TWI682011B - Metal surface treatment agent - Google Patents

Metal surface treatment agent Download PDF

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TWI682011B
TWI682011B TW106112628A TW106112628A TWI682011B TW I682011 B TWI682011 B TW I682011B TW 106112628 A TW106112628 A TW 106112628A TW 106112628 A TW106112628 A TW 106112628A TW I682011 B TWI682011 B TW I682011B
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metal surface
surface treatment
treatment agent
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silane coupling
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TW106112628A
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TW201809155A (en
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廣神宗直
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日商信越化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust

Abstract

本發明提供作為塗料等之塗覆的前處理劑而使用於金屬表面時，可對金屬表面賦予優異加工性、密著性及耐腐蝕性之非鉻酸鹽金屬表面處理劑。 The present invention provides a non-chromate metal surface treatment agent that can impart excellent workability, adhesion, and corrosion resistance to a metal surface when used on a metal surface as a pretreatment agent for coating of paints and the like.

上述金屬表面處理劑含有以下述通式(1)表示之苯并***化合物及矽烷偶合劑，

Figure 106112628-A0202-11-0001-1
The above metal surface treatment agent contains a benzotriazole compound represented by the following general formula (1) and a silane coupling agent,
Figure 106112628-A0202-11-0001-1

[式中，R1相互獨立表示氫原子或碳數1~10之烷基，R2表示碳數1~10之伸烷基，R3及R4相互獨立表示氫原子、碳數1~10之烷基或以下述通式(2)表示之基，但R3及R4之至少一者為以下述式(2)表示之基：-R5-OH (2) [In the formula, R 1 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkylene group having 1 to 10 carbon atoms, and R 3 and R 4 independently represent a hydrogen atom and 1 to 10 carbon atoms. Alkyl group or a group represented by the following general formula (2), but at least one of R 3 and R 4 is a group represented by the following formula (2): -R 5 -OH (2)

(式中，R5表示碳數1~10之伸烷基)]。 (In the formula, R 5 represents an alkylene group having 1 to 10 carbon atoms)].

Description

金屬表面處理劑 Metal surface treatment agent

本發明係關於金屬表面處理劑，更詳言之，係關於不含鉻之非鉻酸鹽金屬表面處理劑。 The present invention relates to a metal surface treatment agent, and more specifically, to a non-chromate metal surface treatment agent not containing chromium.

以往，作為金屬之表面處理劑，已廣泛使用鉻酸鹽或磷酸鉻酸鹽等之鉻系表面處理劑。 Conventionally, chromium-based surface treatment agents such as chromate and phosphate chromate have been widely used as metal surface treatment agents.

然而，打聽最近之環境規範之動向，由於鉻具有之毒性尤其是致癌性，未來有限制其使用之可能性，因此期望開發具有與鉻酸鹽處理劑同等密著性、耐腐蝕性之不含鉻(非鉻酸鹽)之金屬表面處理劑。 However, to inquire about the recent environmental regulations, due to the toxicity of chromium, especially carcinogenicity, and the possibility of restricting its use in the future, it is expected to develop non-free materials with the same adhesion and corrosion resistance as chromate treatment agents. Chromium (non-chromate) metal surface treatment agent.

作為非鉻酸鹽金屬表面處理劑，例如於專利文獻1中，揭示含有水溶性樹脂、含硫羰基之化合物、磷酸離子及水分散系氧化矽之非鉻酸鹽防鏽處理劑，但該系統雖耐腐蝕性優異，但加工性及與基材之密著性不充分。 As a non-chromate metal surface treatment agent, for example, in Patent Document 1, a non-chromate anti-rust treatment agent containing a water-soluble resin, a sulfocarbonyl group-containing compound, a phosphate ion, and a water-dispersible silica is disclosed, but this system Although it has excellent corrosion resistance, it has insufficient workability and adhesion to the substrate.

專利文獻2中，揭示含2種以上矽烷偶合劑之酸性表面處理劑，但該系統於進行處理金屬表面之處理後，於要求耐腐蝕性及加工性之情況下，耐腐蝕性不足。 Patent Document 2 discloses an acidic surface treatment agent containing two or more kinds of silane coupling agents, but the system has insufficient corrosion resistance after the treatment of the metal surface is required when corrosion resistance and workability are required.

作為解決該等缺點之技術，於專利文獻3中，揭示以矽烷偶合劑、水分散性氧化矽及鋯或鈦離子為必須成分之 非鉻酸鹽金屬表面處理劑。該表面處理劑之耐腐蝕性及加工性雖已改善，但對基材之塗佈性及與上層被膜之密著強度等方面仍不充分。 As a technique for solving these shortcomings, Patent Document 3 discloses that a silane coupling agent, water-dispersible silica, and zirconium or titanium ions are essential components. Non-chromate metal surface treatment agent. Although the corrosion resistance and workability of the surface treatment agent have been improved, the coating properties on the substrate and the adhesion strength with the upper coating film are still insufficient.

又，專利文獻4中，揭示含有具有與水系乳液反應之特定官能基之矽烷偶合劑之鋼構造物用表面處理劑，但該情況下，所要求之耐腐蝕性僅係對於如濕潤試驗之比較溫和之試驗，而不具有可耐受嚴苛耐腐蝕試驗之耐腐蝕性。 In addition, Patent Document 4 discloses a surface treatment agent for a steel structure containing a silane coupling agent having a specific functional group that reacts with an aqueous emulsion, but in this case, the required corrosion resistance is only for comparison such as a wet test It is a mild test without corrosion resistance that can withstand severe corrosion resistance tests.

專利文獻5中，揭示於金屬等之表面處理劑中使用含有咪唑基之有機矽化合物，且於專利文獻6中，揭示於金屬等之表面處理劑中使用含有苯并***基之有機矽化合物，但均不具有於耐腐蝕性或深拉(deep drawing)性等可充分滿足之性能。 Patent Document 5 discloses the use of organosilicon compounds containing imidazolyl groups in surface treatment agents such as metals, and Patent Document 6 discloses the use of organosilicon compounds containing benzotriazole groups in surface treatment agents such as metals. , But none of them have fully satisfied performance such as corrosion resistance or deep drawing.

專利文獻7中，揭示含有水系乳液、及於3價過渡金屬離子上配位β-二酮2分子及水2分子之化合物、以及含有矽烷偶合劑之防鏽用表面處理劑。該表面處理劑之特徵為3價過渡金屬錯合物藉由乾燥而成為難溶性化合物而展現防鏽能力、塗膜密著能力，但所要求之耐腐蝕性無法耐受過於嚴苛之環境，有十二萬分應改良之空間。 Patent Document 7 discloses a compound containing an aqueous emulsion, 2 molecules of β-diketone and 2 molecules of water coordinated to a trivalent transition metal ion, and a surface treatment agent for rust prevention containing a silane coupling agent. The characteristic of this surface treatment agent is that trivalent transition metal complexes become insoluble compounds by drying to exhibit rust prevention ability and coating film adhesion ability, but the required corrosion resistance cannot withstand excessively harsh environments. There is 120,000 points of room for improvement.

如以上，迄今未知有以薄膜而能以高水準展現耐腐蝕性、加工密著性、塗佈性、接著強度等諸特性之金屬表面處理劑，而期望開發具有此等性能之表面處理劑。 As described above, there is no known metal surface treatment agent that can exhibit various characteristics such as corrosion resistance, process adhesion, coating property, and adhesive strength at a high level as a thin film, and it is desired to develop a surface treatment agent having such properties.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平11-29724號公報 [Patent Document 1] Japanese Patent Laid-Open No. 11-29724

[專利文獻2]日本特開平8-073775號公報 [Patent Document 2] Japanese Patent Laid-Open No. 8-073775

[專利文獻3]日本特開2001-316845號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2001-316845

[專利文獻4]日本特開平10-60315號公報 [Patent Document 4] Japanese Patent Laid-Open No. 10-60315

[專利文獻5]日本特開2000-297093號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2000-297093

[專利文獻6]日本特開平6-279463號公報 [Patent Document 6] Japanese Patent Laid-Open No. 6-279463

[專利文獻7]日本特開2007-297648號公報 [Patent Document 7] Japanese Patent Application Publication No. 2007-297648

本發明係鑒於上述情況而完成者，目的在於提供作為塗料等之塗覆的前處理劑而對於金屬表面使用時，可對金屬表面賦予優異加工性、密著性及耐腐蝕性之非鉻酸鹽金屬表面處理劑。 The present invention has been completed in view of the above circumstances, and an object thereof is to provide a non-chromic acid that can impart excellent workability, adhesion, and corrosion resistance to a metal surface when used as a pretreatment agent for the coating of a paint or the like when used on the metal surface. Salt metal surface treatment agent.

本發明人等欲解決上述課題而積極檢討之結果，發現含有具有醇基之苯并***化合物與矽烷偶合劑作為必須成分之組成物，由於上述醇基與矽烷偶合劑中之烷氧基矽烷基反應而使苯并***層與矽氧烷層成為一體，而獲得防鏽耐腐蝕性優異之被膜，故可較好地作為金屬表面處理劑，因而完成本發明。 As a result of an active review by the present inventors to solve the above-mentioned problems, it was found that a composition containing an alcohol group-containing benzotriazole compound and a silane coupling agent as an essential component, due to the alkoxysilane in the alcohol group and silane coupling agent Based on the reaction, the benzotriazole layer and the siloxane layer are integrated, and a coating film excellent in rust prevention and corrosion resistance is obtained, so it can be preferably used as a metal surface treatment agent, thus completing the present invention.

亦即，本發明提供 That is, the present invention provides

1. 一種金屬表面處理劑，其特徵為含有以下述通式(1)表示之苯并***化合物及矽烷偶合劑，

Figure 106112628-A0202-12-0004-2
[式中，R1相互獨立表示氫原子或碳數1~10之烷基，R2表示碳數1~10之伸烷基，R3及R4相互獨立表示氫原子、碳數1~10之烷基、或以下述通式(2)表示之基，但R3及R4之至少一者為以下述式(2)表示之基：[化2]-R5-OH (2)(式中，R5表示碳數1~10之伸烷基)]。 1. A metal surface treatment agent characterized by containing a benzotriazole compound represented by the following general formula (1) and a silane coupling agent,
Figure 106112628-A0202-12-0004-2
 [In the formula, R 1 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkylene group having 1 to 10 carbon atoms, and R 3 and R 4 independently represent a hydrogen atom and 1 to 10 carbon atoms. Alkyl group, or a group represented by the following general formula (2), but at least one of R 3 and R 4 is a group represented by the following formula (2): [Chem 2]-R 5 -OH (2)( In the formula, R 5 represents a C 1-10 alkylene group)].

2. 如前述1之金屬表面處理劑，其中前述R2為亞甲基，R3及R4均為以前述通式(2)表示之基，且前述R5為伸乙基。 2. The metal surface treatment agent according to the aforementioned 1, wherein the aforementioned R 2 is a methylene group, R 3 and R 4 are both groups represented by the aforementioned general formula (2), and the aforementioned R 5 is an ethylidene group.

3. 如1或2之金屬表面處理劑，其中前述矽烷偶合劑為具有胺基之矽烷偶合劑。 3. A metal surface treatment agent such as 1 or 2, wherein the aforementioned silane coupling agent is a silane coupling agent having an amine group.

4. 如1或2之金屬表面處理劑，其中前述矽烷偶合劑為具有環氧基之矽烷偶合劑。 4. Metal surface treatment agent such as 1 or 2, wherein the aforementioned silane coupling agent is a silane coupling agent having an epoxy group.

5. 如1~4中任一項之金屬表面處理劑，其中含有有機鈦酸酯。 5. The metal surface treatment agent according to any one of 1 to 4, which contains an organic titanate.

6. 如1~5中任一項之金屬表面處理劑，其中含有水分散性氧化矽或有機溶劑分散性氧化矽。 6. The metal surface treatment agent according to any one of 1 to 5, which contains water-dispersible silica or organic solvent-dispersible silica.

7. 如1~6中任一項之金屬表面處理劑，其中含有選自Fe、Zr、Ti、V、W、Mo、Al、Sn、Nb、Hf、Y、Ho、Bi、La、Ce及Zn之1種以上之金屬的化合物。 7. The metal surface treatment agent according to any one of 1 to 6, which contains Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and A compound of one or more metals of Zn.

8. 如1~7中任一項之金屬表面處理劑，其中含有含硫羰基之化合物。 8. The metal surface treatment agent according to any one of 1 to 7, which contains a compound containing a sulfur carbonyl group.

9. 如1~8中任一項之金屬表面處理劑，其中含有水溶性樹脂或水分散性樹脂。 9. The metal surface treatment agent according to any one of 1 to 8, which contains a water-soluble resin or a water-dispersible resin.

10. 如1~9中任一項之金屬表面處理劑，其中含有磷酸離子。 10. The metal surface treatment agent according to any one of 1 to 9, which contains phosphoric acid ions.

本發明之金屬表面處理劑由於含有具有醇基之苯并***化合物與矽烷偶合劑作為必須成分，故認為於塗液中或處理後之塗膜中苯并***化合物中之醇基與矽烷偶合劑中之烷氧基矽烷基之間產生酯交換反應而使苯并***基與矽氧烷層一體化。 Since the metal surface treatment agent of the present invention contains a benzotriazole compound having an alcohol group and a silane coupling agent as essential components, it is considered that the alcohol group and silane in the benzotriazole compound in the coating liquid or the coating film after treatment The transesterification reaction occurs between the alkoxysilyl groups in the coupling agent to integrate the benzotriazole group with the siloxane layer.

因此，以本發明之金屬表面處理劑處理之塗裝鋼板以高水準展現防鏽耐腐蝕性。 Therefore, the coated steel sheet treated with the metal surface treatment agent of the present invention exhibits high levels of rust and corrosion resistance.

以下針對本發明具體加以說明。 The present invention will be specifically described below.

本發明之金屬表面處理劑含有以下述通式(1)表示 之苯并***化合物及矽烷偶合劑。 The metal surface treatment agent of the present invention is represented by the following general formula (1) The benzotriazole compound and silane coupling agent.

Figure 106112628-A0202-12-0006-3
Figure 106112628-A0202-12-0006-3

式(1)中，R1相互獨立表示氫原子或碳數1~10之烷基，R2表示碳數1~10之伸烷基，R3及R4相互獨立表示氫原子、碳數1~10之烷基、或以下述通式(2)表示之基，但R3及R4之至少一者為以下述式(2)表示之基。 In formula (1), R 1 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkylene group having 1 to 10 carbon atoms, and R 3 and R 4 independently represent a hydrogen atom and a carbon number 1 An alkyl group of ~10, or a group represented by the following general formula (2), but at least one of R 3 and R 4 is a group represented by the following formula (2).

【化4】-R5-OH (2) 【Chemical 4】-R 5 -OH (2)

(式中，R5表示碳數1~10之伸烷基)]。 (In the formula, R 5 represents an alkylene group having 1 to 10 carbon atoms)].

此處，作為碳數1~10之烷基可為直鏈狀、環狀、分支狀之任一者，作為其具體例舉例為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基等之直鏈或分支狀烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基等之環烷基等。 Here, the alkyl group having 1 to 10 carbon atoms may be linear, cyclic, or branched. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Straight-chain or branched alkyl, cyclopropyl, cyclobutyl, such as alkyl, second butyl, third butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Cycloalkyl groups such as alkyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

作為碳數1~10之伸烷基之具體例舉例為亞甲基、伸乙基、三亞甲基、伸丙基、伸異丙基、四亞甲基、伸異丁基、五亞甲基、六亞甲基、七亞甲基、八亞甲基、九亞甲 基、十亞甲基等。 Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylidene, trimethylene, propylidene, isopropylidene, tetramethylene, isobutylidene, and pentamethylene , Hexamethylene, heptamethylene, octamethylene, and nine methylene Base, decamethylene, etc.

其中，作為R1，較好相互獨立為氫原子或碳數1~5之烷基，更好為氫原子、甲基、乙基、正丙基，又更好為為氫原子或甲基，又更好R1之至少1個為甲基，最好R1之任意一個為甲基，其餘為氫原子。 Among them, R 1 is preferably independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and even more preferably a hydrogen atom or a methyl group, More preferably, at least one of R 1 is a methyl group, and preferably any one of R 1 is a methyl group, and the rest are hydrogen atoms.

作為R2較好為碳數1~5之伸烷基，更好為亞甲基、伸乙基、三亞甲基，又更好為亞甲基。 R 2 is preferably a C 1-5 alkylene group, more preferably a methylene group, an ethyl group, a trimethylene group, and even more preferably a methylene group.

作為R3及R4，較好均為上述式(2)表示之基。 R 3 and R 4 are preferably both groups represented by the above formula (2).

作為R5，較好為碳數1~5之伸烷基，更好為亞甲基、伸乙基、三亞甲基，又更好為伸乙基。 R 5 is preferably a C 1-5 alkylene group, more preferably a methylene group, an ethyl group, a trimethylene group, and even more preferably an ethyl group.

作為較佳之以式(1)表示之苯并***化合物舉例為下述通式(3)所示者。 Preferred benzotriazole compounds represented by formula (1) are exemplified by the following general formula (3).

Figure 106112628-A0202-12-0007-4
Figure 106112628-A0202-12-0007-4

(式中，R1表示與上述相同意義)。 (In the formula, R 1 has the same meaning as described above).

尤其可較好地使用2,2’-[[(4-甲基-1H-苯并***-1-基)甲基]亞胺基]雙乙醇(式(4))、2,2’-[[(5-甲基-1H-苯并***-1-基)甲基]亞胺基]雙乙醇(式(5))、2,2’-[[(1H-苯并***-1-基)甲基]亞胺基]雙乙醇(式(6))等。 In particular, 2,2'-[[(4-methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol (formula (4)), 2,2' can be preferably used -[[(5-methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol (formula (5)), 2,2'-[[(1H-benzotriazole -1-yl)methyl]imino]diethanol (formula (6)), etc.

Figure 106112628-A0202-12-0008-5
Figure 106112628-A0202-12-0008-5

又，如下述式(7)所示，苯并***環上之甲基位置未特定之2,2’-[[(甲基-1H-苯并***-1-基)甲基]亞胺基]雙乙醇(城北化學工業(股)製，TT-LYK)雖上市，本發明中亦可較好地使用該化合物。 In addition, as shown in the following formula (7), the methyl position on the benzotriazole ring is unspecified 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl] Amino] diethanol (produced by Chengbei Chemical Industry Co., Ltd., TT-LYK) is marketed, but this compound can also be preferably used in the present invention.

Figure 106112628-A0202-12-0008-6
Figure 106112628-A0202-12-0008-6

另一方面，作為矽烷偶合劑並未特別限定，但可自習知者適當選擇使用，作為其具體例，舉例為具有烷基之矽烷偶合劑、具有芳基之矽烷偶合劑、具有乙烯基之矽烷偶合劑、具有胺基之矽烷偶合劑、具有環氧基之矽烷偶合劑、具有(甲基)丙烯醯基之矽烷偶合劑、具有巰基之矽烷偶合劑，該等可單獨使用1種，亦可併用2種以上。 On the other hand, the silane coupling agent is not particularly limited, but can be appropriately selected and used by those skilled in the art. Specific examples thereof include an alkyl group silane coupling agent, an aryl group silane coupling agent, and a vinyl group silane. Coupling agent, silane coupling agent with amine group, silane coupling agent with epoxy group, silane coupling agent with (meth)acryloyl group, silane coupling agent with mercapto group, these can be used alone, or Use 2 or more types together.

該等中，較好為具有胺基之矽烷偶合劑、具有環氧基之矽烷偶合劑。 Among these, a silane coupling agent having an amine group and a silane coupling agent having an epoxy group are preferred.

作為具有胺基之矽烷偶合劑之具體例，舉例為3-胺基丙基三甲氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三乙氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基甲基二甲氧基矽烷等。 Specific examples of the silane coupling agent having an amine group include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane , 3-aminopropylmethyl diethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ- Aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-amino Propylmethyl diethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, etc.

作為具有環氧基之矽烷偶合劑之具體例舉例為2-(3,4-環氧基環己基)乙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷等。 Specific examples of the silane coupling agent having an epoxy group are 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyl Dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy Propyl methyl diethoxy silane, etc.

本發明之金屬表面處理劑中，矽烷偶合劑之使用量相對於上述苯并***化合物，以質量比計較好為0.1~100倍，更好為1~50倍，又更好為5~30倍左右。 In the metal surface treatment agent of the present invention, the amount of the silane coupling agent is preferably 0.1 to 100 times, more preferably 1 to 50 times, and more preferably 5 to 30 in terms of mass ratio relative to the benzotriazole compound. Times.

本發明之金屬表面處理劑如上述，藉由併用具有羥基之苯并***化合物與矽烷偶合劑，而可發揮高的防鏽耐腐蝕性。 As described above, the metal surface treatment agent of the present invention can exhibit high rust and corrosion resistance by using a benzotriazole compound having a hydroxyl group and a silane coupling agent together.

作為其理由，推測係苯并***基之羥基與矽烷偶合劑之水解性基於組成物中或於塗膜中進行酯交換而一體化， 藉此，苯并***基於金屬表面形成錯合物，而於上層形成矽氧烷層。 As a reason for this, it is speculated that the hydrolyzability of the hydroxyl group of benzotriazolyl group and the silane coupling agent is integrated based on transesterification in the composition or in the coating film, In this way, benzotriazole forms complexes based on the metal surface, and forms a siloxane layer on the upper layer.

本發明之金屬表面處理劑較好除了上述必須成分以外又含有溶劑。作為溶劑舉例為水、可溶解必須成分的苯并***化合物及矽烷偶合劑之有機溶劑及該有機溶劑與水之混合溶劑。 The metal surface treatment agent of the present invention preferably contains a solvent in addition to the above-mentioned essential components. Examples of the solvent include water, an organic solvent that can dissolve essential components, a benzotriazole compound, and a silane coupling agent, and a mixed solvent of the organic solvent and water.

作為有機溶劑之具體例舉例為甲醇、乙醇等之醇系溶劑；甲醯胺、N,N-二甲基甲醯胺、吡咯啶酮、N-甲基吡咯啶酮等之醯胺系溶劑；丙酮、甲基乙基酮、甲基異丁基酮等之酮系溶劑；戊烷、己烷、庚烷等之飽和烴系溶劑；苯、甲苯、二甲苯等之芳香族烴系溶劑等，該等中，較佳為甲醇、乙醇。 Specific examples of the organic solvent include alcohol-based solvents such as methanol and ethanol; acylamine-based solvents such as methylamine, N,N-dimethylformamide, pyrrolidone, and N-methylpyrrolidone; Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; saturated hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene, etc., Among these, methanol and ethanol are preferred.

於含有苯并***化合物、矽烷偶合劑及溶劑之金屬表面處理劑中，考慮所得防鏽耐腐蝕性效果及塗料之液安定性等時，上述苯并***化合物於金屬表面處理劑中較好以0.01~100g/L之濃度含有，更好以0.05~50g/L之濃度含有。 In the case of metal surface treatment agents containing benzotriazole compounds, silane coupling agents and solvents, the above benzotriazole compounds are better It is preferably contained at a concentration of 0.01 to 100 g/L, more preferably at a concentration of 0.05 to 50 g/L.

另一方面，考慮所得防鏽耐腐蝕性效果及塗料之液安定性等時，上述矽烷偶合劑於金屬表面處理劑中較好以0.01~200g/L之濃度含有，更好以0.05~100g/L之濃度含有。 On the other hand, when considering the obtained anti-corrosion and anti-corrosion effect and the liquid stability of the coating, etc., the above-mentioned silane coupling agent is preferably contained in the metal surface treatment agent at a concentration of 0.01 to 200 g/L, more preferably 0.05 to 100 g/ Contains L concentration.

本發明之金屬表面處理劑較好進而含有有機鈦酸酯類。 The metal surface treatment agent of the present invention preferably further contains organic titanates.

該有機鈦酸酯類可使用市售者，其構造等並未特別限 定，作為其具體例舉例為鈦酸四乙酯、鈦酸四異丙酯、鈦酸四正丁酯、鈦酸丁酯二聚物、四(2-乙基己基)鈦酸酯、及該等之聚合物、或乙醯基鈦酸鈦、聚乙醯丙酮鈦、辛基甘胺酸鈦、乳酸鈦、乳酸乙酯鈦、三乙醇胺酸鈦等之鈦螯合化合物等。 Commercially available organic titanate esters can be used, and the structure and the like are not particularly limited. As specific examples, tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetra(2-ethylhexyl) titanate, and the And other polymers, or titanium chelate compounds such as titanium acetylacetonate, titanium titanium acetone, titanium octylglycinate, titanium lactate, titanium ethyl lactate, titanium triethanolamine, etc.

該等可單獨使用1種，亦可併用2種以上。 These can be used alone or in combination of two or more.

使用上述有機鈦酸酯時，其調配量，考慮耐腐蝕性提高效果及金屬表面處理劑之浴安定性時，於金屬表面處理劑中，較好以0.05~100g/L之濃度含有，更好以0.5~60g/L之濃度含有。 When using the above-mentioned organic titanate, the amount of the compound is considered to be contained in a concentration of 0.05 to 100 g/L in the metal surface treatment agent, considering the effect of improving the corrosion resistance and the bath stability of the metal surface treatment agent, and more preferably Contained at a concentration of 0.5~60g/L.

本發明之金屬表面處理劑較好進而含有水分散性氧化矽或有機溶劑分散性氧化矽。該情況下，作為有機溶劑之具體例，舉例為甲醇、乙醇、異丙醇等醇類；丙二醇單甲醚、四氫呋喃等之醚類等。 The metal surface treatment agent of the present invention preferably further contains water-dispersible silica or organic solvent-dispersible silica. In this case, specific examples of the organic solvent include alcohols such as methanol, ethanol, and isopropanol; ethers such as propylene glycol monomethyl ether, tetrahydrofuran, and the like.

作為水或有機溶劑分散性氧化矽並未特別限定，但較好為鈉等之雜質少，為弱鹼系之球狀氧化矽、鏈狀氧化矽、鋁修飾氧化矽。 The water- or organic-solvent-dispersible silica is not particularly limited, but it is preferable that sodium and other impurities are few, and it is a weak alkali-based spherical silica, chain silica, and aluminum-modified silica.

作為球狀氧化矽可使用「SNOWTEX N」、「SNOWTEX UP」(均為日產化學工業(股)製)等之膠體氧化矽、或「AEROSIL」(日本AEROSIL(股)製)等之發煙氧化矽，作為鏈狀氧化矽可使用「SNOWTEX PS」(日產化學工業(股)製)等之氧化矽凝膠，作為鋁修飾氧化矽可使用「ADELITE AT-20A」(ADEKA(股)製)等之各種市售品。 As spherical silica, colloidal silica such as "SNOWTEX N", "SNOWTEX UP" (both manufactured by Nissan Chemical Industry Co., Ltd.), or fumed oxidation such as "AEROSIL" (manufactured by Japan AEROSIL) can be used. Silicone can use "SNOWTEX PS" (manufactured by Nissan Chemical Industry Co., Ltd.) as silicon oxide chains, and "ADELITE AT-20A" (manufactured by ADEKA) for aluminum modified silica. Of various commercially available products.

使用上述水或有機溶劑分散性氧化矽時，其調配量，考慮耐腐蝕性提高效果及金屬表面處理劑之浴安定性時，於金屬表面處理劑中以固形分計，較好以0.05~100g/L之濃度含有，更好以0.5~60g/L之濃度含有。 When the above water or organic solvent dispersible silica is used, the amount of the compound, considering the effect of improving the corrosion resistance and the stability of the bath of the metal surface treatment agent, is calculated as the solid content in the metal surface treatment agent, preferably 0.05 to 100g Contains a concentration of /L, preferably 0.5 to 60g/L.

本發明之金屬表面處理劑較好進而含有選自Fe、Zr、Ti、V、W、Mo、Al、Sn、Nb、Hf、Y、Ho、Bi、La、Ce及Zn之任1種以上之金屬的化合物。 The metal surface treatment agent of the present invention preferably further contains any one or more selected from Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce, and Zn Metal compounds.

作為上述金屬的化合物舉例為上述金屬之碳酸鹽、氧化物、氫氧化物、硝酸鹽、硫酸鹽、磷酸鹽、氟化物、氟酸或其鹽、含氧酸鹽、有機酸鹽等。 Examples of the compound of the above-mentioned metal include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluorides, fluoric acid or salts thereof, oxyacid salts, and organic acid salts of the above-mentioned metals.

作為鋯(Zr)化合物之具體例舉例為碳酸鋯銨、氫氟酸鋯、氟化銨鋯、氟化鉀鋯、氟化鈉鋯、乙醯丙酮鋯、丁醇鋯1-丁醇溶液、正丙醇鋯等。 Specific examples of the zirconium (Zr) compound include ammonium zirconium carbonate, zirconium hydrofluorate, ammonium zirconium fluoride, potassium zirconium fluoride, sodium zirconium fluoride, acetone zirconium zirconium, zirconium butoxide 1-butanol solution, positive Zirconium propoxide, etc.

作為鈦(Ti)化合物之具體例舉例為氫氟酸鈦、氟化銨鈦、草酸鈦鉀、異丙氧化鈦、鈦酸異丙酯、乙氧化鈦、2-乙基-1-己酸鈦、鈦酸肆異丙酯、鈦酸四正丁酯、氟化鉀鈦、氟化鈉鈦等。 Specific examples of titanium (Ti) compounds include titanium hydrofluorate, titanium ammonium fluoride, potassium titanium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, and titanium 2-ethyl-1-hexanoate , Isopropyl titanate, tetra-n-butyl titanate, potassium titanium fluoride, sodium titanium fluoride, etc.

作為釩(V)化合物之具體例舉例為五氧化釩(V)、三氧化釩(III)、二氧化釩(IV)、氫氧化釩(II)、氫氧化釩(III)、硫酸釩(II)、硫酸釩(III)、硫酸氧釩(IV)、氟化釩(III)、氟化釩(IV)、氟化釩(V)、三氯氧釩VOCl3、三氯化釩VCl3、六氟釩酸(III)或其鹽(鉀鹽、銨鹽等)、偏釩酸(V)或其鹽(鈉鹽、銨鹽等)、乙醯丙酮酸釩(IV) VO(OC(=CH2)CH2COCH3)2、乙醯丙酮酸釩(III)V(OC(=CH2)CH2COCH3)3、磷釩鉬酸H15-X[PV12-XMoO40]．nH2O(6<X<12，n<30)等。 Specific examples of vanadium (V) compounds include vanadium pentoxide (V), vanadium trioxide (III), vanadium dioxide (IV), vanadium (II) hydroxide, vanadium (III) hydroxide, and vanadium sulfate (II) ), vanadium (III) sulfate, vanadyl sulfate (IV), vanadium fluoride (III), vanadium fluoride (IV), vanadium fluoride (V), vanadium oxychloride VOCl 3 , vanadium trichloride VCl 3 , Hexafluorovanadic acid (III) or its salts (potassium salt, ammonium salt, etc.), metavanadic acid (V) or its salts (sodium salt, ammonium salt, etc.), vanadium acetonate (IV) VO (OC (= CH 2 )CH 2 COCH 3 ) 2 , vanadium (III) acetylacetonate V(OC(=CH 2 )CH 2 COCH 3 ) 3 , phospho-vanadium molybdate H 15-X [PV 12-X MoO 40 ]. nH 2 O (6<X<12, n<30), etc.

作為鎢(W)化合物之具體例舉例為氧化鎢(IV)、氧化鎢(V)、氧化鎢(VI)、氟化鎢(IV)、氟化鎢(VI)、鎢酸(VI)H2WO4或其鹽(銨鹽、鈉鹽等)、偏鎢酸(VI)H6[H2W12O40]或其鹽(銨鹽、鈉鹽等)、仲鎢酸(VI)H10[H10W12O46]或其鹽(銨鹽、鈉鹽等)等。 Specific examples of the tungsten (W) compound include tungsten (IV) oxide, tungsten oxide (V), tungsten oxide (VI), tungsten fluoride (IV), tungsten fluoride (VI), and tungstic acid (VI) H 2 WO 4 or its salt (ammonium salt, sodium salt, etc.), metatungstic acid (VI) H 6 [H 2 W 12 O 40 ] or its salt (ammonium salt, sodium salt, etc.), paratungstic acid (VI) H 10 [H 10 W 12 O 46 ] or its salt (ammonium salt, sodium salt, etc.), etc.

作為鉬(Mo)化合物之具體例舉例為磷釩鉬酸H15-X[PV12-XMoO40]．nH2O(6<X<12，n<30)、氧化鉬、鉬酸H2MoO4、鉬酸銨、仲鉬酸銨、鉬酸鈉、鉬磷酸化合物(例如鉬磷酸銨(NH4)3[PO4Mo12O36]．3H2O、鉬酸鈉Na3[PO4Mo12O36]．nH2O等)等。 As a specific example of a molybdenum (Mo) compound, phosphorus vanadium molybdate H 15-X [PV 12-X MoO 40 ]. nH 2 O (6<X<12, n<30), molybdenum oxide, molybdenum H 2 MoO 4 , ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdenum phosphate compounds (such as ammonium molybdate phosphate (NH 4 ) 3 [PO 4 Mo 12 O 36 ]. 3H 2 O, sodium molybdate Na 3 [PO 4 Mo 12 O 36 ]. nH 2 O, etc.).

作為鋁(Al)化合物之具體例舉例為硝酸鋁、硫酸鋁、硫酸鉀鋁、硫酸鈉鋁、硫酸銨鋁、磷酸鋁、碳酸鋁、氧化鋁、氫氧化鋁等。 Specific examples of aluminum (Al) compounds include aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, aluminum sulfate aluminum, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, and the like.

作為錫(Sn)化合物之具體例舉例為氧化錫(IV)、錫酸鈉Na2SnO3、氯化錫(II)、氯化錫(IV)、硝酸錫(II)、硝酸錫(IV)、六氟錫酸銨(NH4)2SnF6等。 Specific examples of tin (Sn) compounds include tin (IV) oxide, sodium stannate Na 2 SnO 3 , tin (II), tin (IV), tin (II) nitrate, and tin (IV) nitrate , Ammonium hexafluorostannate (NH 4 ) 2 SnF 6 etc.

作為鈮(Nb)化合物之具體例舉例為五氧化鈮(Nb2O5)、鈮酸鈉(NaNbO3)、氟化鈮(NbF5)、六氟鈮酸銨(NH4)NbF6等。 Specific examples of the niobium (Nb) compound include niobium pentoxide (Nb 2 O 5 ), sodium niobate (NaNbO 3 ), niobium fluoride (NbF 5 ), ammonium hexafluoroniobate (NH 4 ) NbF 6 and the like.

作為鉿(Hf)化合物、釔(Y)化合物、鈥(Ho)化合物、鉍(Bi)化合物及鑭(La)化合物之具體例舉例為氧化鉿、六氟鉿氫酸、氧化釔、乙醯丙酮釔、氧化鈥、氧化鉍、氧化鑭等。 Specific examples of the hafnium (Hf) compound, yttrium (Y) compound, 鈥 (Ho) compound, bismuth (Bi) compound, and lanthanum (La) compound are hafnium oxide, hafnium hexafluoride, yttrium oxide, and acetone acetone Yttrium, yttrium oxide, bismuth oxide, lanthanum oxide, etc.

作為鈰(Ce)化合物之具體例舉例為氧化鈰、乙酸鈰Ce(CH3CO2)3、硝酸鈰(III)或(VI)、硝酸鈰銨、硫酸鈰、氯化鈰等。 Specific examples of the cerium (Ce) compound include cerium oxide, cerium acetate Ce(CH 3 CO 2 ) 3 , cerium (III) or (VI) nitrate, cerium ammonium nitrate, cerium sulfate, cerium chloride, and the like.

作為鋅(Zn)化合物之具體例舉例為氧化鋅、氫氧化鋅、乙酸鋅、硝酸鋅、硫酸鋅、氯化鋅、鋅酸鈉等。 Specific examples of zinc (Zn) compounds include zinc oxide, zinc hydroxide, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, and sodium zincate.

又，上述各金屬化合物各可單獨使用，亦可併用同種之2種以上、亦可併用不同種之2種以上。 In addition, each of the above metal compounds may be used alone, or two or more of the same species may be used in combination, or two or more of different species may be used in combination.

使用上述金屬之化合物時，其調配量，考慮所得耐腐蝕性提高效果、交聯密著性能提高效果及金屬表面處理劑之浴安定性時，於金屬表面處理劑中以各金屬離子之量計，較好為0.01~50g/L之濃度，更好為0.05~5g/L之濃度。 When using the above-mentioned metal compound, the amount of the compound is calculated based on the amount of each metal ion in the metal surface treatment agent when considering the effect of improving the corrosion resistance, the effect of improving the crosslinking adhesion performance, and the bath stability of the metal surface treatment agent The concentration is preferably 0.01-50 g/L, more preferably 0.05-5 g/L.

本發明之金屬表面處理劑較好進而含有含硫羰基化合物。 The metal surface treatment agent of the present invention preferably further contains a sulfur-containing carbonyl compound.

作為含硫羰基化合物之具體例舉例為硫脲、二甲基硫脲、1,3-二甲基硫脲、二丙基硫脲、二丁基硫脲、1,3-二苯基-2-硫脲、2,2-二甲苯基硫脲、硫代乙醯胺、二甲基二硫代胺基甲酸鈉、單硫化四甲基秋蘭姆、二硫化四丁基秋蘭姆、N-乙基-N-苯基二硫代胺基甲酸鋅、二甲基二硫代 胺基甲酸鋅、五亞甲基二硫代胺基甲酸哌啶鹽、二乙基二硫代胺基甲酸鋅、二乙基二硫代胺基甲酸鈉、異丙基黃原酸鋅、伸乙基硫脲、二甲基黃原酸硫化物、二硫代乙二醯二胺、聚二硫代胺基甲酸或其鹽等之含有至少1個硫羰基之化合物，該等可單獨使用，亦可併用2種以上。 Specific examples of the sulfur-containing carbonyl compound include thiourea, dimethylthiourea, 1,3-dimethylthiourea, dipropylthiourea, dibutylthiourea, and 1,3-diphenyl-2 -Thiourea, 2,2-xylylthiourea, thioacetamide, sodium dimethyldithiocarbamate, tetramethylthiuram monosulfide, tetrabutylthiuram disulfide, N- Ethyl-N-phenyl dithiocarbamate zinc, dimethyl dithio Zinc carbamate, piperidine salt of pentamethylene dithiocarbamate, zinc diethyldithiocarbamate, sodium diethyldithiocarbamate, zinc isopropylxanthate, ethylidene Compounds containing at least one thiocarbonyl group such as thiosemicarbazide, dimethylxanthogen sulfide, dithioethylenediamine, polydithiocarbamic acid or its salts, etc. These can be used alone or Two or more types can be used in combination.

使用上述含硫羰基化合物時，其調配量，考慮所得耐腐蝕性提高效果與經濟性之均衡時，於金屬表面處理劑中，較好為0.01~100g/L之濃度，更好為0.1~10g/L之濃度。 When the above sulfur-containing carbonyl compound is used, the amount of the compound is considered to be a balance of 0.01 to 100 g/L, more preferably 0.1 to 10 g in the metal surface treatment agent when considering the balance between the corrosion resistance improvement effect and economic efficiency obtained. /L concentration.

本發明之金屬表面處理劑較好進而含有水溶性樹脂或水分散性樹脂。 The metal surface treatment agent of the present invention preferably further contains a water-soluble resin or a water-dispersible resin.

作為水溶性或水分散性樹脂之具體例舉例為丙烯酸樹脂、環氧系樹脂、胺基甲酸酯系樹脂、乙烯丙烯酸共聚物、酚系樹脂、聚酯系樹脂、聚烯烴系樹脂、醇酸系樹脂、聚碳酸酯系樹脂等，該等可單獨使用，可併用2種以上，進而亦可共聚合使用。 Specific examples of water-soluble or water-dispersible resins are acrylic resins, epoxy resins, urethane resins, ethylene acrylic acid copolymers, phenol resins, polyester resins, polyolefin resins, alkyds Resins, polycarbonate resins, etc., these can be used alone, two or more kinds can be used in combination, and can also be used by copolymerization.

作為水溶性丙烯酸樹脂舉例為以丙烯酸及/或甲基丙烯酸衍生物為主成分之共聚物。作為上述衍生物舉例為丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯等，亦可使用該等與其他丙烯酸系單體之共聚物。 Examples of water-soluble acrylic resins are copolymers containing acrylic acid and/or methacrylic acid derivatives as main components. Examples of the above derivatives include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc. Copolymers of these and other acrylic monomers can also be used.

尤其，共聚物中之丙烯酸及/或甲基丙烯酸單體比例較好為70質量%以上。 In particular, the proportion of acrylic acid and/or methacrylic acid monomers in the copolymer is preferably 70% by mass or more.

水溶性或水分散性樹脂之分子量，考慮充分發揮塗膜之深拉性提高效果同時將黏度設為適當範圍而使 處理性良好時，以凝膠滲透層析法(GPC)測定之聚苯乙烯換算重量平均分子量較好為1萬以上，更好為30~200萬。 The molecular weight of the water-soluble or water-dispersible resin is considered to give full play to the effect of improving the deep drawability of the coating film while setting the viscosity to an appropriate range. When the handleability is good, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 10,000 or more, more preferably 300,000 to 2 million.

使用上述水溶性或水分散性樹脂時，其調配量，考慮所發揮之彎折密著性提高效果及深拉性提高效果、與經濟性時，於金屬表面處理劑中，較好為0.1~100g/L之濃度，更好為5~80g/L之濃度。 When the above water-soluble or water-dispersible resin is used, when the amount of the compound is taken into consideration, the effect of improving the bending adhesiveness and the deep-drawing property, and the economic efficiency are considered. In the metal surface treatment agent, it is preferably 0.1~ The concentration of 100g/L is more preferably 5 to 80g/L.

又，使用樹脂時，為了提高其造膜性，形成更均一且平滑塗膜，亦可使用有機溶劑，再者，亦可使用界面活性劑、調平劑、濡濕性提高劑、消泡劑。 In addition, when a resin is used, in order to improve the film-forming property and form a more uniform and smooth coating film, an organic solvent may be used. Furthermore, a surfactant, a leveling agent, a wettability improver, and a defoaming agent may also be used.

本發明之金屬表面處理劑較好進而含有磷酸離子，藉由添加其，可進一步提高耐腐蝕性。 The metal surface treatment agent of the present invention preferably further contains phosphoric acid ions, and by adding it, the corrosion resistance can be further improved.

該磷酸離子之添加可添加於水中可產生磷酸離子之化合物而進行。 The addition of the phosphate ion can be carried out by adding a compound capable of generating phosphate ion in water.

作為此等化合物，舉例為磷酸、Na3PO4、Na2HPO4、NaH2PO4等之磷酸鹽類、縮合磷酸、聚磷酸、偏磷酸、二磷酸等之縮合磷酸或該等之鹽類，該等可單獨使用，且亦可併用2種以上。 Examples of such compounds include phosphates such as phosphoric acid, Na 3 PO 4 , Na 2 HPO 4 , and NaH 2 PO 4 , condensed phosphoric acid, polyphosphoric acid, metaphosphoric acid, diphosphoric acid, and the like, or salts thereof , These can be used alone, and can also be used in combination of two or more.

使用上述磷酸離子時，其調配量，於金屬表面處理劑中，較好為0.01~100g/L之濃度，更好為0.1~10g/L之濃度。添加量未達0.01g/L時，有耐腐蝕性改善效果不充分之情況，超過100g/L時，有引起鋅系鍍敷鋼材過度蝕刻，引起性能降低，於含有水性樹脂作為其他成分時，引起膠凝化之情況。 When using the above-mentioned phosphoric acid ion, the blending amount in the metal surface treatment agent is preferably a concentration of 0.01 to 100 g/L, more preferably a concentration of 0.1 to 10 g/L. When the addition amount is less than 0.01g/L, the corrosion resistance improvement effect may not be sufficient, and if it exceeds 100g/L, the zinc-based plated steel may be excessively etched, resulting in reduced performance. When the water-based resin is included as another component, A condition that causes gelation.

又，本發明之金屬表面處理劑亦可調配鞣酸 或其鹽、植酸或其鹽等之習知各種金屬表面處理劑用添加劑。 In addition, the metal surface treatment agent of the present invention can also be formulated with tannic acid Conventional additives for various metal surface treatment agents such as salts thereof, phytic acid or salts thereof, etc.

作為使用本發明之金屬表面處理劑進行表面處理之金屬並未特別限定，可使用習知一般金屬，其中較好使用銅、鎳、銀、鋅、鐵、鋁或該等之合金，更好為鋁、銅、銅合金，且亦可較好地利用各種鍍敷鋼材。 The metal subjected to surface treatment using the metal surface treatment agent of the present invention is not particularly limited, and conventional general metals can be used. Among them, copper, nickel, silver, zinc, iron, aluminum, or alloys thereof are preferably used, and more preferably Aluminum, copper, copper alloy, and various plated steel materials can also be used better.

使用本發明之金屬表面處理劑之表面處理方法，可為將上述金屬表面處理劑塗佈於被塗佈物的金屬表面，塗佈後使被塗佈物乾燥之方法，亦可為預先加熱被塗佈物，隨後塗佈上述金屬表面處理劑，利用餘熱乾燥之方法。 The surface treatment method using the metal surface treatment agent of the present invention may be a method of applying the above metal surface treatment agent to the metal surface of the object to be coated, and drying the object to be coated after coating, or it may be heated in advance The coated object is then coated with the above metal surface treatment agent and dried by waste heat.

作為塗佈方法並未特別限定，可採用一般使用之輥塗佈、淋洗塗佈、噴霧、浸漬、刷毛塗佈等。 The coating method is not particularly limited, and generally used roll coating, shower coating, spraying, dipping, brush coating, etc. can be used.

上述乾燥條件於任一情況，均較好於室溫~250℃歷時2秒~1小時，更好於40~180℃歷時5秒~20分鐘。超過250℃時，有產生密著性及耐腐蝕性等之性能劣化之可能性。 In any case, the above drying conditions are preferably room temperature to 250°C for 2 seconds to 1 hour, and more preferably 40 to 180°C for 5 seconds to 20 minutes. If the temperature exceeds 250°C, there is a possibility of deterioration of performance such as adhesion and corrosion resistance.

上述表面處理方法中，上述金屬表面處理劑之塗佈量，考慮所發揮之防鏽性與經濟性時，乾燥後之被膜質量較好為0.1mg/m2以上，更好為0.5~500mg/m2，又更好為1~250mg/m2。 In the above surface treatment method, when the coating amount of the metal surface treatment agent is taken into consideration, the quality of the coating after drying is preferably 0.1 mg/m 2 or more, more preferably 0.5 to 500 mg/ m 2 , and more preferably 1 to 250 mg/m 2 .

使用本發明之金屬表面處理劑表面處理金屬鋼材，乾燥，其次塗佈上層被膜層，可獲得塗裝鋼材。作為金屬鋼材可為預塗佈鋼材、後塗佈鋼材之任一者。又， 本發明中之鋼材係包含鋼板之概念。 The metal steel material is surface-treated with the metal surface treatment agent of the present invention, dried, and then coated with an upper coating layer to obtain a coated steel material. The metallic steel material may be either pre-coated steel material or post-coated steel material. also, The steel material in the present invention includes the concept of a steel plate.

作為上述被膜層，可舉例為根據需要塗佈乾燥非鉻酸鹽底塗後，進而塗佈頂塗之塗裝系統，或具有耐指紋性及潤滑性等之功能之功能塗層等。 Examples of the coating layer include a coating system in which a non-chromate primer is applied and dried as needed, followed by a top coat, or a functional coating having functions such as fingerprint resistance and lubricity.

作為非鉻酸鹽底塗，可使用於底塗調配中不使用鉻酸鹽系防鏽顏料之所有底塗。 As a non-chromate primer, it can be used for all primers that do not use chromate-based anti-rust pigments in the preparation of the primer.

作為此等底塗，較好為使用釩酸系防鏽顏料與磷酸系防鏽顏料之底塗(V/P顏料底塗)、使用矽酸鈣系防鏽顏料之底塗。 As such an undercoat, it is preferable to use a vanadic acid-based antirust pigment and a phosphoric acid-based antirust pigment (V/P pigment undercoat), and a calcium silicate-based antirust pigment.

上述底塗之塗佈膜厚，考慮耐腐蝕性及加工密著性之均衡時，乾燥膜厚較好為1~20μm。 In consideration of the balance of corrosion resistance and processing adhesion, the thickness of the coating film of the above primer is preferably 1 to 20 μm.

上述非鉻酸鹽底塗之燒烤乾燥條件可設為例如金屬表面溫度為150-250℃，時間為10秒-5分鐘。 The baking and drying conditions of the non-chromate primer can be set to, for example, a metal surface temperature of 150-250° C. and a time of 10 seconds-5 minutes.

作為上述頂塗並未特別限定，可使用所有通常之塗裝用頂塗。 The above-mentioned top coat is not particularly limited, and any general top coat for coating can be used.

且，功能塗層亦未特別限定，可使用於目前鉻酸鹽系前處理被膜上實施之塗層等之全部。 In addition, the functional coating is not particularly limited, and can be used for all coatings and the like currently applied to chromate-based pretreatment coatings.

上述非鉻酸鹽底塗、頂塗及功能塗層之塗佈方法並未特別限定，可採用一般使用之輥塗、淋洗塗佈、氣體噴霧、無氣體噴霧、浸漬等。 The coating methods of the above non-chromate primer coating, top coating and functional coating are not particularly limited, and roll coating, shower coating, gas spray, gasless spray, dipping, etc., which are generally used, can be used.

又，頂塗厚度可適當選定，可設為根據其種類而通常之塗膜厚。 In addition, the thickness of the top coat can be selected as appropriate, and it can be set to the thickness of the normal coating film according to the type.

[實施例] [Example]

以下列舉實施例及比較例更具體說明本發明，但本發明並非限定於該等實施例。 The following examples and comparative examples illustrate the present invention more specifically, but the present invention is not limited to these examples.

又，以下中，作為苯并***化合物、矽烷偶合劑、有機鈦酸酯、水分散性氧化矽、生成鋯離子之化合物、含硫羰基化合物、水溶性樹脂及生成磷酸離子之化合物係使用以下市售品。 In the following, the following compounds are used as the benzotriazole compound, silane coupling agent, organic titanate, water-dispersible silica, zirconium ion generating compound, sulfur-containing carbonyl compound, water-soluble resin, and phosphate ion generating compound. Commercial products.

[苯并***化合物] [Benzotriazole compound]

A：TT-LYK(2,2’-[[(甲基-1H-苯并***-1-基)甲基]亞胺基]雙乙醇，城北化學工業(股)製) A: TT-LYK (2,2’-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]diethanol, manufactured by Chengbei Chemical Industry Co., Ltd.)

B：BT-120(苯并***，城北化學工業(股)製) B: BT-120 (benzotriazole, manufactured by Chengbei Chemical Industry Co., Ltd.)

[矽烷偶合劑] [Silane coupling agent]

A：KBE-903(γ-胺基丙基三乙氧基矽烷，信越化學工業(股)製) A: KBE-903 (γ-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

B：KBM-403(γ-縮水甘油氧基丙基三甲氧基矽烷，信越化學工業(股)製) B: KBM-403 (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

C：KBM-603(N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷，信越化學工業(股)製) C: KBM-603 (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

[有機鈦酸酯] [Organic Titanate]

四異丙氧化鈦(東京化成工業(股)製) Titanium tetraisopropoxide (made by Tokyo Chemical Industry Co., Ltd.)

[水分散性氧化矽] [Water-dispersible silica]

甲醇矽溶膠(日產化學工業(股)製) Methanol silica sol (made by Nissan Chemical Industry Co., Ltd.)

[形成鋯離子之化合物] [Compounds forming zirconium ions]

鋯溶膠AC-7(碳酸鋯銨；第一稀元素化學工業(股)製) Zirconium sol AC-7 (ammonium zirconium carbonate; first rare element chemical industry (stock) system)

[含硫羰基化合物] [Sulfur-containing carbonyl compound]

硫脲(東京化成工業(股)製) Thiourea (Tokyo Chemical Industry Co., Ltd.)

[水溶性樹脂] [Water-soluble resin]

聚丙烯酸(重量平均分子量100萬)(東京化成工業(股)製) Polyacrylic acid (weight average molecular weight 1 million) (Tokyo Chemical Industry Co., Ltd.)

[生成磷酸離子之化合物] [Compounds that generate phosphate ions]

磷酸(東京化成工業(股)製) Phosphoric acid (Tokyo Chemical Industry Co., Ltd. system)

[實施例1] [Example 1]

於甲醇500g、水500g之混合溶劑中，添加苯并***化合物A 0.5g及矽烷偶合劑A 9.5g，於室溫攪拌5分鐘，獲得金屬表面處理劑。 To a mixed solvent of 500 g of methanol and 500 g of water, 0.5 g of benzotriazole compound A and 9.5 g of silane coupling agent A were added, and stirred at room temperature for 5 minutes to obtain a metal surface treatment agent.

所得金屬表面處理劑以棒塗佈器No.20於經脫脂乾燥之市售鋁板(TEST PIECE(股)製；70×150×0.4mm)上塗佈成乾燥膜厚成為10μm，於金屬表面溫度105℃乾燥10分鐘。 The obtained metal surface treatment agent was coated on a degreased and dried commercial aluminum plate (made by TEST PIECE; 70×150×0.4 mm) with a bar coater No. 20 to a dry film thickness of 10 μm at the metal surface temperature Dry at 105°C for 10 minutes.

隨後，將含V/P顏料之非鉻酸鹽底塗(日本塗料(股)製)以棒塗佈器No.16塗佈成乾燥膜厚成為5μm，於金屬表面溫度215℃乾燥5分鐘。進而，將作為頂塗之FLEKY COAT 1060(聚酯系頂塗塗料；日本塗料(股)製)以棒塗佈器No.36塗佈成乾燥膜厚成為15μm，於金屬表面溫度230℃乾燥獲得試驗板。 Subsequently, a non-chromate primer (manufactured by Nippon Paint Co., Ltd.) containing V/P pigment was coated with a bar coater No. 16 to a dry film thickness of 5 μm, and dried at a metal surface temperature of 215° C. for 5 minutes. Furthermore, FLEKY COAT 1060 (polyester top coating; manufactured by Nippon Paint Co., Ltd.) as a top coat was coated with a bar coater No. 36 to a dry film thickness of 15 μm and dried at a metal surface temperature of 230° C. Breadboard.

[實施例2] [Example 2]

除了將矽烷偶合劑A變更為矽烷偶合劑B以外，與實施例1同樣調製金屬表面處理劑，進而與實施例1同樣製作試驗板。 Except that the silane coupling agent A was changed to the silane coupling agent B, a metal surface treatment agent was prepared in the same manner as in Example 1, and a test plate was also produced in the same manner as in Example 1.

[實施例3~10] [Examples 3 to 10]

除了苯并***化合物、矽烷偶合劑之種類、有機鈦酸酯、水分散性氧化矽、鋯離子、含硫羰基化合物、水溶性樹脂及磷酸離子分別以表1之濃度調配以外，與實施例1同樣調製金屬表面處理劑，進而與實施例1同樣製作試驗板。 Except for the types of benzotriazole compound, silane coupling agent, organic titanate, water-dispersible silica, zirconium ion, sulfur-containing carbonyl compound, water-soluble resin and phosphoric acid ion, they were prepared at the concentrations shown in Table 1. 1 A metal surface treatment agent was prepared in the same manner, and a test plate was produced in the same manner as in Example 1.

[比較例1、2] [Comparative Examples 1, 2]

除了不使用矽烷偶合劑，且將表1所示之各成分以表1之濃度調配以外，與實施例1同樣調製金屬表面處理劑，進而與實施例1同樣製作試驗板。 A metal surface treatment agent was prepared in the same manner as in Example 1 except that the silane coupling agent was not used and each component shown in Table 1 was prepared at the concentration in Table 1. Further, a test plate was prepared in the same manner as in Example 1.

[比較例3~7] [Comparative Examples 3-7]

除了使用苯并***化合物B，且將表1所示之各成分以表1之濃度調配以外，與實施例1同樣調製金屬表面處理劑，進而與實施例1同樣製作試驗板。 Except that the benzotriazole compound B was used and each component shown in Table 1 was formulated at the concentration in Table 1, a metal surface treatment agent was prepared in the same manner as in Example 1, and a test plate was also prepared in the same manner as in Example 1.

[比較例8] [Comparative Example 8]

除了替代金屬表面處理劑，將市售塗佈型鉻酸鹽處理劑(日本塗料(股)製)以鉻附著料成為20mg/m2般塗佈並乾燥，進而使用含鉻之底塗(日本塗料(股)製)以外，與實施例4同樣製作試驗板。 In addition to replacing metal surface treatment agents, commercially available coating chromate treatment agents (manufactured by Nippon Paint Co., Ltd.) are applied and dried with chromium adhesion material at 20 mg/m 2 , and then a chromium-containing base coat (Japan Except for the paint (product), a test plate was produced in the same manner as in Example 4.

Figure 106112628-A0202-12-0023-7
Figure 106112628-A0202-12-0023-7

針對上述實施例及比較例所得之各試驗板，依據下述評價方法及評價基準評價彎折密著性、深拉性、耐腐蝕性。結果示於表2。 For each test plate obtained in the above examples and comparative examples, the bending adhesion, deep drawability, and corrosion resistance were evaluated according to the following evaluation methods and evaluation criteria. The results are shown in Table 2.

[評價方法] [Evaluation method] (1)彎折密著性 (1) Bending tightness

於20℃環境下，使用錐形心軸試驗機以試驗板夾持2mmΦ之間隔物進行180°彎折加工，於彎折加工部進行3次膠帶剝離，以20倍放大鏡觀察剝離程度，以下述評價基準 評價。 Under a 20°C environment, use a tapered mandrel tester to sandwich a 2 mm Φ spacer between the test plates for 180° bending processing, and perform 3 times of tape peeling at the bending processing portion, and observe the peeling degree with a 20 times magnifying glass, as follows Evaluation criteria Evaluation.

A：未龜裂 A: Not cracked

B：加工部全面龜裂 B: The processing department is completely cracked

C：剝離面積為加工部之未達20% C: The peeling area is less than 20% of the processing department

D：剝離面積為加工之20%以上且未達80% D: The peeling area is more than 20% of the processing and less than 80%

E：剝離面積為加工部之80%以上 E: The peeling area is more than 80% of the processed part

(2)深拉性 (2) Deep drawability

於20℃環境下，以拉伸比：2.3，皺褶抑制壓力：2t，沖頭R：5mm，模具肩R：5mm，於無塗油條件下進行圓筒拉伸試驗。隨後，測定自交叉切割部之塗膜剝離寬度，以下述基準評價。 Under a 20°C environment, a cylinder tensile test was carried out under an oil-free condition with a draw ratio: 2.3, a wrinkle suppression pressure: 2 t, a punch R: 5 mm, and a die shoulder R: 5 mm. Subsequently, the peeling width of the coating film from the cross-cut portion was measured and evaluated according to the following criteria.

A：膨脹寬度未達1mm A: The expansion width is less than 1mm

B：膨脹寬度為1mm以上且未達2mm B: The expansion width is more than 1mm and less than 2mm

C：膨脹寬度為2mm以上且未達3mm C: The expansion width is more than 2mm and less than 3mm

D：膨脹寬度為3mm以上且未達5mm D: The expansion width is more than 3mm and less than 5mm

E：膨脹寬度為5mm以上 E: Expansion width is more than 5mm

(3)耐腐蝕性 (3) Corrosion resistance (切割部) (Cutting section)

於試驗板上進行交叉切割，基於JIS Z 2371進行500小時鹽水噴霧試驗後，測定切割部單側之膨脹寬度，以下述基準評價。 After cross-cutting on the test plate and performing a 500-hour salt spray test based on JIS Z 2371, the swelling width on one side of the cut portion was measured, and the following criteria were used for evaluation.

A：膨脹寬度為0mm A: The expansion width is 0mm

B：膨脹寬度為0mm以上且未達1mm B: The expansion width is more than 0mm and less than 1mm

C：膨脹寬度為1mm以上且未達3mm C: The expansion width is more than 1mm and less than 3mm

D：膨脹寬度為3mm以上且未達5mm D: The expansion width is more than 3mm and less than 5mm

E：膨脹寬度為5mm以上 E: Expansion width is more than 5mm

(端面) (End face)

基於JIS Z 2371對試驗板進行500小時鹽水噴霧試驗後，與切割部同樣基準評價自上毛邊端面之膨脹寬度。 After a 500-hour salt water spray test was performed on the test plate based on JIS Z 2371, the swelling width from the upper burr end surface was evaluated on the same basis as the cut portion.

Figure 106112628-A0202-12-0026-8
Figure 106112628-A0202-12-0026-8

如表2所示可知，使用實施例1~10之金屬表面處理劑形成之被膜發揮良好之防鏽能及基材密著性。 As shown in Table 2, it can be seen that the coatings formed using the metal surface treatment agents of Examples 1 to 10 exhibit good anti-rust performance and substrate adhesion.

[實施例11] [Example 11]

於甲醇500g、水500g之混合溶劑中，添加苯并***化合物A 0.1g及矽烷偶合劑A 9.9g，於室溫攪拌5分鐘，獲得金屬表面處理劑。 To a mixed solvent of 500 g of methanol and 500 g of water, 0.1 g of benzotriazole compound A and 9.9 g of silane coupling agent A were added, and stirred at room temperature for 5 minutes to obtain a metal surface treatment agent.

於所得金屬表面處理劑中浸漬經硫酸洗淨之銅板 (TEST PIECE(股)製；70×150×0.4mm)1分鐘，於金屬表面溫度105℃乾燥10分鐘，獲得試驗板。 Dipping the copper plate washed with sulfuric acid in the resulting metal surface treatment agent (Made by TEST PIECE; 70×150×0.4 mm) for 1 minute, and dried at a metal surface temperature of 105° C. for 10 minutes to obtain a test plate.

[實施例12] [Example 12]

除了將矽烷偶合劑A變更為矽烷偶合劑B以外，與實施例11同樣調製金屬表面處理劑，進而以與實施例11同樣製作試驗板。 Except that the silane coupling agent A was changed to the silane coupling agent B, a metal surface treatment agent was prepared in the same manner as in Example 11, and a test plate was produced in the same manner as in Example 11.

[實施例13] [Example 13]

除了將矽烷偶合劑A變更為矽烷偶合劑C以外，與實施例11同樣調製金屬表面處理劑，進而以與實施例11同樣製作試驗板。 Except that the silane coupling agent A was changed to the silane coupling agent C, a metal surface treatment agent was prepared in the same manner as in Example 11, and a test plate was produced in the same manner as in Example 11.

[實施例14~22] [Examples 14 to 22]

除了苯并***化合物及矽烷偶合劑之種類及調配量分別變更為表3所示般以外，與實施例11同樣調製金屬表面處理劑，進而與實施例11同樣製作試驗板。 Except that the types and formulation amounts of the benzotriazole compound and the silane coupling agent were changed as shown in Table 3, a metal surface treatment agent was prepared in the same manner as in Example 11, and a test plate was also prepared in the same manner as in Example 11.

[比較例9、10] [Comparative Examples 9, 10]

除了不使用矽烷偶合劑，且將苯并***化合物之調配量變更為表3所示之濃度以外，與實施例11同樣調製金屬表面處理劑，進而與實施例11同樣製作試驗板。 A metal surface treatment agent was prepared in the same manner as in Example 11 except that the silane coupling agent was not used and the compounding amount of the benzotriazole compound was changed to the concentration shown in Table 3. Further, a test plate was prepared in the same manner as in Example 11.

[比較例11~14] [Comparative Examples 11-14]

除了將苯并***化合物及矽烷偶合劑之種類及調配量分別變更為表3所示以外，與實施例11同樣調製金屬表面處理劑，進而與實施例11同樣製作試驗板。 Except that the types and formulation amounts of the benzotriazole compound and the silane coupling agent were changed to those shown in Table 3, a metal surface treatment agent was prepared in the same manner as in Example 11, and a test plate was also prepared in the same manner as in Example 11.

Figure 106112628-A0202-12-0028-9
Figure 106112628-A0202-12-0028-9

針對上述實施例11~22及比較例9~14所得之試 驗板，依據下述評價方法及評價基準評價耐熱性及耐腐蝕性。結果示於表4。 For the tests obtained in the above Examples 11-22 and Comparative Examples 9-14 For the panel inspection, heat resistance and corrosion resistance were evaluated according to the following evaluation methods and evaluation criteria. The results are shown in Table 4.

(1)耐熱性 (1) Heat resistance

將試驗板放入150℃之恆溫機中，以下述基準評價1小時後、5小時後之外觀。 The test plate was placed in a 150°C thermostat, and the appearance after 1 hour and 5 hours was evaluated according to the following criteria.

A：未變化 A: No change

B：大致未變化 B: roughly unchanged

C：紅化 C: Redness

D：嚴重紅化 D: Severe redness

E：白化 E: Albino

(2)耐腐蝕性 (2) Corrosion resistance

針對試驗板，基於JIS Z 2371進行24小時、72小時之鹽水噴霧試驗後，以下述基準評價外觀。 For the test panel, after performing the salt spray test for 24 hours and 72 hours based on JIS Z 2371, the appearance was evaluated according to the following criteria.

A：未發生鏽 A: No rust occurred

B：5~20%面積發生鏽 B: Rust occurs in 5~20% area

C：29~50%面積發生鏽 C: Rust occurs in 29~50% of the area

D：50~90%面積發生鏽 D: Rust occurs in 50~90% area

E：90~100%面積發生鏽 E: rust occurred in 90~100% area

Figure 106112628-A0202-12-0030-10
Figure 106112628-A0202-12-0030-10

如表4所示可知，使用實施例11~22之金屬表面處理劑形成之被膜發揮良好之耐熱性及防鏽能。 As shown in Table 4, the coatings formed using the metal surface treatment agents of Examples 11 to 22 exhibit good heat resistance and rust resistance.

Claims (8)

一種金屬表面處理劑，其特徵為含有以下述通式(1)表示之苯并***化合物及矽烷偶合劑，前述矽烷偶合劑為具有胺基之矽烷偶合劑，前述矽烷偶合劑之使用量相對於前述苯并***化合物以質量比計為1~50倍，
Figure 106112628-A0305-02-0033-1
 [式中，R1相互獨立表示氫原子或碳數1~10之烷基，R2表示碳數1~10之伸烷基；R3及R4相互獨立表示氫原子、碳數1~10之烷基、或以下述通式(2)表示之基；但R3及R4之至少一者為以下述式(2)表示之基：-R 5 -OH (2)(式中，R5表示碳數1~10之伸烷基)]。 A metal surface treatment agent characterized by containing a benzotriazole compound represented by the following general formula (1) and a silane coupling agent, the silane coupling agent is a silane coupling agent having an amine group, and the amount of the silane coupling agent used is relatively In the aforementioned benzotriazole compound, the mass ratio is 1 to 50 times,
Figure 106112628-A0305-02-0033-1
 [In the formula, R 1 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkylene group having 1 to 10 carbon atoms; R 3 and R 4 independently represent a hydrogen atom and 1 to 10 carbon atoms. Alkyl group, or a group represented by the following general formula (2); but at least one of R 3 and R 4 is a group represented by the following formula (2): -R 5 -OH (2) (wherein, R 5 represents a C 1-10 alkylene group)]. 如請求項1之金屬表面處理劑，其中前述R2為亞甲基，R3及R4均為以前述通式(2)表示之基，且前述R5為伸乙基。 The metal surface treatment agent according to claim 1, wherein the aforementioned R 2 is a methylene group, R 3 and R 4 are both groups represented by the aforementioned general formula (2), and the aforementioned R 5 is an ethylidene group. 如請求項1或2之金屬表面處理劑，其中含有有機鈦酸酯。 The metal surface treatment agent according to claim 1 or 2, which contains an organic titanate. 如請求項1或2之金屬表面處理劑，其中含有水分散性氧化矽或有機溶劑分散性氧化矽。 The metal surface treatment agent according to claim 1 or 2, which contains water-dispersible silica or organic solvent-dispersible silica. 如請求項1或2之金屬表面處理劑，其中含有選自Fe、Zr、Ti、V、W、Mo、Al、Sn、Nb、Hf、Y、Ho、Bi、La、Ce及Zn之1種以上之金屬的化合物。 The metal surface treatment agent according to claim 1 or 2, which contains one kind selected from Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce and Zn Compounds of the above metals. 如請求項1或2之金屬表面處理劑，其中含有含硫羰基之化合物。 A metal surface treatment agent as claimed in claim 1 or 2, which contains a sulfocarbonyl-containing compound. 如請求項1或2之金屬表面處理劑，其中含有水溶性樹脂或水分散性樹脂。 The metal surface treatment agent according to claim 1 or 2, which contains a water-soluble resin or a water-dispersible resin. 如請求項1或2之金屬表面處理劑，其中含有磷酸離子。 The metal surface treatment agent according to claim 1 or 2, which contains phosphate ions.
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