂にブロックイソシアネートを付加重合させ
た変性エポキシ樹脂単独では焼き付けを行っても硬化が
不十分であって、これだけの使用では良好な塗膜とはな
らない。Further, the modified epoxy resin obtained by addition-polymerizing the block isocyanate with the phenolic glycidyl ether type epoxy resin alone does not cure sufficiently even if it is baked, and the use of this alone does not result in a good coating film.
【００１９】更にビスフェノールＡグリシジルエーテル
をあらかじめ予備縮合させた硬化剤のみでは焼き付け時
に硬化が進みすぎ、塗膜の延性がなくなる。Further, if only a curing agent pre-condensed with bisphenol A glycidyl ether is used, the curing will proceed excessively during baking and the ductility of the coating film will be lost.
【００２０】一方、ブロックイソシアネートを付加重合
していないエポキシ樹脂と本発明の（ｂ）成分の硬化剤
を組み合わせた接着剤組成物は、イソシアネート成分が
ないため延性が不十分で密着性が不足する。On the other hand, an adhesive composition obtained by combining an epoxy resin not subjected to addition polymerization of a blocked isocyanate with a curing agent as the component (b) of the present invention has no isocyanate component and thus has insufficient ductility and insufficient adhesion. .
【００２１】本発明はこれらの硬化した塗膜の状況を逐
一検討を行い、更に配合量を検討することにより貯蔵安
定性に問題がなく、焼き付け硬化速度も適切であり、硬
化後の塗膜がアルミニウム箔に対する密着性に優れ、適
度の延性（硬度と反対傾向になる。）を有するアルミニ
ウム塗装用樹脂組成物が開発できた。According to the present invention, the conditions of these cured coatings are examined step by step, and the blending amount is further examined so that there is no problem in storage stability and the baking and curing speed is appropriate. It has been possible to develop a resin composition for aluminum coating which has excellent adhesion to an aluminum foil and has appropriate ductility (which tends to be opposite to hardness).
【００２２】[0022]
【実施例】厚さ５０μｍ、１Ｎ３０アルミニウム箔を表
１に示す配合比の塗装用エポキシ樹脂組成物５ｇ／ｍ2
塗装し、これを２５０℃、３０ｓｅｃ焼き付けてサンプ
ルとした。[Example] Epoxy resin composition for coating having a thickness of 50 μm and 1N30 aluminum foil having a compounding ratio shown in Table 1 5 g / m 2
It was painted and baked at 250 ° C. for 30 seconds to obtain a sample.
【００２３】〈延性〉該サンプルを幅５ｍｍ、長さ２０
ｍｍのサンプルを作成し、測定温度２０℃、引張速度５
ｍｍ／ｍｉｎの条件で、オートグラフを用い塗膜の伸び
率を測定した。<Ductility> The sample was 5 mm wide and 20 mm long.
mm sample is prepared, measurement temperature is 20 ° C, pulling speed is 5
The elongation of the coating film was measured using an autograph under the condition of mm / min.
【００２４】〈密着性〉東洋精機（株）耐析試験機（Ｍ
ＩＴ型）にて１．５ｋｇｆの負荷で、肩Ｒ ＩＲの金型
を用いて、１３５°の角度で試料（５×２００ｍｍ）を
塗膜側と反対側に曲げ、曲げ戻しを繰り返し、その後の
塗膜の状況を走査型電子顕微鏡で観察し、クラックのな
いときは○、クラックが認められたときは×とした。<Adhesion> Toyo Seiki Co., Ltd. Sedimentation resistance tester (M
(IT type) with a load of 1.5 kgf, using a die for shoulder R IR, bend the sample (5 × 200 mm) at the angle of 135 ° to the side opposite to the coating film side, repeat bending back, and then The condition of the coating film was observed with a scanning electron microscope, and when there was no crack, it was marked with O, and when cracks were found, it was marked with X.
【００２５】〈成形性〉ブランク径６５ｍｍφ、ポンチ
径３２ｍｍφ、肩Ｒ１．３５ｍｍＲの金型で深絞り成形
を行い、限界絞り比（Ｌ．Ｄ．Ｒ．）を求めた。（実際
の容器形状の特定ができないので、１段のＬ、Ｄ、Ｒの
測定により成形性の良否を判断した。この数値であれば
絞り比２．７以上の深絞り２段成形が可能である。）<Moldability> Deep drawing was carried out with a die having a blank diameter of 65 mmφ, a punch diameter of 32 mmφ and a shoulder R of 1.35 mmR to determine the limit drawing ratio (LDR). (Since the actual container shape cannot be specified, the quality of the moldability was judged by measuring L, D, and R in one step. With this value, it is possible to perform deep drawing in two steps with a drawing ratio of 2.7 or more. is there.)
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】ブロックイソシアネートを付加重合させ
たフェノール系グリシジールエーテル型エポキシ樹脂に
対し、ビスフェノール系ジグリシジルエーテルを予備縮
合させたアミノ樹脂を配合したエポキシ系樹脂組成物
は、貯蔵安定性に優れ、イソシアネート基とアルミニウ
ム箔表面の酸化皮膜の水酸基との反応による密着性の向
上並びにブロックイソシアネートによりエポキシ樹脂の
高分子化による延性の向上、適度の架橋密度の高分子量
の塗膜が形成されるため、絞り比２．７以上の深絞り２
段成形した容器のショックラインにおいても塗膜剥れの
ない塗装された深絞り成形用アルミニウム箔が得られ
る。EFFECT OF THE INVENTION An epoxy resin composition prepared by adding an amino resin obtained by precondensing a bisphenol diglycidyl ether to a phenol glycidyl ether type epoxy resin obtained by addition polymerization of a blocked isocyanate is excellent in storage stability. , Because the adhesion between the isocyanate group and the hydroxyl group of the oxide film on the surface of the aluminum foil is improved, and the blocked isocyanate improves the ductility by polymerizing the epoxy resin, and a high-molecular-weight coating film with an appropriate crosslinking density is formed. , Deep drawing with a drawing ratio of 2.7 or more 2
A coated aluminum foil for deep drawing can be obtained which does not peel off even in the shock line of a stage-formed container.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 63/00 ＮＪＴ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C08L 63/00 NJT
Claims (3)
合させたフェノール系グリシジルエーテル型エポキシ樹
脂６０〜９５重量部 （ｂ）ビスフェノール系ジグリシジルエーテルを予備縮
合させたアミノ樹脂４０〜５重量部 からなるアルミニウム塗装用エポキシ系樹脂組成物1. Aluminum comprising (a) 60 to 95 parts by weight of a phenolic glycidyl ether type epoxy resin obtained by addition polymerization of a blocked isocyanate, and (b) 40 to 5 parts by weight of an amino resin precondensed with a bisphenol diglycidyl ether. Epoxy resin composition for painting
おいて、シリコーン樹脂、ポリエチレンワックス、ポリ
プロピレンワックス、フッ素系ワックス、高級脂肪酸ま
たはその誘導体からなるワックスを、全重量の０．０１
〜５重量％添加したアルミニウム塗装用エポキシ系樹脂
組成物。2. The epoxy resin composition according to claim 1, wherein the total weight of the silicone resin, polyethylene wax, polypropylene wax, fluorine-containing wax, wax composed of higher fatty acid or its derivative is 0.01.
An epoxy resin composition for aluminum coating, containing 5% by weight.
組成物を０．５〜１０ｇ／ｍ2 焼き付け塗装された深絞
り成形用アルミニウム箔。3. An aluminum foil for deep drawing, which is baked and coated with 0.5 to 10 g / m 2 of the epoxy resin composition according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6051212A JP2691864B2 (en) | 1994-02-24 | 1994-02-24 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6051212A JP2691864B2 (en) | 1994-02-24 | 1994-02-24 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07233348A true JPH07233348A (en) | 1995-09-05 |
| JP2691864B2 JP2691864B2 (en) | 1997-12-17 |
Family
ID=12880617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6051212A Expired - Fee Related JP2691864B2 (en) | 1994-02-24 | 1994-02-24 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2691864B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000055231A1 (en) * | 1999-03-17 | 2000-09-21 | E.I. Du Pont De Nemours And Company | High solid epoxy, melamine and isocyanate compositions |
| US6544593B1 (en) | 1999-03-17 | 2003-04-08 | E. I. Du Pont De Nemours And Company | High solids clear coating composition |
| US6592944B1 (en) | 1999-03-17 | 2003-07-15 | E. I. Du Pont De Nemours And Company | High solids acid etch and mar resistant clear coating composition |
| US6607833B1 (en) | 1999-03-17 | 2003-08-19 | E. I. Du Pont De Nemours And Company | High solids acid etch resistant clear coating composition |
| US6635314B1 (en) | 1999-03-17 | 2003-10-21 | E. I. Du Pont De Nemours And Company | High solids clear coating composition |
| US6855779B1 (en) | 1999-03-17 | 2005-02-15 | E. I. Du Pont De Nemours And Company | High solid epoxy, melamine and isocyanate compositions |
| KR100521427B1 (en) * | 1997-12-31 | 2006-03-23 | 주식회사 케이씨씨 | Epoxy primer composition |
| CN103122202A (en) * | 2012-12-12 | 2013-05-29 | 孙才清 | Outer bottom oil iron printing paint and iron printing method |
| CN103122203A (en) * | 2012-12-12 | 2013-05-29 | 孙才清 | Inner layer metal decorating paint and metal decorating method |
| CN103122201A (en) * | 2012-12-12 | 2013-05-29 | 孙才清 | Inner iron printing paint for food packaging |
| KR101279089B1 (en) * | 2011-10-11 | 2013-06-26 | 조일원 | Composition for coating to protect against corrosion of aluminuim form |
| JP2015193848A (en) * | 2015-06-05 | 2015-11-05 | 日立化成株式会社 | Heat-radiating coating material, and light-emitting diode (led) illumination, heat sink and solar cell module back sheet each coated therewith |
| JP2016083794A (en) * | 2014-10-23 | 2016-05-19 | 三菱アルミニウム株式会社 | Resin-coated aluminum sheet and method for producing the same |
| CN108176805A (en) * | 2017-12-25 | 2018-06-19 | 上海氟聚化学产品股份有限公司 | A kind of aqua type aluminum alloy mould release agent and preparation method thereof |
-
1994
- 1994-02-24 JP JP6051212A patent/JP2691864B2/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100521427B1 (en) * | 1997-12-31 | 2006-03-23 | 주식회사 케이씨씨 | Epoxy primer composition |
| US6855779B1 (en) | 1999-03-17 | 2005-02-15 | E. I. Du Pont De Nemours And Company | High solid epoxy, melamine and isocyanate compositions |
| US6592944B1 (en) | 1999-03-17 | 2003-07-15 | E. I. Du Pont De Nemours And Company | High solids acid etch and mar resistant clear coating composition |
| US6607833B1 (en) | 1999-03-17 | 2003-08-19 | E. I. Du Pont De Nemours And Company | High solids acid etch resistant clear coating composition |
| US6635314B1 (en) | 1999-03-17 | 2003-10-21 | E. I. Du Pont De Nemours And Company | High solids clear coating composition |
| AU773223B2 (en) * | 1999-03-17 | 2004-05-20 | E.I. Du Pont De Nemours And Company | High solid epoxy, melamine and isocyanate compositions |
| WO2000055231A1 (en) * | 1999-03-17 | 2000-09-21 | E.I. Du Pont De Nemours And Company | High solid epoxy, melamine and isocyanate compositions |
| US6544593B1 (en) | 1999-03-17 | 2003-04-08 | E. I. Du Pont De Nemours And Company | High solids clear coating composition |
| KR101279089B1 (en) * | 2011-10-11 | 2013-06-26 | 조일원 | Composition for coating to protect against corrosion of aluminuim form |
| CN103122203A (en) * | 2012-12-12 | 2013-05-29 | 孙才清 | Inner layer metal decorating paint and metal decorating method |
| CN103122201A (en) * | 2012-12-12 | 2013-05-29 | 孙才清 | Inner iron printing paint for food packaging |
| CN103122202A (en) * | 2012-12-12 | 2013-05-29 | 孙才清 | Outer bottom oil iron printing paint and iron printing method |
| JP2016083794A (en) * | 2014-10-23 | 2016-05-19 | 三菱アルミニウム株式会社 | Resin-coated aluminum sheet and method for producing the same |
| JP2015193848A (en) * | 2015-06-05 | 2015-11-05 | 日立化成株式会社 | Heat-radiating coating material, and light-emitting diode (led) illumination, heat sink and solar cell module back sheet each coated therewith |
| CN108176805A (en) * | 2017-12-25 | 2018-06-19 | 上海氟聚化学产品股份有限公司 | A kind of aqua type aluminum alloy mould release agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2691864B2 (en) | 1997-12-17 |
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