JPH10324824A - Thermosetting double-layer powder coating material and method for forming coating film therefrom - Google Patents

Thermosetting double-layer powder coating material and method for forming coating film therefrom

Info

Publication number
JPH10324824A
JPH10324824A JP9136234A JP13623497A JPH10324824A JP H10324824 A JPH10324824 A JP H10324824A JP 9136234 A JP9136234 A JP 9136234A JP 13623497 A JP13623497 A JP 13623497A JP H10324824 A JPH10324824 A JP H10324824A
Authority
JP
Japan
Prior art keywords
powder coating
thermosetting
coating material
polyester resin
preponderates
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
JP9136234A
Other languages
Japanese (ja)
Inventor
Kazuhiko Onishi
和彦 大西
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.)
Kansai Paint Co Ltd
Original Assignee
Kansai Paint 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 Kansai Paint Co Ltd filed Critical Kansai Paint Co Ltd
Priority to JP9136234A priority Critical patent/JPH10324824A/en
Publication of JPH10324824A publication Critical patent/JPH10324824A/en
Pending legal-status Critical Current

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  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a coating film excellent in finish and film performances by electrocoating a substrate surface-treated with an onium salt compound with a mixed powder coating material being a combination of thermosetting powder coating materials. SOLUTION: The thermosetting double-layer powder coating used is a mixed powder coating of I, II, II or IV. (I) both a thermosetting acrylic resin powder coating A and a polyester resin curing epoxy resin powder coating material (B), (II) both a polyester resin curing acrylic resin powder coating material (C) and a thermosetting epoxy resin powder coating material (D), (III) both C and B, and (IV) both a thermosetting polyester resin powder coating material (E) and component D. The mixing ratio between the respective components in each mixed powder coating material I, II, III or IV is desirably about 30 to 70 wt.%. In the coating films, (I) A preponderates in the upper layer, while B preponderates in the lower layer; (II) C preponderates in the upper layer, while D preponderates in the lower layer, (III) C preponderates in the upper layer, while B preponderates in the lower layer, and (IV) E preponderates in the upper layer, while D preponderates in the lower layer. The treatment is desirably performed with a phosphonium salt compound.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、仕上がり外観、塗膜性
能に優れた複層粉体塗膜を提供しうる熱硬化型複層粉体
塗料及びその塗膜形成方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting multilayer powder coating material capable of providing a multilayer powder coating film having excellent finished appearance and coating film performance, and a method for forming the coating film.

【0002】[0002]

【従来技術】
従来より、熱硬化型粉体塗料は家電製品、
自動車、車両、事務用品、鋼製家具、建材等の工業用製
品分野において屋外又は屋内用途として広く使用されて
いる。上記した熱硬化型粉体塗料としては、アクリル樹
脂粉体塗料、ポリエステル樹脂粉体塗料及びエポキシ樹
脂粉体塗料が主に使用されている。
[Prior art]
Conventionally, thermosetting powder coatings have been used for home appliances,
It is widely used for outdoor or indoor applications in the field of industrial products such as automobiles, vehicles, office supplies, steel furniture, and building materials. As the above-mentioned thermosetting powder coating, acrylic resin powder coating, polyester resin powder coating and epoxy resin powder coating are mainly used.

【0003】しかしながら、これらの粉体塗料から形成
される塗膜において、アクリル樹脂粉体塗膜は太陽光等
により塗膜の劣化が少ないので塗膜表面の外観を重視す
る屋外用途に多く採用されているが耐食性に劣るといっ
た欠点があり、またエポキシ樹脂粉体塗膜はアクリル樹
脂粉体塗膜とは反対に耐食性は優れるが耐候性が劣ると
いった欠点がるために主に屋内用途として使用されてい
る。またポリエステル樹脂粉体塗料から形成される塗膜
はエポキシ樹脂粉体塗料と比べて耐食性が劣るといった
欠点がある。
[0003] However, among the coating films formed from these powder coatings, acrylic resin powder coating films are often used in outdoor applications where the appearance of the coating film surface is emphasized because the coating film deteriorates little due to sunlight or the like. However, epoxy resin powder coatings are used mainly for indoor applications because of their drawbacks such as poor corrosion resistance and poor weather resistance, contrary to acrylic resin powder coatings. ing. Further, a coating film formed from a polyester resin powder coating has a drawback that corrosion resistance is inferior to an epoxy resin powder coating.

【0004】このような粉体塗料の欠点を改良する粉体
塗料として、例えばアクリル樹脂粉体塗料とエポキシ樹
脂粉体塗料又はポリエステル樹脂粉体塗料との混合物を
表面処理鋼鈑に粉体塗装したのち、加熱硬化して上層を
アクリル樹脂粉体塗膜、下層をエポキシ樹脂粉体塗膜又
はポリエステル樹脂粉体塗膜に複層塗膜を形成させる粉
体塗料(特開昭54ー105135号公報参照)が記載
されている。
[0004] As a powder coating for improving the disadvantages of such a powder coating, for example, a mixture of an acrylic resin powder coating and an epoxy resin powder coating or a polyester resin powder coating is powder-coated on a surface-treated steel plate. Then, heat-curing to form a multilayer coating film on the upper layer of an acrylic resin powder coating film and the lower layer of an epoxy resin powder coating film or a polyester resin powder coating (Japanese Patent Application Laid-Open No. 54-105135) Reference).

【0005】しかしながら、このものから形成される複
層粉体塗膜は仕上がり外観が十分でないこと及び耐食性
などの性能が劣るといった欠点が残されていた。
[0005] However, the multilayer powder coating film formed therefrom still has disadvantages such as insufficient finished appearance and poor performance such as corrosion resistance.

【0006】[0006]

【発明が解決しようとする課題】本発明は、仕上がり外
観、塗膜性能に優れた複層粉体塗膜を提供することを目
的とする。
SUMMARY OF THE INVENTION An object of the present invention is to provide a multilayer powder coating film having excellent finished appearance and coating film performance.

【0007】[0007]

【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、特定の熱硬化性粉
体塗料の混合粉体塗料を素材に静電粉体塗装することに
より、仕上がり外観及び性能に優れた熱硬化塗膜を形成
すことを見出し、本発明を完成した。
Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a mixed powder coating of a specific thermosetting powder coating is applied to a material by electrostatic powder coating. As a result, it was found that a thermosetting coating film having excellent finished appearance and performance was formed, and the present invention was completed.

【0008】即ち、本発明は、 1、熱硬化型アクリル樹脂粉体塗料(A)とポリエステ
ル樹脂硬化型エポキシ樹脂粉体塗料(B)との混合粉体
塗料であることを特徴とする熱硬化型複層粉体塗料
(I)、 2、ポリエステル樹脂硬化型アクリル樹脂粉体塗料
(C)と熱硬化型エポキシ樹脂粉体塗料(D)との混合
粉体塗料であることを特徴とする熱硬化型複層粉体塗料
(II)、 3、ポリエステル樹脂硬化型アクリル樹脂粉体塗料
(C)とポリエステル樹脂硬化型エポキシ樹脂粉体塗料
(B)との混合粉体塗料であることを特徴とする熱硬化
型複層粉体塗料(III)、 4、熱硬化型ポリエステル樹脂粉体塗料(E)と熱硬化
型エポキシ樹脂粉体塗料(D)との混合粉体塗料である
ことを特徴とする熱硬化型複層粉体塗料(IV)、 5、基材表面をオニウム塩化合物で処理し、次いで熱硬
化型複層粉体塗料を静電粉体塗装し、加熱硬化させるこ
とを特徴とする熱硬化型複層粉体塗膜の形成方法、 6、熱硬化型粉体塗料が上記1〜4に記載の混合粉体塗
料であることを特徴とする熱硬化型複層粉体塗膜の形成
方法、 7、上記オニウム塩化合物がホスホニウム塩化合物であ
ることを特徴とする上記5又は6に記載の熱硬化型複層
粉体塗膜の形成方法に係わる。
That is, the present invention provides: 1. A thermosetting resin composition comprising a mixed powder coating of a thermosetting acrylic resin powder coating (A) and a polyester resin curing type epoxy resin powder coating (B). A multi-layered powder coating (I), 2, a mixed powder coating of a polyester resin curing type acrylic resin powder coating (C) and a thermosetting epoxy resin powder coating (D). Curable multi-layer powder coating (II), 3. Mixed powder coating of polyester resin-curable acrylic resin powder coating (C) and polyester resin-curable epoxy resin powder coating (B) Thermosetting type multi-layer powder coating (III), 4, mixed powder coating of thermosetting polyester resin powder coating (E) and thermosetting epoxy resin powder coating (D) Thermosetting multilayer powder coating (IV), 5, groups A method for forming a thermosetting multilayer powder coating film, which comprises treating the surface with an onium salt compound, then applying a thermosetting multilayer powder coating material to an electrostatic powder, and curing by heating; The method for forming a thermosetting multilayer powder coating film, wherein the curable powder coating material is the mixed powder coating material described in any one of the above items 1 to 4, 7. The onium salt compound is a phosphonium salt compound 7. The method for forming a thermosetting multilayer powder coating film according to the above item 5 or 6, wherein

【0009】まず、熱硬化型複層粉体塗料(I)〜(I
V)について説明する。
First, thermosetting double-layer powder coatings (I) to (I)
V) will be described.

【0010】熱硬化型複層粉体塗料(I):該粉体塗料
(I)は、熱硬化型アクリル樹脂粉体塗料(A)とポリ
エステル樹脂硬化型エポキシ樹脂粉体塗料(B)との混
合粉体塗料である。
Thermosetting double layer powder coating (I): The powder coating (I) is composed of a thermosetting acrylic resin powder coating (A) and a polyester resin curing epoxy resin powder coating (B). It is a mixed powder coating.

【0011】粉体塗料(A) 粉体塗料(A)としては、それ自体で静電粉体塗装が可
能で加熱により硬化する従来から公知の粉体塗料、例え
ば酸エポキシ硬化型アクリル樹脂系粉体塗料(a)、ブ
ロックイソシアネート硬化型アクリル樹脂系粉体塗料
(b)等が挙げられる。
Powder coating (A) As the powder coating (A), a conventionally known powder coating which can be electrostatic powder coated by itself and is cured by heating, for example, an acid epoxy-curable acrylic resin powder Body paint (a) and blocked isocyanate-curable acrylic resin-based powder paint (b).

【0012】上記粉体塗料(a)としては、エポキシ基
含有ラジカル重合性不飽和モノマー(例えばグリシジル
(メタ)アクリレート、メチルグリシジル(メタ)アク
リレート等)、ガラス転移温度が40℃以上の硬質アク
リルモノマー(例えばメチルメタクリレート、エチルメ
タクリレート、iso-ブチルメタクリレート、ter-
ブチルメタクリレート、ter-ブチルアクリレート
等)及び必要に応じてガラス転移温度が40℃以未満の
軟質アクリルモノマー(例えばメチルアクリレート、エ
チルアクリレート、n-ブチルメタクリレート、iso-
ブチルアクリレート、2エチルヘキシル(メタ)アクリ
レート、ステアリルメタクリレート等)、アクリルモノ
マー以外のラジカル重合性不飽和モノマー(例えばスチ
レン、ビニルトルエン、α-メチルスチレン、(メタ)
アクリルニトリル、(メタ)アクリルアミド等)、上記
エポキシ基以外の官能基含有ラジカル重合性不飽和モノ
マー(例えばヒドロキシエチル(メタ)アクリレート、
ヒドロキシプロピル(メタ)アクリレート等)をラジカ
ル共重合反応させて得られるエポキシ基含有アクリル基
体樹脂にポリカルボン酸架橋剤(例えばアジピン酸、ア
ゼライン酸、ドデカン二酸、無水アジピン酸、無水トリ
メリット酸等)を配合してなるものである。
The powder coating (a) includes a radical polymerizable unsaturated monomer containing an epoxy group (eg, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate), a hard acrylic monomer having a glass transition temperature of 40 ° C. or higher. (Eg, methyl methacrylate, ethyl methacrylate, iso-butyl methacrylate, ter-
Butyl methacrylate, ter-butyl acrylate, etc.) and, if necessary, a soft acrylic monomer having a glass transition temperature of less than 40 ° C. (eg, methyl acrylate, ethyl acrylate, n-butyl methacrylate, iso-
Butyl acrylate, 2 ethylhexyl (meth) acrylate, stearyl methacrylate, etc.), radical polymerizable unsaturated monomers other than acrylic monomers (eg, styrene, vinyltoluene, α-methylstyrene, (meth)
Acrylonitrile, (meth) acrylamide, etc.), functional group-containing radically polymerizable unsaturated monomer other than the epoxy group (for example, hydroxyethyl (meth) acrylate,
A polycarboxylic acid crosslinking agent (eg, adipic acid, azelaic acid, dodecane diacid, adipic anhydride, trimellitic anhydride, etc.) is applied to an epoxy group-containing acrylic base resin obtained by a radical copolymerization reaction of hydroxypropyl (meth) acrylate or the like. ) Is blended.

【0013】また上記粉体塗料(b)としては、水酸基
含有ラジカル重合性不飽和モノマー(例えばヒドロキシ
エチル(メタ)アクリレート、ヒドロキシプロピル(メ
タ)アクリレート等)、ガラス転移温度が40℃以上の
硬質アクリルモノマー(例えばメチルメタクリレート、
エチルメタクリレート、iso-ブチルメタクリレー
ト、ter-ブチルメタクリレート、ter-ブチルアク
リレート等)及び必要に応じてガラス転移温度が40℃
以未満の軟質アクリルモノマー(例えばメチルアクリレ
ート、エチルアクリレート、n-ブチルメタクリレー
ト、iso-ブチルアクリレート、2エチルヘキシル
(メタ)アクリレート、ステアリルメタクリレート
等)、アクリルモノマー以外のラジカル重合性不飽和モ
ノマー(例えばスチレン、ビニルトルエン、α-メチル
スチレン、(メタ)アクリルニトリル、(メタ)アクリ
ルアミド等)、上記水酸基以外の官能基含有ラジカル重
合性不飽和モノマー(例えばグリシジル(メタ)アクリ
レート、メチルグリシジル(メタ)アクリレート 等)
をラジカル共重合反応させて得られる水酸基含有アクリ
ル基体樹脂にブロックポリイソシアネート架橋剤(例え
ばヘキサメチレンジイソシアネート、トリメチレンジイ
ソシアネート、イソホロンジイソシアネート、水素添加
キシリレンジイソシアネート等の脂肪族又は脂環族ポリ
イソシアネート化合物をフェノール類、ラクタム類、ア
ルコール類、オキシム類等の化合物によりイソシアネー
ト基をブロック化したもの)を配合してなるものであ
る。
The powder coating (b) may be a hydroxyl-containing radically polymerizable unsaturated monomer (eg, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc.), a hard acrylic resin having a glass transition temperature of 40 ° C. or higher. Monomers (eg, methyl methacrylate,
Ethyl methacrylate, iso-butyl methacrylate, ter-butyl methacrylate, ter-butyl acrylate, etc.) and, if necessary, a glass transition temperature of 40 ° C.
Less than a soft acrylic monomer (eg, methyl acrylate, ethyl acrylate, n-butyl methacrylate, iso-butyl acrylate, 2ethylhexyl (meth) acrylate, stearyl methacrylate, etc.), a radical polymerizable unsaturated monomer other than an acrylic monomer (eg, styrene, Vinyltoluene, α-methylstyrene, (meth) acrylonitrile, (meth) acrylamide, etc.), radical-polymerizable unsaturated monomers containing functional groups other than the above hydroxyl groups (eg, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, etc.)
To a hydroxyl group-containing acrylic base resin obtained by a radical copolymerization of Phenols, lactams, alcohols, oximes, etc.).

【0014】上記基体樹脂と架橋剤の配合割合は、基体
樹脂100重量部に対して架橋剤が10〜100重量部
の範囲で配合される。
The mixing ratio of the base resin and the crosslinking agent is such that the crosslinking agent is mixed in the range of 10 to 100 parts by weight with respect to 100 parts by weight of the base resin.

【0015】粉体塗料(B) 該粉体塗料(B)としては、それ自体で静電粉体塗装が
可能で加熱により硬化する従来から公知の粉体塗料、例
えばビスフェノール・エピクロルヒドリン型エポキシ基
体樹脂(例えば、油化シェル株式会社製、商品名エピコ
ート1004、エピコート1007)、ノボラック型エ
ポキシ基体樹脂(例えば、)等のエポキシ樹脂に高酸価
ポリエステル樹脂を配合してなるものである。
Powder coating (B) As the powder coating (B), a conventionally known powder coating which can be applied by itself to electrostatic powder coating and is cured by heating, for example, bisphenol / epichlorohydrin type epoxy base resin (For example, Epicoat 1004, Epicoat 1007, manufactured by Yuka Shell Co., Ltd.), and epoxy resin such as novolak type epoxy base resin (for example) mixed with a high acid value polyester resin.

【0016】該高酸価ポリエステル樹脂としては、例え
ば(無水)フタル酸、イソフタル酸、テレフタル酸、イ
ソフタル酸ジメチル、テレフタル酸ジメチル、ヘキサヒ
ドロ(無水)フタル酸、テトラヒドロ(無水)フタル酸
等の芳香族又は脂環族ジカルボン酸と(ポリ)エチレン
グリコール、(ポリ)プロピレングリコール、ブチレン
グリコール、ブチレングリコール、ネオペンチルグリコ
ール、1,6−ヘキサンジオール、ジメチルプロピオン
酸等の2価アルコール、必要に応じて安息香酸等のモノ
カルボン酸、(無水)トリメリット酸等の3価以上のカ
ルボン酸、トリメチロールエタン、トリメチロールプロ
パン、グリセリン、ペンタエリスリットール等の3価以
上のアルコールとを反応させて得られる酸価約20〜3
00KOHmg/gのポリエステル樹脂を使用すること
ができる。
Examples of the high acid value polyester resin include aromatic resins such as (phthalic anhydride), isophthalic acid, terephthalic acid, dimethyl isophthalate, dimethyl terephthalate, hexahydro (anhydride) phthalic acid, and tetrahydro (anhydride) phthalic acid. Or an alicyclic dicarboxylic acid and a dihydric alcohol such as (poly) ethylene glycol, (poly) propylene glycol, butylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, dimethylpropionic acid, and, if necessary, benzoic acid It is obtained by reacting a monocarboxylic acid such as an acid, a trivalent or higher carboxylic acid such as (anhydride) trimellitic acid, and a trivalent or higher alcohol such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol. Acid value about 20-3
A polyester resin of 00 KOH mg / g can be used.

【0017】上記基体樹脂と高酸価ポリエステル樹脂の
配合割合は、基体樹脂100重量部に対して高酸価ポリ
エステル樹脂が50〜200重量部の範囲で配合され
る。
The mixing ratio of the base resin and the high acid value polyester resin is such that the high acid value polyester resin is mixed in the range of 50 to 200 parts by weight with respect to 100 parts by weight of the base resin.

【0018】該混合粉体塗料(I)を加熱して得られる
塗膜は上層に粉体塗料(A)成分が多く、また下層に粉
体塗料(B)成分が多い塗膜で形成される。
The coating film obtained by heating the mixed powder coating material (I) is formed of a coating film containing a large amount of the powder coating material (A) in the upper layer and a coating film containing a large amount of the powder coating material (B) in the lower layer. .

【0019】熱硬化型複層粉体塗料(II):ポリエス
テル樹脂硬化型アクリル樹脂粉体塗料(C)と熱硬化型
エポキシ樹脂粉体塗料(D)との混合粉体塗料である。
Thermosetting double layer powder coating (II): A mixed powder coating of a polyester resin curing type acrylic resin powder coating (C) and a thermosetting epoxy resin powder coating (D).

【0020】粉体塗料(C) 上記(a)に記載のエポキシ基含有アクリル樹脂と上記
(B)に記載の高酸価ポリエステル樹脂に配合してなる
ものである。
Powder coating (C) It is obtained by blending the epoxy group-containing acrylic resin described in (a) and the high acid value polyester resin described in (B).

【0021】粉体塗料(D) 該粉体塗料(D)としては、例えば、上記ビスフェノー
ル・エピクロルヒドリン型エポキシ基体樹脂、ノボラッ
ク型エポキシ基体樹脂に、例えばアジピン酸、(無水)
トリメリット酸等のポリカルボン酸化合物、ベンジル−
4−ヒドロキシフェニルメチルスルホニウムヘキサフル
オロアンチモネ−ト等の芳香族スルホニウム塩のカチオ
ン重合触媒、ジシアンジアミド等のアミド化合物、アジ
ピン酸ジヒドラジド等のカルボン酸ジヒドラジド化合
物、イミダゾリン、イミダゾール等のエポキシ用架橋剤
を配合したものを使用することができる。
Powder coating (D) Examples of the powder coating (D) include the above-mentioned bisphenol / epichlorohydrin type epoxy base resin and novolak type epoxy base resin, for example, adipic acid, (anhydrous)
Polycarboxylic acid compounds such as trimellitic acid, benzyl-
Formulated with a cationic polymerization catalyst for aromatic sulfonium salts such as 4-hydroxyphenylmethylsulfonium hexafluoroantimonate, amide compounds such as dicyandiamide, carboxylic acid dihydrazide compounds such as adipic dihydrazide, and epoxy crosslinking agents such as imidazoline and imidazole. Can be used.

【0022】基体樹脂と硬化剤との配合割合は、基体樹
脂100重量部当たりカチオン重合触媒の場合には約
0.01〜10重量部、好ましくは約0.1〜5重量部
の範囲、カチオン重合触媒以外の場合には約10〜10
0重量部、好ましくは約15〜80重量部の範囲が好適
である。
The mixing ratio of the base resin and the curing agent is in the range of about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight in the case of a cationic polymerization catalyst per 100 parts by weight of the base resin. About 10 to 10 in cases other than polymerization catalyst
A range of 0 parts by weight, preferably about 15 to 80 parts by weight, is suitable.

【0023】該混合粉体塗料(II)を加熱して得られ
る塗膜は上層に粉体塗料(C)成分が多く、また下層に
粉体塗料(D)成分が多い塗膜で形成される。
The coating film obtained by heating the mixed powder coating material (II) is formed of a coating film containing a large amount of the powder coating material (C) in the upper layer and a coating film containing a large amount of the powder coating material (D) in the lower layer. .

【0024】熱硬化型複層粉体塗料(III):上記粉
体塗料(C)と上記粉体塗料(B)との混合粉体塗料で
ある。該混合粉体塗料(II)を加熱して得られる塗膜
は上層に粉体塗料(C)成分が多く、また下層に粉体塗
料(B)成分が多い塗膜で形成される。
Thermosetting double layer powder coating (III): A mixed powder coating of the above powder coating (C) and the above powder coating (B). A coating film obtained by heating the mixed powder coating material (II) is formed of a coating film containing a large amount of the powder coating material (C) in the upper layer and a coating film containing a large amount of the powder coating material (B) in the lower layer.

【0025】熱硬化型複層粉体塗料(IV):粉体塗料
(E)と上記粉体塗料(D)との混合粉体塗料である。
Thermosetting double layer powder coating (IV): a mixed powder coating of powder coating (E) and powder coating (D).

【0026】粉体塗料(E) 粉体塗料(E)としては、それ自体で静電粉体塗装が可
能で加熱により硬化する従来から公知の粉体塗料、例え
ばブロックイソシアネート硬化型ポリエステル樹脂系粉
体塗料等が挙げられる。
Powder coating (E) As the powder coating (E), a conventionally known powder coating which can be electrostatic powder coated by itself and is cured by heating, for example, a blocked isocyanate-curable polyester resin powder Body paint and the like.

【0027】該粉体塗料(E)としては、例えば(無
水)フタル酸、イソフタル酸、テレフタル酸、イソフタ
ル酸ジメチル、テレフタル酸ジメチル、ヘキサヒドロ
(無水)フタル酸、テトラヒドロ(無水)フタル酸等の
芳香族又は脂環族ジカルボン酸と(ポリ)エチレングリ
コール、(ポリ)プロピレングリコール、ブチレングリ
コール、ブチレングリコール、ネオペンチルグリコー
ル、1,6−ヘキサンジオール、ジメチルプロピオン酸
等の2価アルコール、必要に応じて安息香酸等のモノカ
ルボン酸、(無水)トリメリット酸等の3価以上のカル
ボン酸、トリメチロールエタン、トリメチロールプロパ
ン、グリセリン、ペンタエリスリットール等の3価以上
のアルコールとを反応させて得られる水酸基価約20〜
300KOHmg/gの水酸基含有ポリエステル樹脂に
上記ブロックポリイソシアネート架橋剤を配合してなる
塗料を使用することができる。
Examples of the powder coating (E) include aromatic phthalic acid such as (phthalic anhydride), isophthalic acid, terephthalic acid, dimethyl isophthalate, dimethyl terephthalate, hexahydro (phthalic anhydride), and tetrahydro (phthalic anhydride). Aliphatic or alicyclic dicarboxylic acids and dihydric alcohols such as (poly) ethylene glycol, (poly) propylene glycol, butylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, and dimethylpropionic acid, if necessary It is obtained by reacting with monocarboxylic acid such as benzoic acid, trivalent or more carboxylic acid such as (anhydride) trimellitic acid, and trivalent or more alcohol such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol. Hydroxyl value of about 20 to
A paint obtained by blending the above blocked polyisocyanate crosslinking agent with a hydroxyl group-containing polyester resin of 300 KOH mg / g can be used.

【0028】基体樹脂と硬化剤との配合割合は、基体樹
脂100重量部当たり約10〜100重量部、好ましく
は約15〜80重量部の範囲が好適である。
The mixing ratio of the base resin and the curing agent is preferably about 10 to 100 parts by weight, and more preferably about 15 to 80 parts by weight, per 100 parts by weight of the base resin.

【0029】該混合粉体塗料(IV)を加熱して得られ
る塗膜は上層に粉体塗料(E)成分が多く、また下層に
粉体塗料(B)成分が多い塗膜で形成される。
A coating film obtained by heating the mixed powder coating material (IV) is formed of a coating film containing a large amount of the powder coating material (E) in the upper layer and a coating film containing a large amount of the powder coating material (B) in the lower layer. .

【0030】本発明の粉体塗料において、上層を形成す
る粉体塗料には抗菌剤を配合することができる。具体的
には、例えば、特に銀イオンを担持させた無機系抗菌剤
を配合することができる。該抗菌剤としては、銀イオン
を担持させた無機化合物であれば特に制限なく従来公知
のものが使用できる。銀イオンを担持させる無機化合物
としては、活性炭、活性アルミナ、シリカゲル等の無機
系吸着剤、ゼオライト、ヒドロキシアパタイト、リン酸
ジルコニウム、リン酸チタン、チタン酸カリウム、含水
酸化ビスマス、含水酸化ジルコニウムなどが挙げられ
る。
In the powder coating of the present invention, an antibacterial agent can be added to the powder coating forming the upper layer. Specifically, for example, an inorganic antibacterial agent particularly supporting silver ions can be blended. As the antibacterial agent, a conventionally known one can be used without any particular limitation as long as it is an inorganic compound carrying silver ions. Examples of the inorganic compound supporting silver ions include activated carbon, activated alumina, inorganic adsorbents such as silica gel, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrated bismuth, hydrated zirconium, and the like. Can be

【0031】これらの無機化合物に銀イオンを担持させ
る方法には、特に制限なく従来知られた担持方法がいず
れも採用できる。例えば物理吸着又は化学吸着により担
持させる方法、イオン交換反応により担持させる方法、
結合剤により担持させる方法、銀化合物を無機化合物に
打ち込むことにより担持させる方法、蒸着、溶解析出反
応、スパッタ等の薄膜形成法により無機化合物の表面に
銀化合物の薄層を形成させることにより担持させる方法
等が挙げられる。上記無機化合物の中で、無機イオン交
換体は銀イオンを強固に担持できることから好ましく、
特にゼオライトやリン酸ジルコニウム塩などが好適に使
用できる。
The method for supporting silver ions on these inorganic compounds is not particularly limited, and any conventionally known supporting method can be employed. For example, a method of supporting by physical adsorption or chemical adsorption, a method of supporting by ion exchange reaction,
A method in which a silver compound is supported by a binder, a method in which a silver compound is supported by being driven into an inorganic compound, and a method in which a thin layer of a silver compound is formed on the surface of the inorganic compound by a thin film forming method such as vapor deposition, dissolution deposition reaction, or sputtering. Method and the like. Among the above inorganic compounds, the inorganic ion exchanger is preferable because it can strongly support silver ions,
In particular, zeolite and zirconium phosphate can be preferably used.

【0032】該化合物の具体例としては、例えば「ノバ
ロンAG−300」(東亜合成化学社製、銀イオン担持
リン酸ジルコニウム)、「ゼオミックAW−10D」
(シナネンニュ−セラミック社製、銀イオン担持ゼオラ
イト)などの市販品も利用できる。
Specific examples of the compound include “NOVALON AG-300” (manufactured by Toagosei Chemical Co., Ltd., zirconium phosphate carrying silver ion), and “Zeomic AW-10D”.
Commercially available products such as (Sinanen-Ceramic Co., Ltd., silver ion-supporting zeolite) can also be used.

【0033】銀イオンを担持させた無機系抗菌剤の粒径
は、塗装後の仕上り性、抗菌剤の有効面積などから平均
粒径0.001〜20μm以下、好ましくは0.01〜
10μmの微粒子状であることが望ましい。
The particle size of the inorganic antibacterial agent carrying silver ions is from 0.001 to 20 μm, preferably from 0.01 to 20 μm, based on the finish after coating and the effective area of the antibacterial agent.
It is desirable that the fine particles have a particle size of 10 μm.

【0034】銀イオンを担持させた無機系抗菌剤の配合
割合は、熱硬化性樹脂100重量部に対して好ましくは
0.05〜50重量部、さらに好ましくは0.5〜10
重量部が抗菌効果及び経済性から好適である。
The compounding ratio of the inorganic antibacterial agent carrying silver ions is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the thermosetting resin.
A weight part is preferable from an antibacterial effect and economical efficiency.

【0035】更に、該粉体塗料にはビス(ピリジン−2
−チオ−ル−1−オキシド)亜鉛塩は、いわゆるジンク
ピリチオンを必要に応じて配合することができる。ビス
(ピリジン−2−チオ−ル−1−オキシド)亜鉛塩の粒
径は、塗装後の仕上り性、抗菌剤の有効面積などから平
均粒径0.001〜20μm以下、好ましくは0.01
〜10μmの微粒子状であることが望ましい。
Further, bis (pyridine-2) is added to the powder coating.
The so-called zinc pyrithione can be blended with the (thiol-1-oxide) zinc salt as needed. The particle size of the bis (pyridine-2-thiol-1-oxide) zinc salt is from 0.001 to 20 μm or less, preferably from 0.01 to 20 μm, from the finish after coating and the effective area of the antibacterial agent.
Desirably, it is in the form of fine particles of 10 to 10 μm.

【0036】ビス(ピリジン−2−チオ−ル−1−オキ
シド)亜鉛塩の配合割合は、熱硬化性樹脂100重量部
に対して好ましくは0.001〜20重量部、さらに好
ましくは0.05〜5重量部が抗菌効果、変色防止能及
び経済性から好適である。
The mixing ratio of bis (pyridine-2-thiol-1-oxide) zinc salt is preferably 0.001 to 20 parts by weight, more preferably 0.05 to 100 parts by weight of the thermosetting resin. From 5 to 5 parts by weight is suitable from the viewpoint of antibacterial effect, discoloration preventing ability and economy.

【0037】上層塗膜を形成する粉体塗料には必要に応
じて撥油剤、紫外線安定剤、紫外線吸収剤(ベンゾトリ
アゾール化合物等)を配合することが好ましい。
It is preferable to add an oil repellent, an ultraviolet stabilizer, and an ultraviolet absorber (such as a benzotriazole compound) to the powder coating for forming the upper layer coating film, if necessary.

【0038】本発明の粉体塗料において、下層塗膜を形
成する粉体塗料には必要に応じて防錆剤を配合すること
ができる。更にこれらの上層及び下層を形成する粉体塗
料には必要に応じて着色剤、充填剤、硬化触媒、流動性
調整剤、ハジキ防止剤等の塗料用添加剤が配合できる。
In the powder coating of the present invention, a rust inhibitor can be added to the powder coating forming the lower layer coating film, if necessary. Further, paint additives such as a colorant, a filler, a curing catalyst, a fluidity control agent, and an anti-cissing agent can be added to the powder coating material forming the upper layer and the lower layer, if necessary.

【0039】本発明で使用する粉体塗料(A)〜(E)
は、例えば、溶融混練、粉砕、濾過(篩い)等の行程に
より製造することができる。
Powder coatings (A) to (E) used in the present invention
Can be produced by processes such as melt-kneading, pulverizing, and filtering (sieving).

【0040】本発明の粉体塗料(I)〜(IV)は、例
えば、上記2種類の粉体塗料をヘンシェルミキサーなど
により混合もしくはアトマイザー、ジェットミル等の粉
砕器で乾式混合分散して製造することができる。
The powder coatings (I) to (IV) of the present invention are produced, for example, by mixing the above two types of powder coatings with a Henschel mixer or by dry mixing and dispersing with a pulverizer such as an atomizer or a jet mill. be able to.

【0041】粉体塗料(I)〜(IV)において、粉体
塗料(A)と(B)、粉体塗料(C)と(D)、粉体塗
料(C)と(B)及び粉体塗料(E)と(B)との混合
割合はそれぞれ約30〜70重量%、特に約40〜60
重量%の範囲が好ましい。
In powder coatings (I) to (IV), powder coatings (A) and (B), powder coatings (C) and (D), powder coatings (C) and (B) and powder coatings The mixing ratio of the paints (E) and (B) is about 30 to 70% by weight, especially about 40 to 60% by weight.
A range of weight% is preferred.

【0042】粉体塗料(I)〜(IV)は、平均粒子径
が5〜100μm、好ましくは10〜80μmの範囲が
良い。平均粒子径が5μm未満になると、静電粉体塗装
作業性が低下し、一方100μmを越えると塗着効率、
塗膜外観等が低下するので好ましくない。
The powder coatings (I) to (IV) have an average particle diameter of 5 to 100 μm, preferably 10 to 80 μm. When the average particle diameter is less than 5 μm, the workability of the electrostatic powder coating decreases, while when the average particle diameter exceeds 100 μm, the coating efficiency and
It is not preferable because the appearance of the coating film is deteriorated.

【0043】次に、本発明の塗膜形成方法について説明
する。
Next, the coating film forming method of the present invention will be described.

【0044】本発明の粉体塗膜形成方法は、基材表面を
オニウム塩化合物で処理し、次いで熱硬化型複層粉体塗
料を静電粉体塗装し、加熱硬化させる形成方法である。
The method for forming a powder coating film of the present invention is a method in which the surface of a substrate is treated with an onium salt compound, and then a thermosetting double-layer powder coating material is electrostatically powder-coated and cured by heating.

【0045】本発明方法で使用する基材は、静電粉体塗
装が可能で加熱により基材が変形を起こさない従来から
静電粉体塗装用に使用されているもの使用することがで
きる。具体的には、例えば鉄鋼、銅、ステンレス、合金
鋼、アルミニウム及びその合金、亜鉛、亜鉛メッキ鋼
材、亜鉛合金、スズメッキ鋼材、燐酸亜鉛又は燐酸鉄処
理鋼材などの金属類が挙げられる。該基材としては、板
状であってもパイプ状、箱状等に成型された加工品であ
っても構わない。また、該基材の表面には必要に応じて
プライマー塗装、中塗り塗装を施しても構わない。
The substrate used in the method of the present invention may be any of those conventionally used for electrostatic powder coating, which can be applied with electrostatic powder and does not deform the substrate due to heating. Specific examples include metals such as steel, copper, stainless steel, alloy steel, aluminum and alloys thereof, zinc, galvanized steel, zinc alloy, tin-plated steel, zinc phosphate and iron phosphate-treated steel. The base material may be a plate, a processed product molded into a pipe, a box, or the like. Further, the surface of the base material may be subjected to primer coating or intermediate coating as needed.

【0046】上記基材を処理するオニウム塩化合物とし
ては、一般式 [(R)4 Y]+ X− 又は[(R)3
S]+ X− で表されるものが好ましい。式中、Rは同
一もしくは異なって水素原子、低級アルキル基(例えば
メチル、エチル、プロピル、ブチル、ヘキシル等)、ヒ
ドロキシ低級アルキル基(例えばヒドロキシメチル、ヒ
ドロキシエチル、ヒドロキシプロピル、ヒドロキシブチ
ル、ヒドロキシヘキシル等)、ハロ低級アルキル基(例
えば臭素化メチル、臭素化エチル等)、低級アルコキシ
低級アルキル基( 例えばメトキシメチル、メトキシエ
チル、メトキシプロピル、メトキシブチル、メトキシヘ
キシル等)、シクロアルキル基(例えばシクロヘキシ
ル、シクロヘキシルメチル、シクロペンチル等)、アリ
ール基(例えばフェニル、トルイル、キシリル等)又は
アラルキル基(例えばベンジル基等)などの有機基が挙
げられる。Yは窒素原子又は燐原子である。Xは負イオ
ンを示すものであって、例えばハロゲンイオン(例えば
塩素、臭素、フッ素、ヨウ素等)、無機酸根(例えば硫
酸根、燐酸根等)、有機酸根(例えば酢酸根、ベンジル
スルホン酸根、水酸根等)等が挙げられる。上記した低
級なる意味は炭素数6以下のものを示す。上記した一般
式において、特にRが低級アルキル基、フェニル基、ベ
ンジル基のものXがハロゲンイオンのアンモニウム又は
ホスホニウム塩化合物が好ましい。
As the onium salt compound for treating the above-mentioned substrate, a general formula [(R) 4Y] + X- or [(R) 3
Those represented by [S] + X− are preferable. In the formula, R is the same or different and is a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, propyl, butyl, hexyl, etc.), a hydroxy lower alkyl group (eg, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, etc.) ), Halo-lower alkyl groups (eg, methyl bromide, ethyl bromide, etc.), lower alkoxy lower alkyl groups (eg, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxyhexyl, etc.), cycloalkyl groups (eg, cyclohexyl, cyclohexyl) Organic groups such as methyl, cyclopentyl, etc.), aryl groups (eg, phenyl, toluyl, xylyl, etc.) and aralkyl groups (eg, benzyl group, etc.). Y is a nitrogen atom or a phosphorus atom. X represents a negative ion, for example, a halogen ion (eg, chlorine, bromine, fluorine, iodine, etc.), an inorganic acid group (eg, a sulfate group, a phosphate group, etc.), an organic acid group (eg, an acetate group, a benzylsulfonic acid group, water) Acid radicals). The above lower meaning means those having 6 or less carbon atoms. In the above-mentioned general formula, an ammonium or phosphonium salt compound in which R is a lower alkyl group, a phenyl group or a benzyl group and X is a halogen ion is particularly preferred.

【0047】上記オニウム塩化合物としては、例えば塩
化テトラメチルホスホニウム、塩化テトラエチルホスホ
ニウム、塩化テトラブチルホスホニウム、塩化トリメチ
ルエチルホスホニウム、塩化トリフェニルベンジルホス
ホニウム、臭素化テトラメチルホスホニウム、臭素化ト
リフェニルベンジルホスホニウム等の如きホスホニウム
塩化合物類;塩化テトラメチルアンモニウム、塩化テト
ラエチルアンモニウム、塩化テトラブチルアンモニウ
ム、塩化トリメチルエチルアンモニウム、塩化トリフェ
ニルベンジルアンモニウム、臭素化テトラメチルアンモ
ニウム、臭素化トリフェニルベンジルアンモニウム等の
如きアンモニウム塩化合物類;塩化トリメチルスルホニ
ウム、塩化テトラエチルスルホニウム、塩化テトラブチ
ルスルホニウム、塩化トリメチルエチルスルホニウム、
塩化トリフェニルベンジルスルホニウム等の如きスルホ
ニウム塩化合物類が挙げられる。
Examples of the onium salt compound include tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrabutylphosphonium chloride, trimethylethylphosphonium chloride, triphenylbenzylphosphonium chloride, tetramethylphosphonium bromide, and triphenylbenzylphosphonium bromide. Phosphonium salt compounds such as; ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylethylammonium chloride, triphenylbenzylammonium chloride, tetramethylammonium bromide, and triphenylbenzylammonium bromide ; Trimethylsulfonium chloride, tetraethylsulfonium chloride, tetrabutylsulfonium chloride, salt Trimethyl ethyl sulfonium,
And sulfonium salt compounds such as triphenylbenzylsulfonium chloride.

【0048】本発明方法は上記基材にオニウム塩化合物
を水に溶解もしくは分散した水性処理剤を塗布し、乾燥
を行ったのち、粉体塗料を静電粉体塗装を行い、焼き付
けることにより実施できる。該オニウム塩化合物はそれ
自体水に溶解し易いものであるが、必要に応じて水性有
機溶剤(アルコール類、ケトン類、エステル類)等を配
合することができる。水性処理剤の固形分は約0.01
〜30重量%の範囲が好ましい。また処理方法は、刷
毛、ローラー、スプレー、浸漬等の手段により行うこと
ができる。処理量は乾燥膜厚で約0.01〜10ミクロ
ンの範囲が好ましい。乾燥は室温もしくは加熱により行
うことができる。加熱する場合は約40〜140℃の範
囲で行うことが好ましい。静電粉体塗装はコロナ静電塗
装や摩擦帯電粉体塗装などが含まれる。粉体膜厚は約4
0〜100ミクロンの範囲が好ましい。粉体塗料の焼き
付けは、通常約120〜200℃で約20〜40分間の
範囲で行うことができる。
The method of the present invention is carried out by applying an aqueous treating agent obtained by dissolving or dispersing an onium salt compound in water to the above-mentioned substrate, followed by drying, followed by electrostatic powder coating of the powder coating and baking. it can. The onium salt compound itself is easily soluble in water, but may be mixed with an aqueous organic solvent (alcohols, ketones, esters) and the like, if necessary. The solid content of the aqueous treating agent is about 0.01
The range is preferably from 30 to 30% by weight. The treatment can be performed by means such as brush, roller, spray, immersion and the like. The treatment amount is preferably in the range of about 0.01 to 10 microns in dry film thickness. Drying can be performed at room temperature or by heating. When heating, it is preferable to carry out in the range of about 40 to 140 ° C. Electrostatic powder coating includes corona electrostatic coating and triboelectric powder coating. Powder film thickness is about 4
A range from 0 to 100 microns is preferred. The baking of the powder coating can be usually performed at about 120 to 200 ° C. for about 20 to 40 minutes.

【0049】[0049]

【実施例】以下、実施例により本発明を具体的に説明す
る。尚、部及び%はそれぞれ重量部及び重量%を示す。
The present invention will be described below in detail with reference to examples. Parts and% indicate parts by weight and% by weight, respectively.

【0050】アクリル樹脂粉体塗料(A)の製造例 グリシジル基含有アクリル系樹脂(グリシジルメタクリ
レ−ト/スチレン/メチルメタクリレ−ト/n−ブチル
アクリレ−ト=40/10/20/30“重量比”平均
分子量8000、軟化点85℃、平均粒子径約35μ
m)1000重量部、ドデカン二酸290重量部及び二
酸化チタン顔料を500重量部配合したものを2軸エク
ストル−ダ−で溶融混練した後、冷却、粉砕、濾過して
平均粒子径約35μmの白色の粉体塗料(A)を製造し
た。
Production Example of Acrylic Resin Powder Coating (A) Glycidyl group-containing acrylic resin (glycidyl methacrylate / styrene / methyl methacrylate / n-butyl acrylate = 40/10/20/30 "by weight Ratio "average molecular weight 8000, softening point 85 ° C, average particle size about 35μ
m) A mixture of 1000 parts by weight, 290 parts by weight of dodecanedioic acid and 500 parts by weight of titanium dioxide pigment is melt-kneaded with a twin-screw extruder, then cooled, pulverized and filtered to obtain a white powder having an average particle diameter of about 35 μm. (A) was manufactured.

【0051】ポリエステル樹脂硬化型エポキシ樹脂粉体
塗料(B)の製造例 ユピカコートGVー230(日本ユピカ株式会社製、商
品名、酸価53、高酸価ポリエステル樹脂、以下同様の
意味を示す)500重量部、エピコ−ト1004(油化
シェル株式会社製、軟化点97〜103℃、平均分子量
約1400、エポキシ樹脂、以下同様の意味を示す)5
00重量部及び弁柄200重量部の配合物を2軸エクス
トル−ダ−で溶融混練した後、冷却、粉砕、濾過して平
均粒子径約30μmの弁柄色の粉体塗料(B)を製造し
た。
Example of Production of Polyester Resin-Curable Epoxy Resin Powder Coating (B) Yupika Coat GV-230 (trade name, acid value 53, high acid value polyester resin, manufactured by Nippon Yupika Co., Ltd.) 500 Parts by weight, Epicoat 1004 (manufactured by Yuka Shell Co., Ltd., softening point 97 to 103 ° C, average molecular weight of about 1400, epoxy resin, hereinafter the same meaning) 5
A mixture of 00 parts by weight and 200 parts by weight of a red stalk is melt-kneaded with a twin-screw extruder, then cooled, pulverized and filtered to produce a powder coating (B) having a red stalk color with an average particle diameter of about 30 μm. did.

【0052】ポリエステル樹脂硬化型アクリル樹脂粉体
塗料(C)の製造例 ユピカコートGVー230を700重量部、グリシジル
基含有アクリル系樹脂(上記粉体塗料(A)で使用した
樹脂と同様のもの)300重量部及び二酸化チタン顔料
500重量部配合したものを2軸エクストル−ダ−で溶
融混練した後、冷却、粉砕、濾過して平均粒子径約30
μmの白色の粉体塗料(C)を製造した。
Production Example of Polyester Resin-Curable Acrylic Resin Powder Coating (C) 700 parts by weight of Yupica Coat GV-230, glycidyl group-containing acrylic resin (same as the resin used in the above powder coating (A)) A mixture of 300 parts by weight and 500 parts by weight of titanium dioxide pigment was melt-kneaded with a twin-screw extruder, then cooled, pulverized and filtered to obtain an average particle diameter of about 30.
A μm white powder coating (C) was produced.

【0053】エポキシ樹脂粉体塗料(D)の製造例 エピコ−ト1004を1000重量部、アジピン酸ジヒ
ドラジッド500重量部、弁柄200重量部の配合物を
2軸エクストル−ダ−で溶融混練した後、冷却、粉砕、
濾過して平均粒子径約30μmの弁柄色の粉体塗料
(D)を製造した。
Production Example of Epoxy Resin Powder Coating (D) A mixture of 1000 parts by weight of Epicoat 1004, 500 parts by weight of adipic dihydrazide, and 200 parts by weight of a red stem was melt-kneaded with a twin-screw extruder. , Cooling, crushing,
Filtration was performed to produce a reddish-colored powder coating material (D) having an average particle size of about 30 μm.

【0054】ポリエステル樹脂粉体塗料(E)の製造例 エステルER−7200(日本エステル社製、商品名、
水酸基含有ポリエステル樹脂、軟化点80℃)1000
重量部、ε−カプロラクタムブロックイソホロンジイソ
シアネ−ト105重量部、TK−1(武田薬品工業株式
会社製、商品名、錫系触媒)10重量部の配合物及び二
酸化チタン顔料を500重量部を配合したものを2軸エ
クストル−ダ−で溶融混練した後、冷却、粉砕、濾過し
て平均粒子径約40μmの白色の粉体塗料(E)を製造
した。
Production Example of Polyester Resin Powder Coating (E) Ester ER-7200 (trade name, manufactured by Nippon Ester Co., Ltd.)
Hydroxyl-containing polyester resin, softening point 80 ° C) 1000
Parts by weight, 105 parts by weight of ε-caprolactam block isophorone diisocyanate, 10 parts by weight of TK-1 (trade name, manufactured by Takeda Pharmaceutical Co., Ltd., tin catalyst) and 500 parts by weight of a titanium dioxide pigment. The mixture was melt-kneaded with a twin-screw extruder, cooled, pulverized and filtered to produce a white powder coating (E) having an average particle size of about 40 μm.

【0055】ポリエステル樹脂粉体塗料(E´)の製造
例 上記粉体塗料(E)の製造例において二酸化チタン顔料
に代えてフタロシアニンブルー青色顔料70重量部に代
えた以外は粉体塗料(E)と同様にして青色の粉体塗料
(E)を製造した。
Production Example of Polyester Resin Powder Coating (E ') Powder coating (E) except that in the production example of powder coating (E) above, 70 parts by weight of phthalocyanine blue pigment were used instead of titanium dioxide pigment. In the same manner as in the above, a blue powder coating material (E) was produced.

【0056】実施例1 上記粉体塗料(A)600部と粉体塗料(B)400部
とをヘンシェルミキサーで混合して混合粉体塗料を製造
した。 実施例1で形成(表面処理有)され
た塗膜の断面図を図1に示す。図1からも明らかなよう
に粉体塗膜(A)が上層にまた粉体塗膜(B)が下層に
分離していることがわかる。
Example 1 A mixed powder coating was produced by mixing 600 parts of the powder coating (A) and 400 parts of the powder coating (B) with a Henschel mixer. FIG. 1 shows a cross-sectional view of the coating film formed in Example 1 (with surface treatment). As is clear from FIG. 1, the powder coating (A) is separated into the upper layer and the powder coating (B) is separated into the lower layer.

【0057】実施例2 表1に記載の配合で実施例1と同様にして混合粉体塗料
を製造した。
Example 2 A mixed powder coating was produced in the same manner as in Example 1 with the composition shown in Table 1.

【0058】次いで、実施例1と同様にして複層粉体塗
膜を形成した。
Next, a multilayer powder coating film was formed in the same manner as in Example 1.

【0059】実施例3 表1に記載の配合で実施例1と同様にして混合粉体塗料
を製造した。
Example 3 A mixed powder coating was produced in the same manner as in Example 1 with the composition shown in Table 1.

【0060】次いで、実施例1と同様にして複層粉体塗
膜を形成した。
Next, a multilayer powder coating was formed in the same manner as in Example 1.

【0061】実施例4 表1に記載の配合で実施例1と同様にして混合粉体塗料
を製造した。
Example 4 A mixed powder coating was produced in the same manner as in Example 1 with the composition shown in Table 1.

【0062】次いで、実施例1と同様にして複層粉体塗
膜を形成した。
Next, a multilayer powder coating film was formed in the same manner as in Example 1.

【0063】比較例1 表1に記載の配合で実施例1と同様にして混合粉体塗料
を製造した。
Comparative Example 1 A mixed powder coating was produced in the same manner as in Example 1 with the composition shown in Table 1.

【0064】次いで、実施例1と同様にして複層粉体塗
膜を形成した。
Next, a multilayer powder coating film was formed in the same manner as in Example 1.

【0065】比較例1で形成(表面処理無)された塗膜
の断面図を図2に示す。図2から明らかなように粉体塗
膜(A)と(D)とが上層及び下層に完全に分離しない
でお互いに不連続な塗膜が形成されている。
FIG. 2 shows a cross-sectional view of the coating film formed in Comparative Example 1 (without surface treatment). As is clear from FIG. 2, the powder coatings (A) and (D) are not completely separated into an upper layer and a lower layer, and discontinuous coating films are formed.

【0066】比較例2 表1に記載の配合で実施例1と同様にして混合粉体塗料
を製造した。
Comparative Example 2 A mixed powder coating was produced in the same manner as in Example 1 with the composition shown in Table 1.

【0067】次いで、実施例1と同様にして複層粉体塗
膜を形成した。
Next, a multilayer powder coating film was formed in the same manner as in Example 1.

【0068】実施例及び比較例の各種粉体塗料の塗膜性
能試験結果を表1に示す。
Table 1 shows the coating film performance test results of the various powder coatings of the examples and comparative examples.

【0069】[0069]

【表1】 [Table 1]

【0070】表1において試験は次の様にして行った。In Table 1, the test was performed as follows.

【0071】塗膜性能試験 塗装板の調整:表面処理無;燐酸亜鉛処理鋼板に乾燥膜
厚が約80μmになるように静電粉体塗装し、180℃
で30分間焼付けを行ったものを試験として使用した。
Test of coating film performance Preparation of coated plate: no surface treatment; electrostatic powder coating on zinc phosphate treated steel plate so that dry film thickness is about 80 μm;
Baked for 30 minutes was used as a test.

【0072】表面処理有;燐酸亜鉛処理鋼鈑に1%塩化
ベンジルテトラフェニルホスホニウム塩(溶媒、水/プ
ロパノール=30/70重量比)溶液を乾燥膜厚が約
0.5ミクロンになるように刷毛塗りし、次いで80℃
で10分間乾燥を行った板に、膜厚が約60μmになる
ように静電粉体塗装を行い、180℃で30分間焼き付
けを行ったものを試験板として使用した。
With a surface treatment; a 1% benzyltetraphenylphosphonium chloride (solvent, water / propanol = 30/70 weight ratio) solution is applied to a zinc phosphate-treated steel sheet so that the dry film thickness becomes about 0.5 μm. Apply, then 80 ° C
A plate dried at 10 ° C. for 10 minutes was subjected to electrostatic powder coating so as to have a film thickness of about 60 μm, and baked at 180 ° C. for 30 minutes, and used as a test plate.

【0073】塗膜分離性:塗装板を切断した後、断面を
研磨紙2000番で研磨して塗膜断面を平滑にして塗膜
分離性を評価した。○は分離良好なもの、△は分離はす
るが上下に分離しないもの、×は全く分離しないでまだ
ら模様となるもの。
Coating separability: After cutting the coated plate, the cross section was polished with abrasive paper No. 2000 to smooth the coating cross section, and the coating separability was evaluated. ○: good separation, Δ: separation but not vertical separation, ×: no separation and mottled pattern.

【0074】塗膜外観:塗膜表面を目視で観察し評価し
た。◎は平滑性、チヂミ等の異常がないもの、○は平滑
性、チヂミ等があるが実用上問題がないもの、△は平滑
性、チヂミ等の異常が認められるもの、×は平滑性、チ
ヂミ等の異常が著しく認められるもの。
Coating appearance: The coating surface was visually observed and evaluated. ◎ indicates that there is no abnormality such as smoothness and shrinkage, ○ indicates that there is smoothness and shrinkage but there is no practical problem, Δ indicates that there is an abnormality such as smoothness and shrinkage, and x indicates smoothness and shrinkage. Those with remarkable abnormalities such as

【0075】鏡面反射率:JIS K−5400の60
度、20度の鏡面光沢度を測定した。
Specular reflectance: 60 according to JIS K-5400
And 20 degrees of specular gloss.

【0076】耐溶剤性:塗膜表面をアセトンをしみ込ま
せたガーゼを指で強く往復10回擦ったのち塗膜表面を
観察した。○は異常なし、△はツヤ引けを生じたもの、
×はツヤ消しになったもの。
Solvent resistance: A gauze impregnated with acetone was soaked on the surface of the coating film ten times with a finger, and the surface of the coating film was observed. ○ indicates no abnormality, △ indicates glossiness,
×: matte.

【0077】耐衝撃性:JIS K-5400 8.
3.2に従って試験を行った。衝撃芯径1/2インチ、
落錘重量500gで試験した。ワレ、剥がれのない高さ
を測定した。
Impact resistance: JIS K-5400
The test was performed according to 3.2. Impact core diameter 1/2 inch,
The test was conducted with a drop weight of 500 g. The height without cracking and peeling was measured.

【0078】エリクセン値:JIS K−5400
8.2に従って試験を行った。
Erichsen value: JIS K-5400
The test was performed according to 8.2.

【0079】塗膜が割れ及び剥がれが生じるまでの鋼球
を押し出す破断距離(cm)を求めた。
The breaking distance (cm) at which the steel ball was extruded until the coating film cracked and peeled off was determined.

【0080】[0080]

【発明の効果】本発明によれば、上記した構成を有する
ことから塗膜の分離性に優れ、且つ塗膜性能に優れた複
層粉体塗膜を形成することができる。
According to the present invention, it is possible to form a multi-layer powder coating film having excellent separability of the coating film and excellent coating film performance due to having the above constitution.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本発明の実施例を示す複層粉体塗膜の断面図。FIG. 1 is a cross-sectional view of a multilayer powder coating film showing an example of the present invention.

【図2】本発明の比較例を示す複層粉体塗膜の断面図。FIG. 2 is a sectional view of a multilayer powder coating film showing a comparative example of the present invention.

【符号の説明】[Explanation of symbols]

1 粉体塗膜(A) 2 粉体塗膜(B) 3 粉体塗膜(E) 4 燐酸亜鉛処理鋼鈑に1%塩化ベンジルテトラフェニ
ルホスホニウム塩で処理した燐酸亜鉛処理鋼鈑 5 燐酸亜鉛処理鋼鈑
Reference Signs List 1 powder coating (A) 2 powder coating (B) 3 powder coating (E) 4 zinc phosphate-treated steel sheet treated with 1% benzyltetraphenylphosphonium chloride on zinc phosphate-treated steel sheet 5 zinc phosphate Treated steel plate

Claims (7)

【特許請求の範囲】[Claims] 【請求項1】熱硬化型アクリル樹脂粉体塗料(A)とポ
リエステル樹脂硬化型エポキシ樹脂粉体塗料(B)との
混合粉体塗料であることを特徴とする熱硬化型複層粉体
塗料。
1. A thermosetting double-layer powder coating material which is a mixed powder coating of a thermosetting acrylic resin powder coating material (A) and a polyester resin curing type epoxy resin powder coating material (B). .
【請求項2】ポリエステル樹脂硬化型アクリル樹脂粉体
塗料(C)と熱硬化型エポキシ樹脂粉体塗料(D)との
混合粉体塗料であることを特徴とする熱硬化型複層粉体
塗料。
2. A thermosetting multi-layer powder coating material which is a mixed powder coating of a polyester resin curing type acrylic resin powder coating material (C) and a thermosetting epoxy resin powder coating material (D). .
【請求項3】ポリエステル樹脂硬化型アクリル樹脂粉体
塗料(C)とポリエステル樹脂硬化型エポキシ樹脂粉体
塗料(B)との混合粉体塗料であることを特徴とする熱
硬化型複層粉体塗料。
3. A thermosetting double-layer powder, which is a mixed powder coating of a polyester resin-curable acrylic resin powder coating (C) and a polyester resin-curable epoxy resin powder coating (B). paint.
【請求項4】熱硬化型ポリエステル樹脂粉体塗料(E)
と熱硬化型エポキシ樹脂粉体塗料(D)との混合粉体塗
料であることを特徴とする熱硬化型複層粉体塗料。
4. Thermosetting polyester resin powder coating (E)
And a thermosetting epoxy resin powder coating (D).
【請求項5】基材表面をオニウム塩化合物で処理し、次
いで熱硬化型複層粉体塗料を静電粉体塗装し、加熱硬化
させることを特徴とする熱硬化型複層粉体塗膜の形成方
法。
5. A thermosetting multi-layer powder coating film characterized by treating a substrate surface with an onium salt compound, then applying a thermosetting multi-layer powder coating material to an electrostatic powder, and heat-curing. Formation method.
【請求項6】熱硬化型粉体塗料が上記請求項1乃至4に
記載の混合粉体塗料であることを特徴とする熱硬化型複
層粉体塗膜の形成方法。
6. A method for forming a thermosetting multilayer powder coating film, wherein the thermosetting powder coating material is the mixed powder coating material according to any one of claims 1 to 4.
【請求項7】上記オニウム塩化合物がホスホニウム塩化
合物であることを特徴とする請求項5又は6に記載の熱
硬化型複層粉体塗膜の形成方法。
7. The method for forming a thermosetting double-layer powder coating according to claim 5, wherein the onium salt compound is a phosphonium salt compound.
JP9136234A 1997-05-27 1997-05-27 Thermosetting double-layer powder coating material and method for forming coating film therefrom Pending JPH10324824A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9136234A JPH10324824A (en) 1997-05-27 1997-05-27 Thermosetting double-layer powder coating material and method for forming coating film therefrom

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9136234A JPH10324824A (en) 1997-05-27 1997-05-27 Thermosetting double-layer powder coating material and method for forming coating film therefrom

Publications (1)

Publication Number Publication Date
JPH10324824A true JPH10324824A (en) 1998-12-08

Family

ID=15170429

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPH10324824A (en)

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